JP5467446B2 - Carbon fiber detachment prevention method from carbon fiber reinforced plastic - Google Patents
Carbon fiber detachment prevention method from carbon fiber reinforced plastic Download PDFInfo
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- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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Description
本件発明は、炭素繊維強化プラスチックからの炭素繊維の脱落防止方法に関する。 The present invention relates to a method for preventing carbon fibers from falling out of a carbon fiber reinforced plastic .
プラスチックに繊維等のフィラーを混在させて成型した繊維強化プラスチック（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ：以下、「ＦＲＰ」と称する。）は、強度や剛性が同等であれば、鉄やアルミニウム等の金属材料に比べると軽量である。また、ＦＲＰは、対応できる製品の形状に対する自由度も大きいことから、その用途が拡大している。そして、ＦＲＰの中でも、炭素繊維を用いた炭素繊維強化プラスチック（Ｃａｒｂｏｎ Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃｓ：以下、「ＣＦＲＰ」と称する。）は、種々の特性要求に対して、繊維の配向方向や層厚さ等の積層構成で対応することが出来るものである。この炭素繊維には、ポリアクリルニトリル繊維を原料とするＰＡＮ系炭素繊維と、石油ピッチやタール等を原料とするＰＩＴＣＨ系炭素繊維がある。しかし、ＣＦＲＰは炭素繊維、特に機械強度に優れたＰＡＮ系炭素繊維が高価であるため、需要の拡大が遅れている。即ち、ＣＦＲＰの用途は、コスト吸収力のある、釣り竿、ゴルフクラブや自転車等のスポーツ用品、そしてレーシングカーや航空機等に限定されていた。 Fiber Reinforced Plastics (hereinafter referred to as “FRP”) molded by mixing fillers such as fibers with plastics are comparable to metal materials such as iron and aluminum as long as they have the same strength and rigidity. Light weight. In addition, the use of FRP is expanding because it has a high degree of freedom with respect to the shape of products that can be handled. Among the FRPs, carbon fiber reinforced plastic (Carbon Fiber Reinforced Plastics: hereinafter referred to as “CFRP”) uses carbon fibers such as fiber orientation direction and layer thickness in response to various characteristic requirements. This can be handled by a laminated structure. These carbon fibers include PAN-based carbon fibers made from polyacrylonitrile fibers and PITCH-based carbon fibers made from petroleum pitch, tar, or the like. However, since CFRP is expensive carbon fiber, particularly PAN-based carbon fiber having excellent mechanical strength, the expansion of demand is delayed. That is, the use of CFRP has been limited to cost-absorbing fishing rods, sports equipment such as golf clubs and bicycles, and racing cars and aircraft.
ところで、自動車の分野では、地球温暖化防止対策として、燃料消費効率の向上が課題となっている。そして、その１つの手段として、車体の軽量化が計画されている。また、工作機械の分野でも、加工効率の向上等を目的として、装置の大型化と高機能化を目指している。そして、今後とも同様の傾向が続くことは明らかである。 By the way, in the field of automobiles, improvement of fuel consumption efficiency is an issue as a measure against global warming. And as one of the means, weight reduction of the vehicle body is planned. Also in the field of machine tools, the aim is to increase the size and functionality of the equipment for the purpose of improving machining efficiency. It is clear that the same trend will continue in the future.
しかし、上記動向に於いて、自動車用途では、車体の軽量化による機械強度の低下が許容されることは無い。また、工作機械を大型化すると、加工精度を良好に維持するためには、工作機械を安定した基礎の上に設置する必要がある。即ち、大型の工作機械を設置するためには、該機械の質量に応じて設置場所の耐荷重を大きくする必要がある。しかし、耐荷重を大きくするために基礎工事で大量のコンクリートパイルを埋設すると、投資金額が増大してしまう。そこで、大型の工作機械の構造材にも、自動車用途と同様に、軽量化と機械強度維持との両立が要求される。そして、自動車の車体と工作機械の構造材のどちらにも、機械強度の経時変化が許容されることはない。 However, in the above trend, in automotive applications, a decrease in mechanical strength due to weight reduction of the vehicle body is not allowed. Further, when the machine tool is increased in size, it is necessary to install the machine tool on a stable foundation in order to maintain good machining accuracy. That is, in order to install a large machine tool, it is necessary to increase the load resistance of the installation location according to the mass of the machine. However, if a large amount of concrete piles are embedded in the foundation work in order to increase the load resistance, the amount of investment increases. Therefore, structural materials for large machine tools are required to achieve both weight reduction and maintenance of mechanical strength, similar to automotive applications. And neither a car body of a motor vehicle nor a structural material of a machine tool is allowed to change with time in mechanical strength.
上記、軽量化と機械強度維持との両立を課題としている分野では、ＣＦＲＰの特性が注目を浴びている。最近のＣＦＲＰには、鉄やプラスチックに匹敵する設計ノウハウの蓄積があり、量産性にも問題が無くなっている。構造材料にＣＦＲＰを用いると、金属を用いた場合と同等の機械強度を備えながら、質量は２／３以下になる。しかし、ＣＦＲＰは、炭素繊維を重ねたり巻き付けたりした後で樹脂モールドするレジン・トランスファー・モールディング方式、炭素繊維に樹脂を含浸させたプリプレグを重ね巻きして加熱硬化させる方式、そしてプリプレグを用いてホットプレスする方式等で製品の形状を整えるため、出来上がった製品の寸法精度や表面状態は、金属加工品よりも劣っている。 In the above field where balancing light weight and maintaining mechanical strength is an issue, the properties of CFRP are attracting attention. Recent CFRP has accumulated design know-how comparable to iron and plastic, and has no problem in mass productivity. When CFRP is used as the structural material, the mass becomes 2/3 or less while having the same mechanical strength as when metal is used. However, CFRP is a resin transfer molding method in which resin molding is performed after carbon fibers are stacked or wound, a method in which carbon fiber is impregnated with resin and wound in a heat-curing method, and hot using a prepreg. Since the shape of the product is adjusted by a pressing method or the like, the dimensional accuracy and surface state of the finished product are inferior to the metal processed product.
そこで特許文献１には、ＣＦＲＰの表面硬度、耐磨耗性等の機械的強度を補強することを目的として、ＣＦＲＰの脱脂処理を十分に行い、導電性をチェックして導電性が不十分な場合には導電性処理を行い、ＣＦＲＰと密着性が良く、比較的硬度が低く、ＣＦＲＰ−クロムメッキ間でクッションになり、熱膨張係数がＣＦＲＰに近いものとして鉄メッキを施し、更に上層メッキとしてクロムメッキ或いはニッケルメッキの上にクロムメッキを施し、表面研磨する方法が開示されている。 Therefore, in Patent Document 1, for the purpose of reinforcing the mechanical strength such as the surface hardness and wear resistance of CFRP, CFRP is sufficiently degreased to check the conductivity and the conductivity is insufficient. In some cases, the conductive treatment is performed, the adhesiveness with CFRP is good, the hardness is relatively low, the cushion becomes between CFRP and chrome plating, the thermal expansion coefficient is close to that of CFRP, and the iron plating is applied. A method is disclosed in which chromium plating is performed on chromium plating or nickel plating and surface polishing is performed.
この特許文献１に開示の実施例では、ＣＦＲＰ素管を用い、界面活性剤溶液による洗浄、水洗を行い、最後に温水洗をし、導電性が確認されたＣＦＲＰ素管にメッキ厚さ０．３〜１．０ｍｍの電気鉄メッキを行い、更にその上層へ電気クロムメッキを施してその表面を研磨している。そして、このＣＦＲＰ−金属（鉄）間の密着はサーマルテストや剥離テストでは異常なく、十分実用に耐え、従来のＣＦＲＰに銅メッキしたものに比べ遙に優れたものであり、ＣＦＲＰの表面硬度、耐磨耗性を向上させたもので、ＣＦＲＰ単独で設備材料として使用可能であることが開示されている。 In the example disclosed in this Patent Document 1, a CFRP base tube is used, and cleaning with a surfactant solution and water washing are performed, and finally hot water washing is performed. Electroiron plating of 3 to 1.0 mm is performed, and further, electrochrome plating is applied to the upper layer to polish the surface. The adhesion between the CFRP and the metal (iron) is not abnormal in the thermal test and the peel test, and is sufficiently practical and superior to the conventional CFRP copper-plated. The surface hardness of the CFRP, It is disclosed that the wear resistance is improved, and that CFRP alone can be used as an equipment material.
