JP4999072B2 - Surface coating material - Google Patents
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- JP4999072B2 JP4999072B2 JP2007074931A JP2007074931A JP4999072B2 JP 4999072 B2 JP4999072 B2 JP 4999072B2 JP 2007074931 A JP2007074931 A JP 2007074931A JP 2007074931 A JP2007074931 A JP 2007074931A JP 4999072 B2 JP4999072 B2 JP 4999072B2
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- 239000000463 material Substances 0.000 title claims description 189
- 239000011248 coating agent Substances 0.000 title claims description 52
- 238000000576 coating method Methods 0.000 title claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 159
- 229910052799 carbon Inorganic materials 0.000 claims description 119
- 229910052751 metal Inorganic materials 0.000 claims description 62
- 239000002184 metal Substances 0.000 claims description 62
- 229910045601 alloy Inorganic materials 0.000 claims description 39
- 239000000956 alloy Substances 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 239000002109 single walled nanotube Substances 0.000 claims description 33
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 31
- 229910003472 fullerene Inorganic materials 0.000 claims description 28
- 239000011159 matrix material Substances 0.000 claims description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 22
- 238000007772 electroless plating Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 47
- 238000011156 evaluation Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000011135 tin Substances 0.000 description 20
- 238000009713 electroplating Methods 0.000 description 13
- 239000002134 carbon nanofiber Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000002116 nanohorn Substances 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 2
- -1 peanut-type Chemical compound 0.000 description 2
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002072 nanorope Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
本発明は、電気・電子部品等の接点部品、コネクター部品等に有用な導電性、潤滑性、耐摩耗性、及び耐食性に優れる、電気・電子部品の接点部品又はコネクター部品用表面被覆材に関する。 The present invention, the contact parts such as electric and electronic parts, useful conductive to the connector parts, etc., lubricity, wear resistance, and excellent corrosion resistance, relates to the contact component or connector parts for the surface covering material for electric and electronic parts .
従来から、導電性を必要とするコネクター用途に金属からなるめっきをコーティングした構成部品を使うことは知られている。このようなコネクター用途には耐摩耗性が必要とされる。耐摩耗性を向上するために、耐摩耗性を有する粒子として剛性率が高い粒子を複合すると、複合コネクター表面の硬度を向上させることができるが、その反面金属と該粒子との界面でウィスカーが発生するという問題を生ずる。
ウィスカーが発生する金属としてＳｎ、Ｚｎ、Ｃｄ、Ｆｅ、Ａｇ等の金属が知られており、その成長にも潜伏期間があり、最も発生し易く成長速度の大きいものがＳｎである。
Conventionally, it is known to use metal-plated components for connector applications that require electrical conductivity. Wear resistance is required for such connector applications. In order to improve the wear resistance, if the particles having high rigidity are combined as the particles having wear resistance, the hardness of the composite connector surface can be improved. On the other hand, whiskers are formed at the interface between the metal and the particles. This causes a problem that occurs.
Metals such as Sn, Zn, Cd, Fe, and Ag are known as metals that generate whiskers. Their growth has a latent period, and Sn is the most easily generated and has a high growth rate.
一方、金属マトリックス中にカーボンナノファイバー等の炭素構造材料を配合して複合化し、種々の特性を改良する試みがなされている。
特許文献１には、コーティング層が金属マトリックス中に分布された電気伝導性を有する粒子、潤滑性を有する粒子、磨耗耐性を有する粒子および温度耐久性を増加させる性質を有する粒子を組み合わせた電気コネクターまたは電気スイッチ素子が開示されている。
特許文献２には、カーボンナノファイバーの含量や複合体の大きさをコントロール可能で、量産に向く金属・カーボンナノファイバー複合体およびその製造方法を提供することを目的として、溶融状態の金属にカーボンナノファイバーが混入され、該複合物が粒子化され、かつ固化されて成る金属・カーボンナノファイバー複合体が開示されている。
特許文献３には、金属にカーボンナノ材料を複合する複合めっきにおいて、表面を平滑に仕上げることのできる複合めっき技術を提供することを目的として、硫酸ニッケルと塩化ニッケルを主成分とするワット浴に、光沢剤と、ポリアクリル酸と、カーボンナノファイバーとを混合して複合めっき液を調製し、このめっき液に金属材料を投入し、電解めっき処理を施すことで、ニッケルに繊維状カーボンナノ材料を複合させた複合めっき層からなる繊維状ナノカーボン・金属複合材料が開示されている。
On the other hand, attempts have been made to improve various properties by compounding a carbon matrix material such as carbon nanofiber into a metal matrix.
Patent document 1 discloses an electrical connector in which a coating layer is a combination of particles having electrical conductivity distributed in a metal matrix, particles having lubricity, particles having wear resistance, and particles having a property of increasing temperature durability. Or an electrical switch element is disclosed.
In Patent Document 2, the content of carbon nanofibers and the size of the composite can be controlled, and in order to provide a metal / carbon nanofiber composite suitable for mass production and a method for producing the composite, carbon in the molten state is used. A metal / carbon nanofiber composite is disclosed in which nanofibers are mixed, and the composite is made into particles and solidified.
Patent Document 3 discloses a watt bath mainly composed of nickel sulfate and nickel chloride for the purpose of providing a composite plating technique capable of finishing the surface smoothly in composite plating in which a carbon nanomaterial is combined with a metal. A composite plating solution is prepared by mixing brighteners, polyacrylic acid, and carbon nanofibers. A metal material is added to the plating solution, and electrolytic plating treatment is performed. There has been disclosed a fibrous nanocarbon / metal composite material comprising a composite plating layer in which is combined.
特許文献１において、前記潤滑性を有する粒子として、ＰＴＦＥ、ポリイミド及びポリアミド、炭素含有粒子、本質的に純粋な炭素およびグラファイト、セラミック粒子、二硫化モリブデン及び窒化ホウ素、並びに潤滑手段含有カプセル、例えばポリフェニルエーテル又は有機潤滑手段を含有するカプセルが例示されている。前記磨耗耐性を有する粒子として、セラミック粒子、例えば酸化アルミニウム、酸化ジルコニウム、炭化珪素、窒化ホウ素および窒化チタン、並びに炭素質ナノチューブが例示されている。しかしながら、実施例において磨耗耐性等を有する粒子として評価されているのはすべてグラファイトのみである。
特許文献２において、金属と微細炭素繊維とでは比重が大きく異なることやカーボンナノファイバーが溶融湯金属に濡れ難いという性質があることから、微細炭素繊維を均一に溶融金属中に分散する技術が開示されているが、炭素材としてカーボンナノファイバーのみが対象とされている。
特許文献３において、金属にカーボンナノ材料を複合化して表面を平滑に仕上げることのできる複合めっき技術が開示されているが、カーボンナノ材料として繊維状ナノカーボンが開示されているのみである。
従って、潤滑性、耐摩耗性と耐食性を向上して、ウィスカーの発生を抑制する電気・電子部品の接点部品又はコネクター部品用表面被覆材を提供することを目的とする。
In Patent Document 1, as the particles having lubricity, PTFE, polyimide and polyamide, carbon-containing particles, essentially pure carbon and graphite, ceramic particles, molybdenum disulfide and boron nitride, and lubricating means-containing capsules such as poly Capsules containing phenyl ether or organic lubricating means are illustrated. Examples of the wear-resistant particles include ceramic particles such as aluminum oxide, zirconium oxide, silicon carbide, boron nitride and titanium nitride, and carbonaceous nanotubes. However, in the examples, only graphite is evaluated as particles having wear resistance and the like.