そして、特許文献１には、ＣＦＲＰ上への金属めっき素材として鉄を選択した理由の１つとして、ニッケルめっきは、めっき当初はＣＦＲＰとの密着性が良好であるが、めっき皮膜が硬いため、冷熱サイクルを加えると、めっき皮膜の剥離が起こりやすいことが開示されている。 In Patent Document 1, as one of the reasons for selecting iron as a metal plating material on CFRP, nickel plating has good adhesion with CFRP at the beginning of plating, but the plating film is hard. It is disclosed that when a cooling cycle is applied, peeling of the plating film tends to occur.
また、特許文献２には、ＣＦＲＰパイプ製の車輪側チューブを備えた二輪車等のフロントフォークにおいて、車輪側チューブの一層の軽量化を図り、且つ、車輪側チューブと車軸ブラケット又はロッドガイドとの結合強度の強化を図ることを目的として、車体側チューブと車輪側チューブを摺動自在に嵌合した二輪車等のフロントフォークにおいて、前記車輪側チューブがＣＦＲＰパイプ製の本体部を有してなり、該本体部の基端部の外周に、金属製の車軸ブラケットを接着剤を介して嵌着し、該車軸ブラケットと本体部を径方向に貫通する貫通孔を形成し、該貫通孔内にピンを挿入し、該車軸ブラケットと本体部を軸方向及び径方向に結合したものが開示されている。 Further, in Patent Document 2, in a front fork such as a two-wheeled vehicle provided with a wheel side tube made of CFRP pipe, the wheel side tube is further reduced in weight, and the wheel side tube and the axle bracket or the rod guide are combined. For the purpose of enhancing strength, in a front fork such as a motorcycle in which a vehicle body side tube and a wheel side tube are slidably fitted, the wheel side tube has a main body made of CFRP pipe, A metal axle bracket is fitted to the outer periphery of the base end portion of the main body portion with an adhesive to form a through hole that penetrates the axle bracket and the main body portion in the radial direction, and a pin is inserted into the through hole. It is disclosed that the axle bracket and the main body portion are inserted and joined in the axial direction and the radial direction.
この特許文献２に開示の実施例によれば、アウタチューブの本体部は、ＣＦＲＰ材のプリプレッグシートを芯型上に巻き回して形成した内径が同一のパイプを定寸に切断して用いている。本体部は、ＣＦＲＰパイプの内周をホーニング等により機械研磨して平滑にした後、無電解ニッケルめっき（約１０μｍ）を施し、外周については下ブラケットに支持される部分が軸方向で大外径となるような山形状（中心軸を含む縦断面の外形輪郭）に切削加工した後、外径仕上げクロスを巻き回し加工し、加熱処理して固めている。即ち、ＣＦＲＰ表面を切削加工したために炭素繊維が露出した部分には、薄手のプリプレッグを重ね張りして炭素繊維の脱落を防止している。 According to the embodiment disclosed in Patent Document 2, the main body portion of the outer tube is formed by cutting a pipe having the same inner diameter formed by winding a prepreg sheet of CFRP material on a core mold to a fixed size. Yes. The main body is smoothed by mechanical polishing of the inner periphery of the CFRP pipe by honing or the like, and then electroless nickel plating (about 10 μm) is applied, and the portion supported by the lower bracket on the outer periphery has a large outer diameter in the axial direction. After cutting into a mountain shape (external outline of the longitudinal section including the central axis), the outer diameter finishing cloth is wound and processed by heat treatment and hardened. That is, a thin prepreg is overlaid on the exposed portion of the carbon fiber because the CFRP surface is cut to prevent the carbon fiber from falling off.
即ち、ＣＦＲＰに切削加工等を施し、加工によって露出した炭素繊維の破壊や飛散を防止する技術としては、樹脂を用いて被覆する方法が一般的であった。 That is, as a technique for applying a cutting process or the like to CFRP to prevent destruction or scattering of carbon fibers exposed by the process, a method of coating with a resin is generally used.
前述の特許文献１では、ＣＦＲＰをロールとして用いる場合、硬度が低く、熱膨張率がＣＦＲＰに近い鉄の皮膜を電気めっき法を用いて形成することで、冷熱サイクルによる剥離の発生を防止しつつ、ＣＦＲＰの機械強度を補強している。しかし、特許文献１で形成している金属皮膜は、機械強度の向上と耐摩耗性の向上を目的として形成しており、最終的に得られる製品の寸法精度は、原型であるＣＦＲＰの成形精度如何で決まってしまう。また、特許文献１に開示の技術は、電気めっき法を用いる故に、ロールのような単純な形状の製品には適用できるが、金属材料をプレス加工したり、切削加工した製品の形状や、金属製品と同レベルの寸法精度を要求される用途には対応できない技術である。 In the above-mentioned Patent Document 1, when CFRP is used as a roll, an iron film having a low hardness and a thermal expansion coefficient close to that of CFRP is formed by using an electroplating method, thereby preventing occurrence of peeling due to a thermal cycle. The mechanical strength of CFRP is reinforced. However, the metal film formed in Patent Document 1 is formed for the purpose of improving mechanical strength and wear resistance, and the dimensional accuracy of the finally obtained product is the molding accuracy of the original CFRP. How it is decided. The technique disclosed in Patent Document 1 can be applied to a product having a simple shape such as a roll because it uses an electroplating method. However, the shape of a product obtained by pressing or cutting a metal material, This technology cannot be used for applications that require the same level of dimensional accuracy as products.
また、特許文献２に開示の技術は、外形加工を施したＣＦＲＰを構造材料として用い、必要部分に最適サイズに切断したプリプレグを貼り付け、加熱硬化させて仕上げている。しかし、この方法では仕上げ用のプリプレグであっても補強材を備えるため、その厚みが影響して仕上げ可能な寸法精度には限界がある。そして、更に加工精度を上げるためには、当該仕上げ部分を研磨し、表面に樹脂を塗布してから再仕上げを施すことになる。従って、特許文献２に開示の方法は、寸法精度を良好に仕上げるために必要な工程数は多く、人手に頼る部分も多いため、コストダウンが困難な方法である。 Further, the technique disclosed in Patent Document 2 uses CFRP that has undergone outer shape processing as a structural material, and a prepreg that has been cut to an optimum size is attached to a necessary portion, followed by heat curing. However, since this method includes a reinforcing material even for a prepreg for finishing, there is a limit to the dimensional accuracy that can be finished because of its thickness. And in order to raise processing precision further, the said finish part is grind | polished, and after applying resin on the surface, it will re-finish. Therefore, the method disclosed in Patent Document 2 is a method in which cost reduction is difficult because the number of steps necessary to finish the dimensional accuracy satisfactorily is large and there are many parts that rely on human hands.
従って、鋼板をプレス加工したり、金属を切削加工して得られる複雑な形状を備える構造材とほぼ同等の寸法精度と良好な表面状態とを備えるＣＦＲＰに対する要求は潜在的にあった。即ち、プレス鋼板等の代替品として使用可能なＣＦＲＰと、それをプレス鋼板等と同等の製造コストで得るための加工方法が要求されていた。 Accordingly, there is a potential demand for CFRP having a dimensional accuracy and a good surface condition substantially equivalent to a structural material having a complicated shape obtained by pressing a steel plate or cutting a metal. That is, there has been a demand for a CFRP that can be used as a substitute for a pressed steel sheet and a processing method for obtaining it at a manufacturing cost equivalent to that of a pressed steel sheet.
そこで、鋭意研究の結果本件発明者等は、ＣＦＲＰに外形加工を施す等をして炭素繊維が露出したＣＦＲＰの表面に金属皮膜を形成して炭素繊維の脱落を防止すれば、上記課題を解決できることに想到したのである。 Therefore, as a result of earnest research, the present inventors solved the above problems by forming a metal film on the surface of the CFRP where the carbon fiber is exposed by performing external processing on the CFRP to prevent the carbon fiber from falling off. I realized what I could do.
上記課題を解決するための手段について以下述べる。 Means for solving the above problems will be described below.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法： 本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法は、炭素繊維の露出部を有するＣＦＲＰ表面に以下の工程Ａ及び工程Ｂを経て金属皮膜を形成することで炭素繊維の脱落を防止することを特徴としている。 The method for preventing carbon fibers from falling off from the CFRP according to the present invention: The method for preventing the carbon fibers from falling off from the CFRP according to the present invention is a metal film that is subjected to the following steps A and B on the surface of the CFRP having an exposed portion of carbon fibers. It is characterized in that the carbon fiber is prevented from falling off by forming.
工程Ａ： ＣＦＰＲの表面を、過マンガン酸処理、又は、当該過マンガン酸処理と物理的表面処理及び／又は紫外線照射処理を用いて表面処理をし、ＣＦＲＰの表面を粗化する粗化処理工程。
工程Ｂ：工程Ａで得られたＣＦＲＰの表面に無電解めっき法を用いて金属皮膜を形成する無電解めっき工程。
Step A: Roughening treatment step of roughening the surface of CFRP by treating the surface of CFPR with permanganic acid treatment or using the permanganate treatment and physical surface treatment and / or ultraviolet irradiation treatment. .
Step B: An electroless plating step in which a metal film is formed on the surface of the CFRP obtained in Step A using an electroless plating method.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記工程Ｂは、金属皮膜として厚さが１μｍ〜５００μｍのニッケル皮膜を形成するものであることも好ましい。 In the method for preventing carbon fibers from falling off from the CFRP according to the present invention, the step B preferably forms a nickel film having a thickness of 1 μm to 500 μm as the metal film.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、工程Ｃとして、前記工程Ｂで形成された金属皮膜表面に、電気めっき法により電気めっき金属皮膜を形成する工程を付加したことも好ましい。 In the method for preventing carbon fibers from falling off from CFRP according to the present invention, it is also preferable to add, as Step C, a step of forming an electroplated metal film by electroplating on the surface of the metal film formed in Step B. .
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記工程Ｃは、電気めっき金属皮膜として厚さが４μｍ〜５００μｍのニッケル皮膜を形成するものであることも好ましい。 In the method for preventing carbon fibers from falling off from CFRP according to the present invention, it is also preferable that the step C forms a nickel film having a thickness of 4 μm to 500 μm as an electroplated metal film.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、工程Ｄとして、前記工程Ｃ及び／又は工程Ｂで形成された金属皮膜を機械加工する工程を付加したことも好ましい。 In the method for preventing carbon fibers from falling off from CFRP according to the present invention, it is also preferable to add a step of machining the metal film formed in step C and / or step B as step D.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記工程Ｄは、前記機械加工として切削加工又は研磨加工のいずれか一方又は双方を用いるものであることも好ましい。 In the method for preventing carbon fibers from falling off from the CFRP according to the present invention, the step D preferably uses either one or both of cutting and polishing as the machining.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法では、部分的に炭素繊維が露出したＣＦＲＰの、露出した炭素繊維表面にも金属皮膜を形成することにより炭素繊維の脱落を防止する。従って、寸法調整のために外形加工を施したＣＦＲＰであっても、炭素繊維の脱落が無くなり、炭素繊維は飛散しない。そして、外形加工したＣＦＲＰに厚い金属皮膜を形成し、この金属皮膜に更に機械加工を施せば、寸法精度は更に向上する。即ち、軽量でありながら、金属の加工品と同等の強度と寸法精度と外観とを備えたＣＦＲＰを得ることが出来る。 In the method for preventing the carbon fiber from falling off from the CFRP according to the present invention, the carbon fiber is prevented from falling off by forming a metal film on the exposed carbon fiber surface of the CFRP where the carbon fiber is partially exposed. Therefore, even if the CFRP is subjected to external processing for dimension adjustment, the carbon fibers are not dropped off, and the carbon fibers are not scattered. Then, if a thick metal film is formed on the externally processed CFRP and the metal film is further machined, the dimensional accuracy is further improved. That is, it is possible to obtain a CFRP that is light and yet has the same strength, dimensional accuracy, and appearance as a metal processed product.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法： 本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、炭素繊維の露出部を有するＣＦＲＰの表面に金属皮膜を形成することで炭素繊維の脱落を防止する。ＰＡＮ系炭素繊維の断面の一例を図１に示す。図１に示すように、炭素繊維は、マイクロポアを備えており、比表面積が大きい。そして、炭素繊維を用いたＣＦＲＰでは、マトリックス樹脂は、炭素繊維を包み込むように形成されている。即ち、マトリックス樹脂は、炭素繊維のマイクロポアの内部にまでは浸透していない。それ故に、ＣＦＲＰに外形加工を施すと炭素繊維が露出し、当該露出した炭素繊維から炭素繊維の破片が脱落する現象が発生する。外形加工前のＣＦＲＰ表層部の模式断面を、図２（ａ）に示す。このように、炭素繊維２は、その外側をマトリックス樹脂３でモールドされている。これをＣＦＲＰの加工予定面４に沿って外形加工すると、図２（ｂ）に示す模式断面のように、ＣＦＲＰの加工端面５に炭素繊維２が露出する。 Method for preventing carbon fiber from falling off from CFRP according to the present invention: In the method for preventing carbon fiber from falling off from CFRP according to the present invention, carbon fiber is formed by forming a metal film on the surface of CFRP having an exposed portion of carbon fiber. Prevents falling off. An example of a cross section of a PAN-based carbon fiber is shown in FIG. As shown in FIG. 1, the carbon fiber has micropores and has a large specific surface area. In CFRP using carbon fibers, the matrix resin is formed so as to wrap the carbon fibers. That is, the matrix resin does not penetrate into the micropores of the carbon fiber. Therefore, when CFRP is subjected to external processing, carbon fibers are exposed, and a phenomenon occurs in which carbon fiber fragments fall off from the exposed carbon fibers. FIG. 2A shows a schematic cross section of the CFRP surface layer portion before the outer shape processing. Thus, the outside of the carbon fiber 2 is molded with the matrix resin 3. When the outer shape is processed along the planned processing surface 4 of CFRP, the carbon fiber 2 is exposed on the processing end surface 5 of the CFRP as shown in the schematic cross section shown in FIG.
図２（ｂ）に示す露出した炭素繊維から、微細な炭素繊維屑の脱落を確実に防止するためには、脱落防止機能を発揮する物質が、炭素繊維の破断面を覆っていなければならない。そして、マイクロポアの内部までが充填された状態がより好ましい。このような目的に樹脂を用いても、樹脂ワニスの粘度が大きいため、マイクロポア内部までには浸透できない。その結果、炭素繊維との接着力が得られず、炭素繊維の破断面に樹脂の蓋をした状態にしかならない。樹脂を用いて炭素繊維の脱落防止を施した場合の模式断面を図３（ｃ）に示す。図３（ｃ）では、ＣＦＲＰの加工端面５は、被覆樹脂６の接着面とほぼ一致する。 In order to reliably prevent fine carbon fiber scraps from falling off from the exposed carbon fibers shown in FIG. 2 (b), the substance exhibiting the drop-off preventing function must cover the fracture surface of the carbon fibers. And the state where even the inside of the micropore was filled is more preferable. Even if a resin is used for such a purpose, since the viscosity of the resin varnish is large, it cannot penetrate into the micropores. As a result, the adhesive strength with the carbon fiber cannot be obtained, and only the resin lid is put on the fracture surface of the carbon fiber. FIG. 3 (c) shows a schematic cross section when the carbon fiber is prevented from falling off using a resin. In FIG. 3C, the processed end surface 5 of CFRP substantially coincides with the adhesive surface of the coating resin 6.
しかし、後述する無電解めっき法により金属皮膜を形成すれば、無電解めっき液は炭素繊維との濡れ性も良好で、前記マイクロポア内部にも浸透してゆく。従って、露出した炭素繊維のＣＦＲＰ表面付近のマイクロポア内部にも金属皮膜が形成され、更に、時間の経過に従ってマイクロポアが金属で充填されてゆく。その結果、炭素繊維の露出面に金属皮膜を形成した場合には、炭素繊維内部が金属で固着した状態となり、炭素繊維の脱落が防止できる。そして、金属皮膜を厚くして機械加工を施しても、炭素繊維が脱落しない。金属皮膜を形成して炭素繊維の脱落防止を施した場合の模式断面を図３（ｄ）に示す。図３（ｄ）に示すように、金属皮膜７は、ＣＦＲＰの加工端面５よりも内部の炭素繊維２にまで浸透した状態で形成される。 However, if a metal film is formed by an electroless plating method to be described later, the electroless plating solution has good wettability with the carbon fiber and penetrates into the micropores. Therefore, a metal film is also formed inside the micropores in the vicinity of the CFRP surface of the exposed carbon fiber, and the micropores are filled with metal as time passes. As a result, when a metal film is formed on the exposed surface of the carbon fiber, the inside of the carbon fiber is fixed with metal, and the carbon fiber can be prevented from falling off. Even if the metal film is thickened and machined, the carbon fiber does not fall off. FIG. 3D shows a schematic cross section in the case where a metal film is formed to prevent the carbon fibers from falling off. As shown in FIG. 3 (d), the metal film 7 is formed in a state where it penetrates to the carbon fiber 2 inside the processed end surface 5 of CFRP.