Patent Document 2 discloses a technique for uniformly dispersing fine carbon fibers in molten metal because the specific gravity is greatly different between metal and fine carbon fiber and carbon nanofibers are difficult to wet with molten metal. However, only carbon nanofibers are targeted as carbon materials.
Patent Document 3 discloses a composite plating technique capable of compounding a carbon nanomaterial with a metal to finish the surface smoothly, but only fibrous nanocarbon is disclosed as a carbon nanomaterial.
Accordingly, it is an object of the present invention to provide a surface coating material for contact parts or connector parts of electrical / electronic parts that improves lubricity, wear resistance and corrosion resistance and suppresses the occurrence of whiskers .
本発明者らは、上記従来技術に鑑みて、低い剛性率を有する炭素構造材料を表面被覆材に含有させることにより、該炭素構造材料がコネクター等の接点で弾性変形することで潤滑性・耐摩耗性を同時に向上させ、さらにめっき金属内部で発生する内部応力に対して弾性限界が大きい粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで、表面被覆材の耐食性を向上させ、ウィスカー発生を抑制すること等を見出し、本発明を完成するに至った。 In view of the above prior art, the present inventors include a carbon structural material having a low rigidity in the surface coating material, so that the carbon structural material is elastically deformed at a contact point such as a connector so that the lubricity and At the same time, the wear resistance is improved, and the particles with a large elastic limit against the internal stress generated inside the plated metal are deformed. As a result, the inventors have found that the generation of whiskers is suppressed, and the present invention has been completed.
すなわち、本発明は、（１）少なくとも単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が
Ｎｉ、又はＳｎの金属のマトリックス相中に、
該炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合で分散している表面被覆材であって、
電気・電子部品の接点部品又はコネクター部品用表面被覆材、に関する発明である（以下、第１の態様ということがある）。
（２）また、本発明は、少なくとも単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が
Ｎｉ、又はＳｎの合金で、Ｎｉ、Ｓｎのいずれかを１種のみを含み、さらに、前記Ｎｉ，Ｓｎのいずれか１種以外に、その他の元素としてＮｉ，Ｓｎ，Ｃｒ，Ａｕ，Ａｇ、Ｃｕ，Ｐｔ，Ｐｄ，Ｉｎ，Ｂｉ、及びＺｎから選択される１種以上を含む合金からなるマトリックス相中に、
該炭素構造材料１〜３０体積％、及び該合金７０〜９９体積％の割合で分散している表面被覆材であって、
電気・電子部品の接点部品又はコネクター部品用表面被覆材である（以下、第２の態様ということがある）。
また、本発明の第１の態様、及び第２の態様の表面被覆材においては、下記（３）ないし（８）の態様とすることが可能である。
（３）前記炭素構造材料が単層カーボンナノチューブ及び／又はフラーレンで、最大粒径が６ｎｍ以上から８０ｎｍ以下で、アスペクト比が１以上で１０００以下の範囲にあることを特徴とする、前記（１）または（２）に記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
（４）前記炭素構造材料が表面被覆材の最表面層に面積割合で少なくとも５％以上存在していることを特徴とする、前記（１）から（３）のいずれかに記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
（５）前記炭素構造材料が、アミノ基、ヒドロキシル基、メトキシ基、アミド基、及びメチル基から選択される１種または２種以上の官能基で修飾されていることを特徴とする、前記（１）から（４）のいずれかに記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
That is, the present invention is (1) one or more carbon structural materials selected from at least single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and the rigidity is in the range of 0.01 to 0.6 TPa. Carbon structural material
In the matrix phase of the metal of Ni or Sn ,
A surface covering material dispersed in a proportion of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the metal ,
It is an invention relating to a surface coating material for contact parts or connector parts of electrical / electronic parts (hereinafter, sometimes referred to as a first aspect) .
(2) In addition, the present invention is at least one carbon structural material selected from single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and has a rigidity in the range of 0.01 to 0.6 TPa. Carbon structural material
An alloy of Ni or Sn, which contains only one of Ni and Sn, and in addition to any one of Ni and Sn, Ni, Sn, Cr, Au, Ag, Cu as other elements In a matrix phase made of an alloy containing one or more selected from Pt, Pt, Pd, In, Bi, and Zn,
A surface covering material dispersed in a proportion of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the alloy,
It is a surface covering material for contact parts or connector parts of electrical / electronic parts (hereinafter sometimes referred to as a second aspect).
Moreover, in the surface coating material of the 1st aspect of this invention and a 2nd aspect, it is possible to set it as the aspect of following (3) thru | or ( 8 ).
( 3 ) The carbon structural material is a single-walled carbon nanotube and / or fullerene, having a maximum particle size of 6 nm to 80 nm and an aspect ratio of 1 to 1000 , ) or contact component or connector parts for the surface covering material for electric and electronic component according to (2).
( 4 ) The electric / electronic device according to any one of (1) to (3), wherein the carbon structural material is present in the outermost surface layer of the surface coating material in an area ratio of at least 5% or more. Surface covering material for contact parts or connector parts of parts .
( 5 ) The carbon structural material is modified with one or more functional groups selected from an amino group, a hydroxyl group, a methoxy group, an amide group, and a methyl group, The surface covering material for contact parts or connector parts of electrical / electronic parts according to any one of 1) to (4) .
（６）前記炭素構造材料をめっき液中に添加して撹拌下に電解めっきを行うことにより得られた、前記炭素構造材料が前記金属又は合金マトリックス相中に分散している、前記（１）から（５）のいずれかに記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
（７）前記炭素構造材料をめっき液中に添加して撹拌下に無電解めっきを行うことにより得られた、前記炭素構造材料が金属又は合金マトリックス相中に分散している、前記（１）から（５）のいずれかに記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
（８）前記炭素構造材料と、金属又は合金粉末からなる混合粉末を焼結させることにより得られた、前記炭素構造材料が金属又は合金マトリックス相中に分散している、前記（１）から（５）のいずれかに記載の電気・電子部品の接点部品又はコネクター部品用表面被覆材。
(6) the carbon structure material was obtained by performing the electroless plating with stirring was added to the plating solution, wherein the carbon structure material is dispersed in the metal or alloy matrix phase, wherein (1) To (5) A surface covering material for contact parts or connector parts of electrical / electronic parts .
(7) wherein the carbon structure material was obtained by performing the electroless plating with stirring was added to the plating solution, wherein the carbon structure material is dispersed in the metal or alloy matrix phase, wherein (1) To (5) A surface covering material for contact parts or connector parts of electrical / electronic parts .
( 8 ) From the above (1), wherein the carbon structural material obtained by sintering a mixed powder comprising the carbon structural material and a metal or alloy powder is dispersed in a metal or alloy matrix phase ( 5) A surface covering material for contact parts or connector parts of electrical / electronic parts .