そして、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記金属皮膜は、以下の工程Ａ及び工程Ｂを経て形成する。 And in the fall prevention method of the carbon fiber from CFRP which concerns on this invention, the said metal film is formed through the following processes A and B.
工程Ａは、炭素繊維の露出部を有するＣＦＲＰを表面処理し、ＣＦＲＰの表面を粗化する粗化処理工程である。ＣＦＲＰは、熱硬化性樹脂ワニスと炭素繊維とを目的とする形状に整え、当該樹脂を熱硬化して得ることが多い。即ち、ＣＦＲＰの表面は、熱硬化性樹脂が流動化した後に硬化しているため、後の実施例で用いたＣＦＲＰの表面を示す図５のように、ミクロ的には滑らかな表面になっている。そして、このような滑らかな表面に金属皮膜を形成しても、金属皮膜とＣＦＲＰとの間には、良好な密着性が得られない。従って、特許文献１に記載があるように、冷熱サイクルによる剥離が発生する。そこで、ＣＦＲＰ表面を粗化処理して凹凸形状を形成し、アンカー効果により密着性を改善する。しかし、粗化処理によりＣＦＲＰの表面に形成される凹凸形状は、用いる表面処理手法により異なる。従って、目的に応じて、表面処理手法を選択したり、組み合わせて用いることが好ましい。 Step A is a roughening treatment step in which CFRP having an exposed portion of carbon fiber is surface treated to roughen the surface of CFRP. CFRP is often obtained by preparing a thermosetting resin varnish and carbon fiber in a desired shape and thermosetting the resin. That is, since the surface of CFRP is cured after the thermosetting resin is fluidized, it becomes a microscopically smooth surface as shown in FIG. 5 showing the surface of CFRP used in the following examples. Yes. And even if a metal film is formed on such a smooth surface, good adhesion cannot be obtained between the metal film and CFRP. Therefore, as described in Patent Document 1, peeling occurs due to a cooling / heating cycle. Therefore, the CFRP surface is roughened to form an uneven shape, and the adhesion is improved by the anchor effect. However, the concavo-convex shape formed on the surface of the CFRP by the roughening treatment varies depending on the surface treatment method used. Therefore, it is preferable to select a surface treatment method according to the purpose or use it in combination.
そのため、前記工程Ａの表面処理は、過マンガン酸処理、又は、当該過マンガン酸処理と物理的表面処理及び／又は紫外線照射処理を用いる。即ち、過マンガン酸処理、又は、当該過マンガン酸処理と物理的表面処理及び／又は紫外線照射処理を組み合わせて用いてＣＦＲＰの表面を粗化し、アンカー効果を発揮させて金属皮膜とＣＦＲＰとの密着性を改善する。尚、ここで言っている物理的表面処理とはスパッタリングエッチング等を含んでいる。そして、ブラスト処理等の物理的表面処理手法のみを用いて粗化処理した場合、めっき皮膜とＣＦＲＰとの安定した密着性が得られない場合があるが、過マンガン酸処理や紫外線照射処理などの化学的表面処理手法を併用することで、良好な密着性が得られる。上記のように、粗化処理の手法は、費用対効果を考えて処理方法の組み合わせを選択すれば良い。 Therefore, the surface treatment in the step A uses permanganic acid treatment or the permanganic acid treatment and physical surface treatment and / or ultraviolet irradiation treatment. That is, permanganic acid treatment, or a combination of the permanganic acid treatment and physical surface treatment and / or ultraviolet irradiation treatment is used to roughen the surface of the CFRP and exert an anchor effect to adhere the metal film to the CFRP. Improve sex. The physical surface treatment referred to here includes sputtering etching and the like. And when roughening treatment is performed using only a physical surface treatment technique such as blast treatment, stable adhesion between the plating film and CFRP may not be obtained, but permanganic acid treatment, ultraviolet irradiation treatment, etc. Good adhesion can be obtained by using a chemical surface treatment method in combination. As described above, as the roughening processing method, a combination of processing methods may be selected in consideration of cost effectiveness.
そして、前記物理的表面処理にはブラスト処理を用いることが出来る。このブラスト処理は、流体を用いて研磨剤を流動化させ、被加工面に衝突させて処理する手法であり、ドライブラスト処理とウェットブラスト処理とがある。そして、ドライブラスト処理では、ウェットブラスト処理に比べて被加工面に与える加工応力が大きいのが通常である。従って、ＣＦＲＰの表面処理にドライブラスト処理を用いた場合には、ＣＦＲＰ表面に衝突した研磨剤が、衝突部近傍に存在する炭素繊維を破壊してしまうことがある。炭素繊維が破壊されれば、ＣＦＲＰの機械強度が低下し、炭素繊維の脱落に伴う粉塵の発生が多くなるため好ましくない。ドライブラスト処理を用いる場合には、＃１００〜＃１０００程度の切削用の砂を０．０３Ｐａ〜０．５０Ｐａ程度の圧力で噴出させれば、炭素繊維の破壊を抑制した状態で、ＣＦＲＰ表面を粗化することが出来る。 A blasting process can be used for the physical surface treatment. This blasting process is a technique in which a polishing agent is fluidized using a fluid and is made to collide with a surface to be processed, and includes a drive blast process and a wet blast process. In the drive blast process, the processing stress applied to the processing surface is usually larger than in the wet blast process. Therefore, when the drive last process is used for the surface treatment of the CFRP, the abrasive that collides with the CFRP surface may destroy the carbon fibers existing in the vicinity of the collision portion. If the carbon fiber is destroyed, the mechanical strength of the CFRP decreases, and the generation of dust accompanying the dropping of the carbon fiber increases, which is not preferable. In the case of using the drive last process, if the sand for cutting of about # 100 to # 1000 is ejected at a pressure of about 0.03 Pa to 0.50 Pa, the CFRP surface is suppressed in a state where the destruction of the carbon fiber is suppressed. It can be roughened.
しかし、炭素繊維の破壊を回避する必要がある場合には、ウェットブラスト処理を採用することが好ましい。ウェットブラスト処理であれば、研磨剤を水等の溶媒に分散させて用いるため、被処理面に与えるダメージは、ドライブラスト処理に比べて小さくなる。従って、前記物理的表面処理といっても一概に適正な条件を設定することは困難であり、実験を行なった上で目的とする表面状態に適合した研磨メディアの選択とブラスト条件の設定をする必要がある。 However, when it is necessary to avoid the destruction of the carbon fiber, it is preferable to employ wet blasting. In the case of wet blasting, the abrasive is dispersed in a solvent such as water, so that the damage given to the surface to be processed is smaller than in drive blasting. Therefore, it is difficult to set appropriate conditions in general even for the physical surface treatment, and after conducting experiments, selection of polishing media suitable for the target surface condition and setting of blast conditions are performed. There is a need.
上述の過マンガン酸を用いたエッチング処理では、ＣＦＲＰのマトリックス樹脂を、過マンガン酸を含むアルカリの高濃度溶液を高温にして用いて溶解する（以下、「過マンガン酸処理」と称する）。ＣＦＲＰを過マンガン酸処理すると、プラスチックの溶けやすさに応じて溶解が進行するため、粗化表面が得られる。 In the above-described etching process using permanganic acid, the CFRP matrix resin is dissolved using an alkali high-concentration solution containing permanganic acid at a high temperature (hereinafter referred to as “permanganic acid process”). When CFRP is treated with permanganic acid, the dissolution proceeds according to the ease of melting of the plastic, so that a roughened surface is obtained.