本発明の少なくとも単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が金属又は合金マトリックス中に分散している、電気・電子部品の接点部品又はコネクター部品用表面被覆材は、接点で弾性変形することで潤滑性と耐摩耗性が向上し、また表面被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制すると共に導電性にも優れた特性を有する。 One or more carbon structural materials selected from at least single-walled carbon nanotubes, carbon nanohorns, and fullerenes according to the present invention , wherein the carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa is a metal or The surface coating material for contact parts or connector parts of electrical and electronic parts dispersed in the alloy matrix is improved in lubricity and wear resistance by elastic deformation at the contact points, and occurs inside the surface coating metal. By deforming particles made of a carbon structural material that has a large elastic limit against internal stress, the surface coating material is improved in corrosion resistance by suppressing the internal strain of the plated metal, and whisker generation is further suppressed. In addition, it has excellent electrical conductivity.
〔１〕第１、２の態様の表面被覆材
本発明の第１の態様の表面被覆材は、なくとも単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料がＮｉ、又はＳｎの金属のマトリックス相中に、該炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合で分散している表面被覆材であって、電気・電子部品の接点部品又はコネクター部品用表面被覆材である。
また、発明の第２の態様の表面被覆材は、少なくとも単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料がＮｉ、又はＳｎの合金で、Ｎｉ、Ｓｎのいずれかを１種のみを含み、さらに、前記Ｎｉ，Ｓｎのいずれか１種以外に、その他の元素としてＮｉ，Ｓｎ，Ｃｒ，Ａｕ，Ａｇ、Ｃｕ，Ｐｔ，Ｐｄ，Ｉｎ，Ｂｉ、及びＺｎから選択される１種以上を含む合金からなるマトリックス相中に、
該炭素構造材料１〜３０体積％、及び該合金７０〜９９体積％の割合で分散している表面被覆材であって、電気・電子部品の接点部品又はコネクター部品用表面被覆材である。
（１）炭素構造材料の種類
炭素構造材料としては、一般に単層カーボンナノチューブ（以下、ＳＷＣＮＴということがある。）、多層カーボンナノチューブ、カーボンナノホーン、フラーレン、フラーレン重合物、フラーレン誘導体、カーボンナノファイバー、活性炭素等が挙げられるが、本発明で使用する炭素構造材料は、これらの中でも単層カーボンナノチューブ、カーボンナノホーン、カーボンナノファイバー、フラーレン、フラーレン重合物、及びフラーレン誘導体である。
（ｉ）カーボンナノチューブ
カーボンナノチューブとは、グラファイトの１枚面を巻いた筒状形状を有するものをいい、１層に巻かれたものを単層カーボンナノチューブ、２層に巻かれたものを２層カーボンナノチューブ、多層に巻かれたものを多層カーボンナノチューブという。
[1] Surface coating material according to first and second aspects The surface coating material according to the first aspect of the present invention is at least one or more carbons selected from single-walled carbon nanotubes, carbon nanohorns, and fullerenes. In the structural material, the carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa is in a matrix phase of Ni or Sn metal , 1 to 30% by volume of the carbon structural material, and 70 to 99 of the metal. It is a surface coating material dispersed at a volume percentage, and is a surface coating material for contact parts or connector parts of electrical / electronic parts .
The surface covering material of the second aspect of the invention is one or more carbon structural materials selected from at least single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and has a rigidity of 0.01 to 0.00. The carbon structural material in the range of 6 TPa is an alloy of Ni or Sn, including only one of Ni and Sn, and in addition to any one of Ni and Sn, other elements such as Ni, In a matrix phase made of an alloy containing one or more selected from Sn, Cr, Au, Ag, Cu, Pt, Pd, In, Bi, and Zn,
The surface covering material is dispersed at a ratio of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the alloy, and is a surface covering material for contact parts or connector parts of electrical / electronic parts.
(1) Types of carbon structural materials Carbon structural materials are generally single-walled carbon nanotubes (hereinafter sometimes referred to as SWCNTs), multi-walled carbon nanotubes, carbon nanohorns, fullerenes, fullerene polymers, fullerene derivatives, carbon nanofibers, Examples of the carbon structural material used in the present invention include single-walled carbon nanotubes, carbon nanohorns, carbon nanofibers, fullerenes, fullerene polymers, and fullerene derivatives.
(I) Carbon nanotubes Carbon nanotubes have a cylindrical shape in which one sheet of graphite is wound. Single-walled carbon nanotubes are wound in one layer, and two layers are wound in two layers. Carbon nanotubes and those wound in multiple layers are called multi-walled carbon nanotubes.
（ii）カーボンナノホーン
カーボンナノホーンとはグラファイトの１枚面が円錐状に巻かれた形状を有しており、１層に巻かれたものを単層カーボンナノホーンといい、２層に巻かれたものを２層カーボンナノホーンといい、３層以上の多層に巻かれたものを多層カーボンナノホーンという。
（iii）フラーレン
フラーレンとは炭素原子からなるクラスターで、炭素の同素体であり、通常はＣ３６、Ｃ６０、Ｃ７０、Ｃ７６、Ｃ７８、Ｃ８０、Ｃ８２、Ｃ８４などから選ばれる。フラーレン重合物とは、２個のＣ６０が結合して出来た二量体や、さらに密に結合した落花生型などのＣ１２０、３個が結合したトリマーのＣ１８０やｎ個が結合したポリマーなども合成されている。
フラーレン誘導体とは前記フラーレンが官能基化修飾されたものであれば特に限定しないが、本発明では−ＯＨ、−ＯＳＯ３Ｈ、−ＣＯＯＨ、−ＳＯ３Ｈ、−ＯＰＯ（ＯＨ）３の官能基の内、少なくとも１つ以上含むものが好ましい。
(Ii) Carbon nanohorn A carbon nanohorn has a shape in which one surface of graphite is wound in a conical shape, and one wound in one layer is called a single-layer carbon nanohorn and is wound in two layers. Is called a two-layer carbon nanohorn, and a multi-layered carbon nanohorn is a multi-layer carbon nanohorn.
(Iii) Fullerene Fullerene is a cluster composed of carbon atoms and is an allotrope of carbon, and is usually selected from C 36 , C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 and the like. Fullerene polymer The two dimers or the C 60 was able to bond, further tightly bound C 120, such as peanut-type, three are C 180 and n-number of trimers bound is bonded polymer Etc. are also synthesized.
The fullerene derivative is not particularly limited as long as the fullerene is functionally modified, but in the present invention, functional groups of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO (OH) 3 are used. Of these, those containing at least one are preferred.
（２）炭素構造材料の剛性率
本発明で使用する炭素構造材料は、少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料である。剛性率が０．０１未満では、潤滑性と耐摩耗性及び耐食性の向上が不十分であり、剛性率が０．６を超えると金属の内部応力に対して変形できなくなるという不都合を生ずる。好ましい剛性率は、０．３０〜０．５５ＴＰａの範囲である。
このような炭素構造材料を使用することにより、潤滑性と耐摩耗性が向上すると共に、被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制し、導電性にも優れた特性を有する。
（ｉ）炭素構造材料の剛性率の測定法
本発明における剛性率は、参考文献１（Wong E W, Sheehan P E and Lieber C M 1997 Science 277 1971）に記載された下式から算出される剛性率Ｇである。具体的には、剛性率Ｇは、各種炭素構造材料のヤング率を測定し、ポアソン比を０．２として下式から算出される。
Ｇ＝Ｅ／［２（１＋γ）］
Ｅ:ヤング率、
γ:ポアソン比（下記参考文献２から、上式におけるポアソン比はすべて０．２と推定した。）
＊参考文献２：VOLUME 79, NUMBER 7 PHYSICALREVIEW LETTERS 18 AUGUST 1997
Elastic Properties of Carbon Nanotubes and Nanoropes Jian Ping Lu
(2) Stiffness of carbon structural material The carbon structural material used in the present invention is a carbon structural material having a rigidity of at least 0.01 to 0.6 TPa. If the rigidity is less than 0.01, improvement in lubricity, wear resistance and corrosion resistance is insufficient, and if the rigidity exceeds 0.6, there is a disadvantage that the metal cannot be deformed by internal stress. A preferable rigidity is in the range of 0.30 to 0.55 TPa.