例えば、過マンガン酸処理として、以下に示す工程を用いることができる。まず、ＮａＯＨ濃度３０ｇ／Ｌ〜７０ｇ／Ｌとした液を用い、液温を６０℃〜８０℃として１０分間〜６０分間ＣＦＲＰを浸漬して脱脂処理を施す。その後、奥野製薬工業（株）製ＯＰＣ−１４００ニュートライザー等を用い、液温を８０℃程度として５分間〜２０分間膨潤処理を施す。膨潤処理したＣＦＲＰは、奥野製薬工業（株）製ＯＰＣ−１５４０ＭＮとＯＰＣ−１２００エポエッチを混合して調製した溶液等を用い、液温６０℃〜８０℃で１０分間〜１２０分間処理し、表面を粗化する。粗化処理したＣＦＲＰは、液温を４０℃〜８０℃とした奥野製薬工業（株）製ＯＰＣ−１０８０コンディショナー等を用いた溶液に５分間〜３０分間浸漬して中和し、水洗する。 For example, the process shown below can be used as permanganic acid treatment. First, using a solution having a NaOH concentration of 30 g / L to 70 g / L, the solution temperature is set to 60 ° C. to 80 ° C. and CFRP is immersed for 10 minutes to 60 minutes to perform a degreasing treatment. Then, using an OPC-1400 Neutralizer manufactured by Okuno Seiyaku Kogyo Co., Ltd., the liquid temperature is set to about 80 ° C., and a swelling treatment is performed for 5 minutes to 20 minutes. The CFRP subjected to the swelling treatment is treated with a solution prepared by mixing OPC-1540MN manufactured by Okuno Pharmaceutical Co., Ltd. and OPC-1200 epoch etch at a liquid temperature of 60 ° C. to 80 ° C. for 10 minutes to 120 minutes. Roughen. The roughened CFRP is neutralized by immersing it in a solution using an OPC-1080 conditioner manufactured by Okuno Pharmaceutical Co., Ltd. having a liquid temperature of 40 ° C. to 80 ° C. for 5 minutes to 30 minutes, and washed with water.
また、化学的表面処理手法として紫外線照射処理を施せば、めっき皮膜とＣＦＲＰとの密着性は更に優れたものになる。化学的表面処理としての紫外線照射処理では、紫外線が、紫外線を吸収したプラスチックの、分子結合のみを破壊する性質を利用している。即ち、前記ブラスト処理や前記過マンガン酸処理を施すことで得られた、比較的大きな凹凸を備えるＣＦＲＰの粗化表面は、紫外線を照射することにより、小さな、サブミクロンオーダーの凹凸も備える表面になる。金属皮膜を、このサブミクロンオーダーの凹凸を備えるＣＦＲＰ表面に形成すると、金属皮膜は当該微細な凹凸に埋没したアンカーを備えることになる。そして、この微細なアンカーはプラスチックから抜け難いため、金属皮膜とＣＦＲＰとの密着性は、更に良好なものとなるのである。 Further, if an ultraviolet irradiation treatment is performed as a chemical surface treatment technique, the adhesion between the plating film and the CFRP is further improved. In the ultraviolet irradiation treatment as a chemical surface treatment, ultraviolet rays use the property that plastics that have absorbed ultraviolet rays break only molecular bonds. That is, the roughened surface of CFRP having relatively large irregularities obtained by performing the blast treatment or the permanganic acid treatment becomes a surface having small, submicron-order irregularities by irradiating with ultraviolet rays. Become. When the metal film is formed on the CFRP surface having the unevenness of the submicron order, the metal film includes the anchor buried in the fine unevenness. And since this fine anchor is hard to come off from a plastic, the adhesiveness of a metal film and CFRP becomes still better.
紫外線照射処理では、主波長１８０ｎｍ〜４００ｎｍの紫外線を用い、ＣＦＲＰ被めっき物表面における紫外線強度は１ｍｗ／ｃｍ２〜５００ｍｗ／ｃｍ２で、０．５分間以上照射すれば改質することが出来る。ここで選択する紫外線の波長は、処理対象とするプラスチックの吸収率が大きい波長範囲から選択することが好ましい。 In the ultraviolet irradiation treatment, ultraviolet rays having a main wavelength of 180 nm to 400 nm are used, and the ultraviolet intensity on the surface of the CFRP object is 1 mw / cm 2 to 500 mw / cm 2 . The wavelength of the ultraviolet rays selected here is preferably selected from a wavelength range in which the absorption rate of the plastic to be processed is large.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、工程Ｂは、工程Ａで得られたＣＦＲＰ被めっき物表面に、無電解めっき法を用いて金属皮膜を形成する無電解めっき工程である。本件発明では、工程Ａで得られたＣＦＲＰ被めっき物の表面には、粗化されたプラスチック表面と炭素繊維が露出した部分とがあり、露出した炭素繊維表面を覆うように金属皮膜を形成する。この露出した炭素繊維とプラスチック表面とを金属皮膜で被覆するためには、無電解めっき法を用いることが好ましい。無電解めっき法を用いれば、無電解めっき液がマイクロポアを備える炭素繊維の内部まで浸透する。その結果、炭素繊維の内部にも金属皮膜が形成され、炭素繊維の脱落が無くなる。しかも、炭素繊維の内部を充填するように金属皮膜が成長する。従って、金属皮膜を備えるＣＦＲＰの金属皮膜に機械加工を施しても、炭素繊維が脱落することが無くなる。 In the method for preventing carbon fibers from falling off from CFRP according to the present invention, the process B is an electroless plating process in which a metal film is formed on the surface of the CFRP workpiece obtained in the process A using an electroless plating method. is there. In the present invention, the surface of the CFRP object to be plated obtained in step A has a roughened plastic surface and a portion where the carbon fiber is exposed, and a metal film is formed so as to cover the exposed carbon fiber surface. . In order to coat the exposed carbon fiber and the plastic surface with a metal film, it is preferable to use an electroless plating method. If the electroless plating method is used, the electroless plating solution penetrates to the inside of the carbon fiber provided with micropores. As a result, a metal film is also formed inside the carbon fiber, and the carbon fiber does not fall off. Moreover, the metal film grows so as to fill the inside of the carbon fiber. Therefore, even if machining is performed on the metal film of CFRP provided with the metal film, the carbon fiber does not fall off.
また、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記工程Ｂは、金属皮膜として厚さが１μｍ〜５００μｍのニッケル皮膜を形成するものであることも好ましい。ニッケルは、耐食性が良好な金属であり、装飾用から電子回路まで広汎な用途に対応できる金属である。そのため、めっき方法も多岐に亘り開発されている。従って、無電解ニッケルめっきを選択すると、厚膜を形成する用途においても、安定しためっき操作が可能である。 Moreover, in the method for preventing carbon fibers from falling off from CFRP according to the present invention, the step B preferably forms a nickel film having a thickness of 1 μm to 500 μm as a metal film. Nickel is a metal with good corrosion resistance and can be used for a wide range of applications from decoration to electronic circuits. Therefore, a wide variety of plating methods have been developed. Therefore, when electroless nickel plating is selected, stable plating operation is possible even in applications where thick films are formed.
ここで、本件発明で言っているニッケル皮膜の厚さとは、粗化処理などにより増大した比表面積を無視し、ＣＦＲＰの表面を平滑面と見なしたときの厚さであることを断っておく。前述のように、ＣＦＲＰの被めっき面は、プラスチック部分は粗化されており、炭素繊維が露出した部分の比表面積は大きい。この様な、ミクロ的に見れば広い表面であっても、１μｍ厚さのニッケル皮膜が形成されていれば、炭素繊維の脱落が防止できる。そして、４μｍ厚さのニッケルめっき皮膜が形成されると、被めっき面全体には同レベルの導電性が付与されることになり、電気めっきを施すことが容易になる。しかし、工程Ｂで形成するニッケル皮膜厚さは、最終的に得るめっき皮膜の形状や、後工程の設計によって決めれば良い。 Here, the thickness of the nickel film referred to in the present invention is a thickness when the specific surface area increased by the roughening treatment or the like is ignored and the surface of the CFRP is regarded as a smooth surface. . As described above, on the CFRP surface to be plated, the plastic portion is roughened, and the specific surface area of the portion where the carbon fiber is exposed is large. Even if it is such a microscopically wide surface, if a nickel film having a thickness of 1 μm is formed, it is possible to prevent the carbon fibers from falling off. When a nickel plating film having a thickness of 4 μm is formed, the same level of conductivity is imparted to the entire surface to be plated, and it becomes easy to perform electroplating. However, the thickness of the nickel film formed in the process B may be determined by the shape of the plating film finally obtained and the design of the subsequent process.