By using such a carbon structural material, lubricity and wear resistance are improved, and particles made of a carbon structural material having a large elastic limit against internal stress generated inside the coating metal are deformed. The surface coating material is improved in corrosion resistance by influencing the plated metal such as internal strain relaxation, whisker generation is suppressed, and the conductivity is excellent.
(I) Method of measuring rigidity of carbon structural material The rigidity in the present invention is the rigidity G calculated from the following equation described in Reference Document 1 (Wong EW, Sheehan PE and Lieber CM 1997 Science 277 1971). is there. Specifically, the rigidity G is calculated from the following equation by measuring the Young's modulus of various carbon structural materials and setting the Poisson's ratio to 0.2.
G = E / [2 (1 + γ)]
E: Young's modulus
γ: Poisson ratio (From Reference Document 2 below, all Poisson ratios in the above equation were estimated to be 0.2)
* Reference 2: VOLUME 79, NUMBER 7 PHYSICALREVIEW LETTERS 18 AUGUST 1997
Elastic Properties of Carbon Nanotubes and Nanoropes Jian Ping Lu
（ii）炭素構造材料の剛性率
本発明で使用する炭素構造材料のうち単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンの剛性率を表１に示す。尚、これらの測定に使用した炭素構造材料を以下に示す。
（ｉ）フラーレン
フロンティアカーボン（株）製、商品名：フラーレンＣ６０−ＳＵＨ
（ii）カーボンナノホーン
ＮＥＣ（株）製、カーボンナノホーン
（iii）単層カーボンナノチューブ、
Sun Nanotech Co Ltd製、商品名：SUNNANO（SWNT）
（iv）２ないし１０層の多層カーボンナノチューブ
Sun Nanotech Co Ltd製、商品名：SUNNANO（B-MWNT）
（ｖ）気相成長炭素繊維
昭和電工（株）製、商品名：ＶＧＣＦ
（vi）活性炭素
米国スーペリア・グラファイト社製、商品名：ＣＧＣ鱗片状黒鉛Ｎｏ２９３５
(Ii) Rigidity of carbon structural material Table 1 shows the rigidity of single-walled carbon nanotubes, carbon nanohorns, and fullerenes among the carbon structural materials used in the present invention. The carbon structural materials used for these measurements are shown below.
(I) Fullerene Frontier Carbon Co., Ltd., trade name: Fullerene C60-SUH
(Ii) carbon nanohorn manufactured by NEC Corporation, carbon nanohorn (iii) single-walled carbon nanotube,
Product name: SUNNANO (SWNT), manufactured by Sun Nanotech Co Ltd
(Iv) 2 to 10 multi-walled carbon nanotubes
Product name: SUNNANO (B-MWNT), manufactured by Sun Nanotech Co Ltd
(V) Vapor growth carbon fiber, Showa Denko Co., Ltd., trade name: VGCF
(Vi) Activated carbon, manufactured by US Superior Graphite Co., Ltd., trade name: CGC scale-like graphite No2935
（３）炭素構造材料の形状
本発明で使用する炭素構造材料の最大粒径が６ｎｍ以上から８０ｎｍ以下で、アスペクト比が１以上で１０００以下が好ましい。
炭素構造材料のアスペクト比が１０００を超えると長すぎて絡まり分散性が悪くなる場合がある。炭素構造材料のアスペクト比は、より好ましくは１〜１００であり、特に好ましくは１〜１０である。
また、炭素構造材料の最大長さが１０ｎｍ以上の炭素構造材料を５０質量％含むことが望ましい。炭素構造材料の最大長さが１０ｎｍ以上の炭素構造材料を５０質量％含むことにより表面での炭素構造材料の脱落がより効果的に防止される。このような、アスペクト比、と炭素構造材料の長さは、走査電子顕微鏡（ＳＥＭ）を用いて測定することが可能である。
尚、後述するように最大粒径も走査電子顕微鏡（ＳＥＭ）を用いて測定する。
(3) Shape of carbon structural material The carbon structural material used in the present invention preferably has a maximum particle size of 6 nm to 80 nm and an aspect ratio of 1 to 1000 .
If the aspect ratio of the carbon structural material exceeds 1000 , the carbon structure material may be too long and entangled, resulting in poor dispersibility. The aspect ratio of the carbon structural material is more preferably 1 to 100, and particularly preferably 1 to 10.
In addition, it is desirable that the carbon structural material includes 50% by mass of a carbon structural material having a maximum length of 10 nm or more. By including 50% by mass of the carbon structural material having a maximum length of 10 nm or more, the carbon structural material is more effectively prevented from falling off at the surface. Such an aspect ratio and the length of the carbon structural material can be measured using a scanning electron microscope (SEM).
As will be described later, the maximum particle size is also measured using a scanning electron microscope (SEM) .
（４）炭素構造材料の官能基による修飾
炭素構造材料は、アミノ基、ヒドロキシル基、メトキシ基、アミド基、及びメチル基から選択される１種以上の官能基で修飾されていることが望ましい。
炭素構造材料をこのような官能基で修飾することにより、炭素構造材料をめっき液中に添加して、撹拌下に電解めっき又は無電解めっきにより基材上に前記炭素構造材料を金属又は合金マトリックス中に分散させて表面被覆材を形成する際に、炭素構造材料が金属又は合金への親和性を増加させて、マトリックス中への分散をより容易にする。
炭素構造材料へのこのような修飾方法は下記方法により行うことができる。
尚、炭素構造材料このような官能基を付与するタイミングは、電解めっき又は無電解めっきを行う直前が望ましい。
（ｉ）ヒドロキシル基
プラズマ処理、又は酸化剤等の反応試薬により形成できる。
（ii）アミノ基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成した後、SOCl2を用いてヒドロキシル基を塩素に置換する。さらにこの塩素部分をアンモニアを用いてアミノ基に置換する。
（iii）メトキシ基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成し、塩基の存在下、ヒドロキシル基にヨードメタンや硫酸ジメチルなどのメチル化剤を反応させてメトキシ基を形成する。
（iv）アミド基
大気中において、４００℃ないし５４０℃で熱処理によりカルボキシル基を形成し、SOCl2でカルボキシル基のヒドロキシル基を塩素に置換する。さらにアンモニアを用いてこの塩素部分をアミノ基に置換することにより、アミド基を形成する。
（ｖ）メチル基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成し、メタノールと酸触媒下で反応させてメチル基を形成する。
(4) Modification of carbon structural material with functional group The carbon structural material is desirably modified with one or more functional groups selected from an amino group, a hydroxyl group, a methoxy group, an amide group, and a methyl group.
By modifying the carbon structural material with such a functional group, the carbon structural material is added to the plating solution, and the carbon structural material is placed on the substrate by electrolytic plating or electroless plating under stirring. When dispersed in to form a surface coating, the carbon structural material increases the affinity for the metal or alloy, making it easier to disperse into the matrix.
Such a modification method to the carbon structural material can be performed by the following method.
It is desirable that the carbon structural material be provided with such a functional group immediately before electrolytic plating or electroless plating.
(I) Hydroxyl group It can be formed by a plasma treatment or a reaction reagent such as an oxidizing agent.
(Ii) amino group plasma treatment, or after the formation of the hydroxyl groups by reaction reagents such as oxidizing agents, to replace the hydroxyl group to chlorine using SOCl 2. Furthermore, this chlorine part is substituted with an amino group using ammonia.
(Iii) Methoxy group A hydroxyl group is formed by a plasma treatment or a reaction reagent such as an oxidizing agent, and in the presence of a base, a methylating agent such as iodomethane or dimethyl sulfate is reacted with the hydroxyl group to form a methoxy group.
(Iv) Amide group A carboxyl group is formed by heat treatment at 400 ° C. to 540 ° C. in the atmosphere, and the hydroxyl group of the carboxyl group is replaced with chlorine with SOCl 2 . Furthermore, an amide group is formed by substituting this chlorine part with an amino group using ammonia.
(V) Methyl group A hydroxyl group is formed by a plasma treatment or a reaction reagent such as an oxidizing agent, and reacted with methanol under an acid catalyst to form a methyl group.
〔２〕金属又は合金
本発明の表面被覆材のマトリックスを構成する金属又は合金に使用可能である金属として、第１の態様の金属は、Ｎｉ、又はＳｎであり
第２の態様の金属は、Ｎｉ、又はＳｎの合金で、Ｎｉ、Ｓｎのいずれかを１種のみを含み、さらに、前記Ｎｉ，Ｓｎのいずれか１種以外に、その他の元素としてＮｉ，Ｓｎ，Ｃｒ，Ａｕ，Ａｇ、Ｃｕ，Ｐｔ，Ｐｄ，Ｉｎ，Ｂｉ、及びＺｎから選択される１種以上を含む合金が挙げられる。
すなわち、電気・電子部品等の接点部品は常温下で接触抵抗が低いことは勿論のこと、自動車用の電気・電子部品等の接点部品に使用されるものについては、良好な耐熱性を有していると共に高温下でも接触抵抗を低く維持できることが要求される。また、コネクター部品に使用される表面被覆材については、コネクター部品を接続するときの負荷、すなわち挿入力が低減する材料であることが望まれている。そして、接点部品を構成する表面被覆材については、一般的に長期的な安定性を有することが望まれている。
このような観点からも上記例示した金属又は合金が使用できる。
[2] Metal or alloy As the metal that can be used for the metal or alloy constituting the matrix of the surface coating material of the present invention, the metal of the first aspect is Ni or Sn.
The metal of the second aspect is an alloy of Ni or Sn, and includes only one of Ni and Sn, and, in addition to any one of Ni and Sn, Ni, Sn as other elements , Cr, Au, Ag, Cu, Pt, Pd, In, Bi, and an alloy containing at least one selected from Zn .
That is, contact parts such as electric / electronic parts have low contact resistance at room temperature, and those used for contact parts such as electric / electronic parts for automobiles have good heat resistance. In addition, the contact resistance is required to be kept low even at high temperatures. Further, it is desired that the surface covering material used for the connector part is a material that reduces a load when the connector part is connected, that is, an insertion force. And it is generally desired for the surface covering material constituting the contact parts to have long-term stability.
Such exemplified above metal or alloy from the viewpoint can be used.
〔３〕表面被覆材
（１）表面被覆材の形成
本発明の表面被覆材は、電解めっき法、無電解めっき法、焼結法等により炭素構造材料を金属又は合金マトリックス中へ分散させることにより形成されるがこれらの具体的方法については後述する。
[3] Surface coating material (1) Formation of surface coating material The surface coating material of the present invention is obtained by dispersing a carbon structural material in a metal or alloy matrix by an electrolytic plating method, an electroless plating method, a sintering method, or the like. Although formed, these specific methods will be described later.
（２）表面被覆材中の前記炭素構造材料と、金属又は合金の体積割合
本発明の表面被覆材は、それぞれ炭素構造材料が１〜３０体積％、及び金属又は合金が７０〜９９体積％からなる。
このような体積割合とすることにより、表面被覆材が接点で適度に弾性変形して潤滑性と耐摩耗性が向上し、また表面被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制する。
上記体積割合の表面被覆材は、例えば電解めっき浴もしくは無電解めっき浴の溶液中の金属と炭素構造材料の配合割合を該体積割合とすればよく、また焼結法により表面被覆材を形成するときはそれぞれの粒子の配合割合を前記体積割合とすればよい。
(2) Volume ratio of the carbon structural material and metal or alloy in the surface coating material The surface coating material of the present invention comprises 1 to 30% by volume of carbon structural material and 70 to 99% by volume of metal or alloy, respectively. Become.
By setting such a volume ratio, the surface coating material is appropriately elastically deformed at the contact point to improve lubricity and wear resistance, and the elastic limit is large against internal stress generated inside the surface coating metal. The deformation of the particles made of the carbon structural material improves the corrosion resistance of the surface coating material by affecting the plated metal such as internal strain relaxation, and further suppresses the occurrence of whiskers.
The above-mentioned volume ratio of the surface coating material may be, for example, the mixing ratio of the metal and the carbon structural material in the solution of the electrolytic plating bath or the electroless plating bath, and the surface coating material is formed by a sintering method. In some cases, the mixing ratio of each particle may be the volume ratio.
（３）表面被覆材の最表面層における炭素構造材料の面積割合
炭素構造材料は、表面被覆材の最表面層に面積割合で少なくとも５％以上存在していることが望ましい。
このような割合とすることにより、表面被覆材において上記した潤滑性、耐摩耗性、耐食性、及びウィスカー発生の抑制効果が効果的に発揮される。より好ましい表面被覆材の最表面層における炭素構造材料の面積割合は５ないし１０％である。
尚、上記表面被覆材の最表面層における炭素構造材料の面積割合はめっき又は粉末焼結を行う際の金属（金属イオンの状態で存在する）と炭素構造材料の配合割合から推定可能である。すなわち、該炭素構造材料の面積割合は、電解めっきと無電解めっきを行う場合には浴中の金属もしくは合金と炭素構造材料の配合割合、又は粉末焼結を行う場合には金属もしくは合金粉末と炭素構造材料粉末の配合割合（体積ベース）の２／３乗を目安に推定することが可能である。
尚、このような面積割合であることの確認は、走査電子顕微鏡（ＳＥＭ）を用いて確認することが可能である。
(3) Area ratio of carbon structural material in outermost surface layer of surface covering material It is desirable that the carbon structural material is present in the outermost surface layer of the surface covering material in an area ratio of at least 5% or more.