そして、５００μｍの厚さを超えて無電解ニッケルめっきを施すには長時間を要する。また、消費する無電解めっき液量も多くなってコストがかさみ、工業的な生産性を維持できなくなる。従って、５００μｍを超える、過大な厚さとすることは好ましくない。また、ＣＦＲＰには一旦外形加工を施してあるため、５００μｍ厚さのニッケル皮膜を備えていれば、機械加工を施すことにより、寸法精度を容易に微調整出来る。 And it takes a long time to apply electroless nickel plating exceeding the thickness of 500 μm. In addition, the amount of electroless plating solution to be consumed increases and costs increase, making it impossible to maintain industrial productivity. Therefore, it is not preferable to make the thickness over 500 μm. In addition, since the outer shape is once applied to the CFRP, if a nickel film having a thickness of 500 μm is provided, the dimensional accuracy can be easily finely adjusted by applying the machining.
工程Ｂで無電解ニッケルめっきを施すには、市販の無電解ニッケルめっき液を用いた公知の方法が採用できる。しかし、ニッケルめっき皮膜とＣＦＲＰとの密着性を安定させるためには、内部応力（引張り応力）が小さいニッケルめっき皮膜が得られるめっき方法を選択することが好ましい。例えば、以下の工程を用いて無電解ニッケル皮膜を得ることが出来る。ＣＦＲＰを水洗後、定法でアルカリ脱脂処理する。そしてこのＣＦＲＰに、ＳｎＣｌ２濃度を０．０１ｇ／Ｌ〜０．５０ｇ／Ｌとした塩化第一錫水溶液と、ＰｄＣｌ２濃度を０．０１ｇ／Ｌ〜０．５０ｇ／Ｌとした塩化パラジウム水溶液とに交互に浸漬処理する、感受性・活性化法で触媒付与処理を施す。その後、無電解ニッケルめっき液として日本カニゼン製ＳＫ−１００等を用い、液温を４０℃〜９０℃として、触媒が付与されたＣＦＲＰを、所定のメッキ厚さが得られるまでの時間浸漬する。 In order to perform electroless nickel plating in step B, a known method using a commercially available electroless nickel plating solution can be employed. However, in order to stabilize the adhesion between the nickel plating film and the CFRP, it is preferable to select a plating method capable of obtaining a nickel plating film having a small internal stress (tensile stress). For example, an electroless nickel film can be obtained using the following steps. After CFRP is washed with water, it is alkali degreased by a conventional method. And this CFRP, a stannous chloride aqueous solution for the SnCl 2 concentration of 0.01g / L~0.50g / L, and an aqueous palladium chloride solution to the PdCl 2 concentration of 0.01g / L~0.50g / L The catalyst is applied by the sensitivity / activation method, in which the substrate is alternately immersed. Thereafter, SK-100 manufactured by Nihon Kanisen Co., Ltd. is used as the electroless nickel plating solution, the solution temperature is set to 40 ° C. to 90 ° C., and CFRP to which the catalyst is applied is immersed for a time until a predetermined plating thickness is obtained.
また、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、工程Ｃとして、前記工程Ｂで形成された金属皮膜表面に、電気めっき法により電気めっき金属皮膜を形成する工程を付加したことも好ましい。前述のように、無電解めっき法のみを用いて厚い金属層を形成することは、工業的な生産性の面で不利である。また、異種金属を組み合わせた複合金属層を形成することもある。複合金属層を形成するのであれば、無電解めっき法を用いて第１の金属皮膜を形成してＣＦＲＰ表面の導電性を均一にし、電気めっき法を用いて第２の電気めっき金属皮膜を形成することが、生産性の面からは好ましい。そして、工程Ｃにおいても、下地である無電解めっき皮膜との密着性を良好にするためには、内部応力（引張り応力）が小さいめっき皮膜が得られるめっき方法を選択することがより好ましい。 In addition, in the method for preventing carbon fibers from falling off from CFRP according to the present invention, a step of forming an electroplated metal film by an electroplating method on the surface of the metal film formed in step B is added as step C. Is also preferable. As described above, forming a thick metal layer using only an electroless plating method is disadvantageous in terms of industrial productivity. In addition, a composite metal layer in which different metals are combined may be formed. If a composite metal layer is to be formed, the electroless plating method is used to form the first metal film to make the CFRP surface conductive and the electroplating method is used to form the second electroplated metal film. It is preferable from the viewpoint of productivity. And also in the process C, in order to make the adhesiveness with the electroless plating film which is a foundation | substrate favorable, it is more preferable to select the plating method from which the plating film with a small internal stress (tensile stress) is obtained.
更に、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、前記工程Ｃは、電気めっき金属皮膜として厚さが４μｍ〜５００μｍのニッケル皮膜を形成するものであることも好ましい。電気ニッケルめっき法は、無電解ニッケルめっきと同様、装飾用から電子回路まで広汎な用途に対応しているため、めっき方法も多岐に亘り開発されている。そして、用いるめっき液の組成や電流密度の選択により、その表面状態を、黒色から光沢までの広い範囲に作り込むことが出来る。 Furthermore, in the method for preventing carbon fibers from falling off from the CFRP according to the present invention, it is also preferable that the step C forms a nickel film having a thickness of 4 μm to 500 μm as an electroplated metal film. Similar to electroless nickel plating, the electro nickel plating method can be used for a wide range of applications from decoration to electronic circuits. And by selecting the composition of the plating solution to be used and the current density, the surface state can be made in a wide range from black to gloss.
また、炭素繊維表面へ金属皮膜を形成するには、工程Ｂでは、つき廻り性の良好な無電解ニッケルめっきを施すことが好ましい。従って、工程Ｃにおいても電気めっき金属皮膜としてニッケル皮膜を形成すれば、金属皮膜間の密着性も良好になる。ここで形成する電気めっきニッケル皮膜の厚さについては、ニッケル皮膜の外観調整を行うのであれば、４μｍの厚さで十分である。一方、電気めっきニッケル皮膜の厚さが５００μｍあれば、寸法調整を目的とした機械加工を施すことが出来る。 Moreover, in order to form a metal film on the carbon fiber surface, in the process B, it is preferable to perform electroless nickel plating with good throwing power. Therefore, if a nickel film is formed as an electroplated metal film in the process C, the adhesion between the metal films is also improved. As for the thickness of the electroplated nickel film formed here, a thickness of 4 μm is sufficient if the appearance of the nickel film is adjusted. On the other hand, if the thickness of the electroplated nickel film is 500 μm, machining for the purpose of dimension adjustment can be performed.
工程Ｃで電気ニッケルめっきを施すには、無電解めっきの場合と同様、市販の電気ニッケルめっき液を用いることが出来る。しかし、ワット浴やスルファミン酸浴等を、自身で調製して用いることも可能である。例えば、ワット浴を用いるのであれば、硫酸ニッケル７水塩３００ｇと塩化ニッケル７水塩５０ｇをイオン交換水に溶解し、ホウ酸等を用いてｐＨを４．５程度に調整する。そして、このめっき液を用い、液温を５５℃として陰極電流密度３Ａ／ｄｍ２で電解すると、ニッケルの電気めっき皮膜を得ることが出来る。 In order to perform electro nickel plating in the step C, a commercially available electro nickel plating solution can be used as in the case of electroless plating. However, a Watt bath, a sulfamic acid bath, or the like can be prepared and used by itself. For example, if a Watt bath is used, 300 g of nickel sulfate heptahydrate and 50 g of nickel chloride heptahydrate are dissolved in ion exchange water, and the pH is adjusted to about 4.5 using boric acid or the like. When this plating solution is used and electrolysis is performed at a cathode current density of 3 A / dm 2 at a liquid temperature of 55 ° C., a nickel electroplating film can be obtained.
更に、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法においては、工程Ｄとして、前記工程Ｃ及び／又は工程Ｂで形成された金属皮膜を機械加工する工程を付加したことも好ましい。ＣＦＲＰの成形後に外形加工が施され、露出した炭素繊維が金属で被覆されているＣＦＲＰの寸法精度を向上させるには、加工精度が良好な、機械加工を施すことが好ましい。機械加工で寸法調整すれば、寸法精度の作り込みが出来る。また、表面仕上げを施す場合でも、各種金属素材に対する加工経験が豊富であり、目的に対して最適な手法を選択すれば、金属皮膜の表面を、狙いの状態に仕上げることが出来る。そして、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法を用いた金属被覆ＣＦＲＰであれば、ＣＦＲＰを被覆している金属皮膜に機械加工を施しても、炭素繊維の脱落が起こることは無い。 Furthermore, in the method for preventing carbon fibers from falling off from CFRP according to the present invention, it is also preferable to add a step of machining the metal film formed in step C and / or step B as step D. In order to improve the dimensional accuracy of CFRP in which outer shape processing is performed after CFRP molding and exposed carbon fibers are coated with metal, it is preferable to perform machining with good processing accuracy. If the dimensions are adjusted by machining, dimensional accuracy can be built. In addition, even when surface finishing is performed, processing experience with various metal materials is abundant, and the surface of the metal film can be finished in a target state by selecting an optimum method for the purpose. And if it is a metal-coated CFRP using the method for preventing carbon fibers from falling off from the CFRP according to the present invention, even if the metal film covering the CFRP is machined, the carbon fibers will not fall off. .
前記工程Ｄは、前記機械加工として切削加工又は研磨加工のいずれか一方又は双方を用いるものであることも好ましい。形状や寸法精度の調整を行うのであれば、旋盤加工や、フライス盤加工等の切削加工を用いることが好ましい。 The step D preferably uses one or both of cutting and polishing as the machining. In order to adjust the shape and dimensional accuracy, it is preferable to use a cutting process such as a lathe process or a milling process.
また、金属皮膜の表面を光沢面に加工する場合には、主に研磨加工を施す。光沢面を得ることを目的とすれば、金属皮膜として光沢ニッケル皮膜を形成しておくことが好ましい。しかし、電子回路分野における光沢ニッケルめっきは、金めっきの下地めっきとして施すことが多く、ニッケルめっき皮膜の表面状態は、あえて鏡面にはしていない。しかし、この光沢ニッケル面は、バフを用いて研磨加工を施したり、狭い範囲に対してはウェットブラスト処理を用いて研磨加工を施すことにより、鏡面に近い光沢面に仕上げることが出来る。 Further, when the surface of the metal film is processed into a glossy surface, polishing is mainly performed. For the purpose of obtaining a glossy surface, it is preferable to form a bright nickel film as the metal film. However, bright nickel plating in the field of electronic circuits is often applied as a gold plating base plating, and the surface state of the nickel plating film is not intended to be a mirror surface. However, the glossy nickel surface can be finished to a glossy surface close to a mirror surface by polishing with a buff or by applying wet polishing to a narrow area.
本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法を用いて得られる金属被覆ＣＦＲＰ： 本件発明に係るＣＦＲＰからの炭素繊維脱落防止方法を用いて得られる金属被覆ＣＦＲＰは、前述のように、金属皮膜を形成する前のＣＦＲＰに、一旦外形加工を施している。従って、通常の製造方法から得られるＣＦＲＰに比べると、寸法精度は良好である。この良好な寸法精度を備えるＣＦＲＰに、炭素繊維の脱落防止を目的として金属皮膜を形成すれば、寸法精度に優れた金属被覆ＣＦＲＰが得られる。そして、金属としてニッケルを選択すれば、耐食性にも優れたものとなる。また、前記金属被覆層に更に外形加工を施した金属被覆ＣＦＲＰは、金属を加工して得られる構造体とほぼ同等の寸法精度を備える金属被覆ＣＦＲＰである。 Carbon fibers metallized CFRP obtained by using the captive method from CFRP according to the present invention: a metal-coated CFRP obtained by using the carbon fiber falling-off prevention method from CFRP according to the present invention, as described above, metal the CFRP before forming the film, are once subjected to contour machining. Therefore, the dimensional accuracy is better than that of CFRP obtained from a normal manufacturing method. If a metal film is formed on the CFRP having good dimensional accuracy for the purpose of preventing the carbon fibers from falling off, a metal-coated CFRP having excellent dimensional accuracy can be obtained. And if nickel is selected as a metal, it will also be excellent in corrosion resistance. The metal-coated CFRP obtained by further processing the metal-coated layer is a metal-coated CFRP having a dimensional accuracy substantially equivalent to that of a structure obtained by processing a metal.
また、研磨加工を施した金属被覆ＣＦＲＰであれば、例えば、従来は軽合金等を使用していた液晶表示部のバックパネルに用いることが出来る。例えば、まず液晶のバックパネルを、反射鏡と一体化した形状にＣＦＲＰを成型して機械加工を施す。そして、形状を整えた該バックパネルの反射鏡部分に、例えばニッケルめっきを施して研磨し、鏡面仕上げした金属被覆ＣＦＲＰとするのである。この金属被覆ＣＦＲＰを用いて製作されたバックライトの反射鏡は、加工工程数が少なくて低コストでありながら軽量で、且つ、十分な実用性を備えるものとなる。そして、鏡面仕上げを施した前記ニッケルめっきの上に更にクロムめっきを施した金属被覆ＣＦＲＰは、鏡面の反射率と耐久性が更に向上する。このような反射鏡は、軽量であるため大型化が可能であり、産業用設備の照明装置の反射鏡として用いることが出来る。 Further, a metal-coated CFRP that has been subjected to polishing can be used, for example, for a back panel of a liquid crystal display unit that conventionally uses a light alloy or the like. For example, a CFRP is first molded into a shape in which a liquid crystal back panel is integrated with a reflecting mirror and then machined. Then, the reflecting mirror portion of the back panel whose shape has been adjusted is polished by applying, for example, nickel plating to obtain a mirror-finished metal-coated CFRP. A reflector for a backlight manufactured using this metal-coated CFRP has a small number of processing steps, is low in cost, and has sufficient practicality. And the metal-coated CFRP in which chrome plating is further performed on the nickel plating having a mirror finish further improves the reflectivity and durability of the mirror surface. Such a reflecting mirror is lightweight and can be increased in size, and can be used as a reflecting mirror for a lighting device of an industrial facility.
実施例１では、ＰＡＮ系炭素繊維を用いたＣＦＲＰ板を、被めっき材として用いた。この被めっき材に、粗化処理として過マンガン酸処理を１２０分間施し、その後６０μｍ厚さの無電解ニッケルめっきを施した。試験条件を、実施例２、実施例３及び比較例の条件と合わせて、後の表１に示す。 In Example 1, a CFRP plate using PAN-based carbon fibers was used as a material to be plated. This material to be plated was subjected to permanganic acid treatment as a roughening treatment for 120 minutes, and then electroless nickel plating having a thickness of 60 μm was performed. The test conditions are shown in Table 1 later together with the conditions of Example 2, Example 3, and Comparative Example.
過マンガン酸処理は、イオン交換水に奥野製薬工業（株）製ＯＰＣ−１５４０ＭＮを１００ｇ／Ｌ、ＯＰＣ−１２００エポエッチを１００ｇ／Ｌとなるよう加えて調製した過マンガン酸処理液を用い、図２に示す工程で処理した。過マンガン酸処理前の被めっき材表面を図５に、１２０分間の過マンガン酸処理後の被めっき材表面を図６に示す。 The permanganic acid treatment was performed using a permanganic acid treatment solution prepared by adding OPC-1540MN manufactured by Okuno Pharmaceutical Co., Ltd. to 100 g / L and OPC-1200 Epoch etch at 100 g / L in ion exchange water. It processed in the process shown to. The surface of the material to be plated before permanganic acid treatment is shown in FIG. 5, and the surface of the material to be plated after 120 minutes of permanganic acid treatment is shown in FIG.
前記で得られた被めっき材に、図７に示す工程で無電解ニッケルめっきを施した。得られたニッケル皮膜は、試験材ＣＦＲＰの固定治具部分に僅かにフクレが観察されたため、膨れ評価は△とした。そして、このニッケル皮膜とＣＦＲＰとの密着強度を評価したところ、８．２ｋｇｆ／ｃｍ２であった。上記評価結果を、実施例２及び比較例の結果と併せて、後の表２に示す。 The plated material obtained above was subjected to electroless nickel plating in the step shown in FIG. In the obtained nickel film, a slight swelling was observed in the fixing jig portion of the test material CFRP. And when adhesive strength of this nickel membrane | film | coat and CFRP was evaluated, it was 8.2kgf / cm < 2 >. The evaluation results are shown in Table 2 later together with the results of Example 2 and the comparative example.
実施例２では、過マンガン酸処理を６０分間とした以外は実施例１と同じ条件で無電解ニッケルめっきを施した。試験条件を、実施例１、実施例３及び比較例の条件と合わせて、後の表１に示す。 In Example 2, electroless nickel plating was performed under the same conditions as in Example 1 except that the permanganate treatment was performed for 60 minutes. The test conditions are shown in Table 1 later together with the conditions of Example 1, Example 3, and Comparative Example.