By setting it as such a ratio, the above-mentioned lubricity, wear resistance, corrosion resistance, and whisker generation suppressing effect are effectively exhibited in the surface coating material. The area ratio of the carbon structural material in the outermost surface layer of the surface covering material is more preferably 5 to 10%.
In addition, the area ratio of the carbon structural material in the outermost surface layer of the surface covering material can be estimated from the blending ratio of the metal (present in the state of metal ions) and the carbon structural material when performing plating or powder sintering. That is, the area ratio of the carbon structural material is the blending ratio of the metal or alloy in the bath and the carbon structural material when performing electroplating and electroless plating, or the metal or alloy powder when performing powder sintering. It is possible to estimate using the 2/3 power of the mixing ratio (volume basis) of the carbon structural material powder as a guide.
In addition, confirmation of such an area ratio can be confirmed using a scanning electron microscope (SEM).
〔４〕電解めっきにより形成される表面被覆材
電解めっきにより形成される表面被覆材は、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料を炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合になるようにめっき液中に添加して、撹拌下に電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散して形成される。
具体例としては、めっき浴中にめっき液を調製すると共に、上記した所定量の炭素構造材料を金属又は合金マトリックス中分散させて撹拌下に、アノードとカソードである基材間に印加してめっきを行うことにより、炭素構造材料が金属又は合金マトリックス中に分散している、表面被覆材を形成することができる。めっき液に炭素構造材料を含む以外は公知の電解めっき方法を採用してめっきを行うことができる。
〔５〕無電解めっきにより形成される表面被覆材
無電解めっきにより形成される表面被覆材は、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料を炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合になるようにめっき液中に添加して、撹拌下に無電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散して形成される。
具体例としては、無電解めっき浴中に無電解めっき液を調製すると共に、所定量の炭素構造材料を撹拌下に分散させながら、還元剤の存在下に金属イオンを還元して基材上に金属又は合金と共に炭素構造材料をめっきすることにより表面被覆材を形成することができる。めっき液に炭素構造材料を含む以外は公知の無電解めっき方法を採用してめっきを行うことができる。
[4] Surface coating material formed by electrolytic plating
The surface coating material formed by electrolytic plating is one or more carbon structural materials selected from single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and the rigidity is in the range of 0.01 to 0.6 TPa. A certain carbon structural material is added to the plating solution so as to have a ratio of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the metal, and the carbon structural material is formed on the substrate by electrolytic plating with stirring. There is formed by dispersing the metal or alloy matrix.
As a specific example, a plating solution is prepared in a plating bath, and the above-mentioned predetermined amount of carbon structural material is dispersed in a metal or alloy matrix and applied between the anode and cathode substrates while stirring. By performing the above, it is possible to form a surface coating material in which the carbon structural material is dispersed in the metal or alloy matrix. Except for including a carbon structural material in the plating solution, a known electrolytic plating method can be employed for plating.
[5] Surface coating material formed by electroless plating
The surface covering material formed by electroless plating is one or more carbon structural materials selected from single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and has a rigidity of 0.01 to 0.6 TPa. The carbon structural material is added to the plating solution so that the ratio of the carbon structural material is 1 to 30% by volume and the metal is 70 to 99% by volume, and the carbon is formed on the substrate by electroless plating with stirring. A structural material is formed dispersed in a metal or alloy matrix.
As a specific example, while preparing an electroless plating solution in an electroless plating bath and dispersing a predetermined amount of carbon structural material with stirring, metal ions are reduced in the presence of a reducing agent on the substrate. A surface covering material can be formed by plating a carbon structural material together with a metal or an alloy. Except for including a carbon structural material in the plating solution, a known electroless plating method can be employed for plating.
〔６〕末焼結法により形成される表面被覆材
末焼結法により形成される表面被覆材は、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上の炭素構造材料で、剛性率が０．０１ないし０．６ＴＰａの範囲にある炭素構造材料と、金属又は合金粉末からなる混合粉末を炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合になるように焼結させることにより基材上に前記炭素構造材料が金属又は合金間に分散して形成される。上記粉末焼結させる温度条件は、金属又は合金が焼結する温度にまで加熱することにより、金属又は合金が融着現象を生じさせて炭素構造材料に焼結する温度である。
Surface coating material formed by the surface coating material powder sintering method, which is formed by [6] late sintering method, single-walled carbon nanotubes, one or more carbon structure selected from carbon nanohorn, and fullerene The material is a carbon structural material having a modulus of rigidity in the range of 0.01 to 0.6 TPa and a mixed powder composed of metal or alloy powder in a proportion of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the metal the carbon structure material is formed by dispersing between the metal or alloy on a substrate by sintering such that. The temperature condition for the powder sintering is a temperature at which the metal or alloy is heated to a temperature at which the metal or alloy is sintered to cause the metal or alloy to cause a fusing phenomenon and sinter into the carbon structural material.
以下に実施例により本発明をより具体的に説明するが本発明はこれらの方法に限定されるものではない。
本実施例１ないし５に使用した炭素構造材料を以下に示す。
尚、下記の（iv）２ないし１０層の多層カーボンナノチューブ、（ｖ）気相成長炭素繊維、及び（vi）活性炭素は表２〜４中に参考例として示す。
（１）炭素構造材料
（ｉ）フラーレン
フロンティアカーボン（株）製、商品名：フラーレンＣ６０−ＳＵＨ
（ii）カーボンナノホーン
ＮＥＣ（株）製、カーボンナノホーン
（iii）単層カーボンナノチューブ、
Sun Nanotech Co Ltd製、商品名：SUNNANO（SWNT）
（iv）２ないし１０層の多層カーボンナノチューブ
Sun Nanotech Co Ltd製、商品名：SUNNANO（B-MWNT）
（ｖ）気相成長炭素繊維
昭和電工（株）製、商品名：ＶＧＣＦ
（vi）活性炭素
米国スーペリア・グラファイト社製、商品名：ＣＧＣ鱗片状黒鉛Ｎｏ２９３５
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these methods.
The carbon structural materials used in Examples 1 to 5 are shown below.
The following (iv) 2- to 10-layer multi-walled carbon nanotubes, (v) vapor-grown carbon fibers, and (vi) activated carbon are shown in Tables 2 to 4 as reference examples.
(1) Carbon structural material (i) Fullerene Frontier Carbon Co., Ltd., trade name: Fullerene C60-SUH
(Ii) carbon nanohorn manufactured by NEC Corporation, carbon nanohorn (iii) single-walled carbon nanotube,
Product name: SUNNANO (SWNT), manufactured by Sun Nanotech Co Ltd
(Iv) 2 to 10 multi-walled carbon nanotubes
Product name: SUNNANO (B-MWNT), manufactured by Sun Nanotech Co Ltd
(V) Vapor growth carbon fiber, Showa Denko Co., Ltd., trade name: VGCF
(Vi) Activated carbon, manufactured by US Superior Graphite Co., Ltd., trade name: CGC scale-like graphite No2935
（２）炭素構造材料の剛性率とアスペクト比
炭素構造材料の剛性率とアスペクト比を表１に示す。
（ｉ）アスペクト比の測定
アスペクト比と最大粒径は走査電子顕微鏡（ＳＥＭ）を用いてそれぞれの炭素構造材料を１０個ずつ観察し、最大サイズ（又は長さ）と最小サイズ（又は粒径）をそれぞれ測定して、そのそれぞれについて個々にアスペクト比を計算して、その計算値の平均値からアスペクト比を求めた。
（ii）剛性率の測定
参考文献（Wong E W, Sheehan P E and Lieber C M 1997 Science 277 1971）に記載の方法を採用した。先ず各種ナノカーボンのヤング率を測定し、ポアソン比を０．２として下式から剛性率Ｇを算出した。
Ｇ＝Ｅ／［２（１＋γ）］
Ｅ：ヤング率、γ：ポアソン比
(2) Stiffness and aspect ratio of carbon structural material Table 1 shows the rigidity and aspect ratio of carbon structural material.
(I) Measurement of aspect ratio The aspect ratio and the maximum particle size are observed with 10 pieces of each carbon structural material using a scanning electron microscope (SEM), and the maximum size (or length) and the minimum size (or particle size). Were measured , the aspect ratio was calculated individually for each of them, and the aspect ratio was determined from the average of the calculated values .
(Ii) Rigidity measurement The method described in Reference (Wong EW, Sheehan PE and Lieber CM 1997 Science 277 1971) was adopted. First, the Young's modulus of various nanocarbons was measured, and the rigidity G was calculated from the following equation with a Poisson's ratio of 0.2.
G = E / [2 (1 + γ)]
E: Young's modulus, γ: Poisson's ratio
［実施例１］
電解めっきによりニッケルマトリックス中に炭素構造材料が分散している表面被覆剤を調製して、摺動性の評価を行った。
（１）サンプルの調製
ＮｉＳＯ４・６Ｈ２Ｏ、ＮｉＣｌ２・６Ｈ２Ｏ、Ｈ３ＢＯ３をそれぞれ１：０．２：０．５の質量割合で溶解されているＮｉめっき浴１リットル（Ｌ）中に、表２に示す割合の炭素構造材料を分散させ、攪拌しながら、２０℃、５３ＲＨで２Ａ／ｄｍ２の電流密度で通電して接点材にめっきを行った。
（２）評価方法
動摩擦係数の測定
バウデン型摩擦試験器を用い、荷重２９４ｍＮ、摺動距離１０ｍｍ、摺動速度１００Ｍ／ｍｉｎ、摺動回数１回の条件下で測定。なお、相手材としては、板厚０．２５ｍｍの黄銅条にリフローＳｎめっきを１μｍ施したのち、０．５ｍｍＲに張り出し加工を行ったものを用いた。
（３）評価結果
評価結果をまとめて表２に示す。
表２から、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆材中の体積割合が１〜３０体積％において、ブランクと比較して動摩擦係数が低下しており、摺動性の向上が確認された。
[Example 1]
A surface coating agent in which a carbon structural material was dispersed in a nickel matrix was prepared by electrolytic plating , and slidability was evaluated.
(1) Preparation of sample 1 liter of Ni plating bath in which NiSO 4 · 6H 2 O, NiCl 2 · 6H 2 O, and H 3 BO 3 are dissolved at a mass ratio of 1: 0.2: 0.5 (L ), The carbon structural material in the ratio shown in Table 2 was dispersed, and while stirring, the contact material was plated by energizing at 20 ° C. and 53 RH at a current density of 2 A / dm 2 .
(2) Evaluation Method Measurement of Dynamic Friction Coefficient Using a Bowden friction tester, measurement was performed under the conditions of a load of 294 mN, a sliding distance of 10 mm, a sliding speed of 100 M / min, and a sliding frequency of once. In addition, as a counterpart material, a brass strip having a thickness of 0.25 mm was subjected to reflow Sn plating of 1 μm and then subjected to an overhanging process to 0.5 mmR.
(3) Evaluation results Table 2 summarizes the evaluation results.
From Table 2, with respect to single-walled carbon nanotubes, carbon nanohorns, and fullerenes, the volume fraction in the surface coating material is 1 to 30% by volume, and the dynamic friction coefficient is lower than that of the blank, and the slidability is improved. confirmed.
［実施例２］
電解めっきによりニッケルマトリックス中に炭素構造材料が分散している表面被覆剤を調製して耐食性の評価をフェロキシル試験に基づいて行った。
（１）サンプルの調製
実施例１に記載したと同様の方法で評価用のサンプルを調製した。
（２）評価方法
フェロキシル試験は、JIS H B617付属書３の規定に準じて行った。
すなわち、試験紙をフェロシアン化カリウム、フェリシアン化カリウム及び塩化ナトリウムの混合液に浸し、めっき面にはり付けて、めっき面のピンホール発生の有無を観察した。
（３）評価結果
評価結果をまとめて表３に示す。
尚、表中ピンホールが確認されない場合は○、ピンホールが確認された場合は×印で表示した。
表３から、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆材中の体積割合１ないし３０体積％の場合に、ブランクと比較して耐食性が向上することが確認された。
[Example 2]
A surface coating agent in which a carbon structural material is dispersed in a nickel matrix was prepared by electrolytic plating, and corrosion resistance was evaluated based on a ferroxyl test.
(1) Preparation of sample A sample for evaluation was prepared in the same manner as described in Example 1.
(2) Evaluation method The ferroxyl test was conducted according to the provisions of JIS H B617 Annex 3.
That is, the test paper was immersed in a mixed solution of potassium ferrocyanide, potassium ferricyanide, and sodium chloride and adhered to the plated surface, and the presence or absence of pinholes on the plated surface was observed.
(3) Evaluation results Table 3 summarizes the evaluation results.
In the table, the case where no pinhole was confirmed was indicated by ○, and the case where a pinhole was confirmed was indicated by ×.
From Table 3, it was confirmed that the single-walled carbon nanotubes, carbon nanohorns, and fullerenes have improved corrosion resistance as compared with the blank when the volume ratio in the surface coating material is 1 to 30% by volume.
［実施例３］
電解めっきによりスズマトリックス中に炭素構造材料が分散している表面被覆剤を調製して、ウィスカーの成長評価試験を行った。
（１）サンプルの調製
Ｈ２ＳＯ４・６Ｈ２Ｏ、ＳｎＳＯ４・６Ｈ２Ｏが１：１の質量割合で溶解されているＳｎめっき浴１Ｌ中に表４に示す配合割合の炭素構造材料を分散させ、攪拌しながら、２０℃、相対湿度５２％の条件下で接点材へ２Ａ／ｄｍ２の電流密度で通電してめっきを行った。
（２）評価方法
短絡を引き起こすウィスカーの成長し易さを調べた。すなわち、上記で調製したサンプルを温度５０℃のエアバス内に１ヶ月放置した後、ウィスカーの発生の有無を顕微鏡観察により調べた。
（３）評価結果
評価結果をまとめて表４に示す。
表４から、単層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆剤中の体積割合１ないし３０体積％において、ウィスカーの発生が観察されなかった。
[Example 3]
A surface coating agent in which a carbon structural material is dispersed in a tin matrix was prepared by electrolytic plating, and a whisker growth evaluation test was performed.
(1) Preparation of sample Carbon structural materials having the blending ratios shown in Table 4 in 1 L of Sn plating bath in which H 2 SO 4 .6H 2 O and SnSO 4 .6H 2 O are dissolved at a mass ratio of 1: 1 are prepared. While being dispersed and stirred, the contact material was plated at a current density of 2 A / dm 2 under conditions of 20 ° C. and a relative humidity of 52%.