得られたニッケル皮膜には膨れが観察されず、評価は○とした。そして、このニッケル皮膜とＣＦＲＰとの密着強度は、９．１ｋｇｆ／ｃｍ２であった。上記評価結果を、実施例１及び比較例の結果と併せて、後の表２に示す。また、ここで得られたニッケルめっきＣＦＲＰの外観写真を図８に、ニッケル皮膜剥離試験後のＣＦＲＰの表面の外観写真を図９に示す。 No swelling was observed in the obtained nickel film, and the evaluation was good. The adhesion strength between the nickel film and CFRP was 9.1 kgf / cm 2 . The evaluation results are shown in Table 2 later together with the results of Example 1 and Comparative Example. Moreover, the external appearance photograph of the nickel plating CFRP obtained here is shown in FIG. 8, and the external appearance photograph of the surface of the CFRP after the nickel film peeling test is shown in FIG.
実施例３では、端面を切削加工したＣＦＲＰに実施例２と同様の粗化処理と無電解ニッケルめっきとを施し、露出した炭素繊維の被覆状態を観察した。ＣＦＲＰを炭素繊維織布に対して直角に切削加工した部分の表面状態を図１０に示す。そして、前記炭素繊維の露出部分に無電解ニッケルめっきを施した部分の断面を図１１に示す。図１１に見られるように、炭素繊維の周囲及び破断面にニッケルめっきが施されている。また、ＣＦＲＰの外形加工表面近傍のニッケルめっき状態を示す断面の拡大写真を図１２に示す。図１２左上に観察されている炭素繊維の断面は、図１の示す炭素繊維の断面形状とは明らかに異なっており、炭素繊維の内部表面の全面にニッケルめっき皮膜が形成されている。この状態であれば、炭素繊維の脱落は起こらない。 In Example 3, the same roughening treatment and electroless nickel plating as in Example 2 were applied to the CFRP whose end face was cut, and the exposed carbon fiber coating state was observed. FIG. 10 shows a surface state of a portion obtained by cutting CFRP at a right angle with respect to the carbon fiber woven fabric. And the cross section of the part which gave the electroless nickel plating to the exposed part of the said carbon fiber is shown in FIG. As can be seen in FIG. 11, nickel plating is applied to the periphery and the fracture surface of the carbon fiber. Moreover, the enlarged photograph of the cross section which shows the nickel plating state of the external shape processed surface of CFRP is shown in FIG. The cross section of the carbon fiber observed in the upper left of FIG. 12 is clearly different from the cross section of the carbon fiber shown in FIG. 1, and a nickel plating film is formed on the entire inner surface of the carbon fiber. In this state, the carbon fiber does not fall off.
比較例では、実施例で用いたと同様の被めっき材に、粗化処理を施さないまま、実施例と同様の工程を用いて、６０μｍ厚さの無電解ニッケルめっきを施した。試験条件を実施例１、実施例２及び実施例３の試験条件と併せて、以下の表１に示す。 In the comparative example, an electroless nickel plating having a thickness of 60 μm was applied to the same material to be plated as used in the example, without performing the roughening treatment, using the same process as in the example. The test conditions are shown in Table 1 below together with the test conditions of Example 1, Example 2, and Example 3.
比較例では、得られたニッケルめっき被膜に密着不良が観察されたため、膨れの評価は×とした。従って、ニッケルめっき皮膜のＣＦＲＰへの密着強度は、測定しなかった。上記評価結果を、実施例１及び実施例２の結果と併せて、以下の表２に示す。また、上記にてニッケルめっきを施したＣＦＲＰの外観写真を、図１３に示す。 In the comparative example, since poor adhesion was observed in the obtained nickel plating film, the evaluation of swelling was x. Therefore, the adhesion strength of the nickel plating film to CFRP was not measured. The evaluation results are shown in Table 2 below together with the results of Example 1 and Example 2. Moreover, the external appearance photograph of CFRP which gave nickel plating in the above is shown in FIG.
外形加工を施す等して部分的に炭素繊維が露出したＣＦＲＰに、本件発明に係るＣＦＲＰからの炭素繊維の脱落防止方法を用いて金属皮膜を形成すると、炭素繊維の脱落が無くなる。また、厚い金属皮膜を形成し、この金属皮膜に切削加工等を施せば、加工品の寸法精度は更に向上する。即ち、軽量でありながら、金属の加工品と同等の強度と寸法精度と外観とを備えるＣＦＲＰを得ることが出来る。また、反射鏡等所定の形状に成型して外形加工等を施した後、ニッケルめっき皮膜を形成して露出した炭素繊維の脱落を防止し、めっき表面を機械加工して鏡面に仕上げれば、液晶表示装置のバックパネル等、光の反射を制御する用途に使用できる。更に、露光装置の光源等に用いる大型の反射鏡とすれば、軽量故に操作性が良好であり、繰り返しの移動操作を行う場合には、移動速度を速くしても位置合わせ精度に優れたものとなる。また、全面に金属皮膜を備えるＣＦＲＰは、屋外で使用してもマトリックス樹脂が直接紫外線の照射を受けることが無く、マトリックス樹脂の劣化が抑制される。従って、屋外でも長期間の使用に耐えることが出来る。 If a metal film is formed on the CFRP in which the carbon fiber is partially exposed by performing external processing or the like using the method for preventing the carbon fiber from falling off from the CFRP according to the present invention, the carbon fiber does not fall off. Further, if a thick metal film is formed and the metal film is subjected to cutting or the like, the dimensional accuracy of the processed product is further improved. That is, a CFRP having a strength, dimensional accuracy, and appearance equivalent to those of a metal processed product can be obtained while being lightweight. Also, after shaping the reflector into a predetermined shape and performing external processing etc., forming a nickel plating film to prevent the exposed carbon fibers from falling off, and machining the plating surface to finish it into a mirror surface, It can be used for controlling the reflection of light, such as a back panel of a liquid crystal display device. Furthermore, if it is a large reflector used as a light source for an exposure apparatus, it is lightweight and has excellent operability. When performing repeated movement operations, it has excellent alignment accuracy even if the movement speed is increased. It becomes. In addition, CFRP having a metal film on the entire surface prevents the matrix resin from being directly irradiated with ultraviolet rays even when used outdoors, thereby suppressing deterioration of the matrix resin. Therefore, it can withstand long-term use even outdoors.
１ ＣＦＲＰ
２ 炭素繊維
３ マトリックス樹脂
４ ＣＦＲＰの加工予定面
５ ＣＦＲＰの加工端面
６ 樹脂皮膜
７ 金属皮膜
1 CFRP
2 Carbon fiber 3 Matrix resin 4 CFRP processing surface 5 CFRP processing end surface 6 Resin film 7 Metal film
Claims (6)
当該炭素繊維強化プラスチック表面に以下の工程Ａ及び工程Ｂを経て金属皮膜を形成することで炭素繊維の脱落を防止することを特徴とする炭素繊維強化プラスチックからの炭素繊維の脱落防止方法。
工程Ａ：炭素繊維強化プラスチックの表面を、過マンガン酸処理、又は、当該過マンガン酸処理と物理的表面処理及び／又は紫外線照射処理を用いて表面処理をし、炭素繊維強化プラスチックの表面を粗化する粗化処理工程。
工程Ｂ：工程Ａで得られた炭素繊維強化プラスチックの表面に無電解めっき法を用いて金属皮膜を形成する無電解めっき工程。 In the method for preventing the carbon fiber from falling off from the carbon fiber reinforced plastic having the exposed portion of the carbon fiber,
A method for preventing carbon fibers from falling off from a carbon fiber reinforced plastic, comprising forming a metal film on the surface of the carbon fiber reinforced plastic through the following steps A and B to prevent the carbon fibers from falling off.
Process A: The surface of carbon fiber reinforced plastic is roughened by permanganic acid treatment or surface treatment using the permanganic acid treatment and physical surface treatment and / or ultraviolet irradiation treatment. Roughening treatment step.
Process B: An electroless plating process in which a metal film is formed on the surface of the carbon fiber reinforced plastic obtained in Process A using an electroless plating method.
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| JPH05286057A (en) * | 1992-04-16 | 1993-11-02 | Sumitomo Chem Co Ltd | Plated roll of fiber-reinforced resin and manufacture thereof |
| JPH06264250A (en) * | 1993-03-10 | 1994-09-20 | Toray Ind Inc | Production of carbon fiber reinforced plastic molded body with metallized surface, and carbon fiber reinforced plastic molded body with metallized surface |
| JPH08246164A (en) * | 1995-03-08 | 1996-09-24 | Toyota Motor Corp | Metal-based composite material and its production |
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2007
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