(2) Evaluation method The ease of growth of whiskers that cause a short circuit was investigated. That is, after the sample prepared above was left in an air bath at a temperature of 50 ° C. for one month, the presence or absence of whisker generation was examined by microscopic observation.
(3) Evaluation results Table 4 summarizes the evaluation results.
From Table 4, with respect to single-walled carbon nanotubes, carbon nanohorns, and fullerenes, no occurrence of whiskers was observed at a volume ratio of 1 to 30% by volume in the surface coating agent.
[実施例４、比較例１]
無電解めっきによりニッケルマトリックス中にＳＷＣＮＴが分散している表面被覆材を調製して、摺動性、腐食性、及びウィスカーの成長評価試験を行った。
（１）サンプルの調製
実施例４として、下記組成のＳＷＣＮＴ１０体積％含む無電解ニッケルめっき液を常法に従って調製した。また、比較例１としてＳＷＣＮＴのみを含まない下記組成のめっき液を調製した。
ＳＷＣＮＴ以外に無電解ニッケルめっき液は、硫酸ニッケル７水和物２５ｇ／Ｌ、次亜リン酸ナトリウム一水和物２０ｇ／Ｌ、ＤＬ−リンゴ酸２５ｇ／Ｌ、乳酸１０ｇ／Ｌ、酢酸５ｇ／Ｌ、安定化剤としてモリブデン５０ｍｇ／Ｌ及びビスマス０．５ｍｇ／Ｌを含む水溶液である。
被めっき試験片として、ＳＰＣＣ−ＳＢの鉄板（サイズ：０．３ｍｍ×５０ｍｍ×５０ｍｍ）を用い、上記各無電解ニッケルめっき液１Ｌ中に、下記めっき条件のもとで浸漬し、無電解ニッケルめっきを行った。
めっき液のｐＨ：４．９、浴温：９０℃、撹拌：空気撹拌、めっき時間：２０分間
（２）評価方法
得られた無電解ニッケルめっき表面被覆材について、摺動性、腐食性、及びウィスカーの発生を評価した。尚、摺動性は前記実施例１、腐食性は前記実施例２、ウィスカー発生の評価は前記実施例３にそれぞれ記載した方法と同じである。
（３）評価結果
評価結果をまとめて表５に示す。表５からＳＷＣＮＴ１０体積％含む表面被覆剤は、摺動性、腐食性、及びウィスカー発生の抑制に優れていることが確認できた。
[Example 4, Comparative Example 1]
A surface coating material in which SWCNT is dispersed in a nickel matrix was prepared by electroless plating, and slidability, corrosivity, and whisker growth evaluation tests were performed.
(1) Preparation of Sample As Example 4, an electroless nickel plating solution containing 10% by volume of SWCNT having the following composition was prepared according to a conventional method. Moreover, the plating solution of the following composition which does not contain only SWCNT as the comparative example 1 was prepared.
In addition to SWCNT, electroless nickel plating solution is nickel sulfate heptahydrate 25 g / L, sodium hypophosphite monohydrate 20 g / L, DL-malic acid 25 g / L, lactic acid 10 g / L, acetic acid 5 g / L An aqueous solution containing 50 mg / L molybdenum and 0.5 mg / L bismuth as a stabilizer.
An SPCC-SB steel plate (size: 0.3 mm x 50 mm x 50 mm) was used as the test piece to be plated, and immersed in 1 L of the above electroless nickel plating solution under the following plating conditions. Went.
PH of plating solution: 4.9, bath temperature: 90 ° C., stirring: air stirring, plating time: 20 minutes (2) Evaluation method About the obtained electroless nickel plating surface coating material, slidability, corrosivity, and The occurrence of whiskers was evaluated. Note that the slidability is the same as the method described in Example 1, the corrosivity is the same as in Example 2, and the evaluation of whisker generation is the same as that described in Example 3.
(3) Evaluation results Table 5 summarizes the evaluation results. From Table 5, it was confirmed that the surface coating agent containing 10% by volume of SWCNT was excellent in slidability, corrosivity, and suppression of whisker generation.
[実施例５、比較例２]
焼結によりニッケル粒子間にＳＷＣＮＴを分散させた表面被覆材を調製して、摺動性、腐食性、及びウィスカーの成長評価試験を行った。
（１）サンプルの調製
（ｉ）無電解還元による焼結用ニッケル粒子の調製
下記組成で、含む無電解ニッケルめっき液を常法に従って調製した。
無電解ニッケルめっき液は、硫酸ニッケル７水和物 ２５ｇ／Ｌ、次亜リン酸ナトリウム一水和物 ２０ｇ／Ｌ、ＤＬ−リンゴ酸 ２５ｇ／Ｌ、乳酸 １０ｇ／Ｌ、酢酸 ５ｇ／Ｌ、安定化剤としてモリブデン５０ｍｇ／Ｌ及びビスマス０．２ｍｇ／Ｌからなる水溶液である。上記各無電解ニッケルめっき浴１Ｌ中で、下記めっき条件のもとで無電解還元によるニッケル粒子を作製した。
めっき液のｐＨ：４．９、浴温：９０℃、撹拌：空気撹拌、めっき時間：２０分間
（ii）ニッケル粒子とＳＷＣＮＴとの焼結
得られたＮｉ粒子とＳＷＣＮＴを体積比９０：１０の割合で混合したものを、ＳＰＣＣ−ＳＢの鉄板（サイズ：０．３ｍｍ×５０ｍｍ×５０ｍｍ）の上部に乗せ、Ａｒガス雰囲気中１０００℃で熱処理を行い、Ｎｉ／ＳＷＣＮＴからなる表面被覆材を形成した。また比較例２としてＳＷＣＮＴを含まないＮｉ粒子のみを同条件で熱処理、焼結して上記と同じＳＰＣＣ−ＳＢの鉄板上に表面被覆材を形成した。
（２）評価方法
得られた表面被覆材について、摺動性、腐食性、及びウィスカー発生を評価した。尚、摺動性は実施例１、腐食性は実施例２、ウィスカー発生の評価は実施例３にそれぞれ記載した方法と同じである。
[Example 5, Comparative Example 2]
A surface coating material in which SWCNTs were dispersed between nickel particles was prepared by sintering, and slidability, corrosiveness, and whisker growth evaluation tests were performed.
(1) Preparation of sample (i) Preparation of nickel particles for sintering by electroless reduction An electroless nickel plating solution containing the following composition was prepared according to a conventional method.
Electroless nickel plating solution is nickel sulfate heptahydrate 25 g / L, sodium hypophosphite monohydrate 20 g / L, DL-malic acid 25 g / L, lactic acid 10 g / L, acetic acid 5 g / L, stabilized It is an aqueous solution consisting of molybdenum 50 mg / L and bismuth 0.2 mg / L as an agent. In each electroless nickel plating bath 1L, nickel particles were produced by electroless reduction under the following plating conditions.
PH of the plating solution: 4.9, bath temperature: 90 ° C., stirring: air stirring, plating time: 20 minutes (ii) Sintering of nickel particles and SWCNT The obtained Ni particles and SWCNT were in a volume ratio of 90:10 What was mixed at a ratio was placed on top of an SPCC-SB iron plate (size: 0.3 mm × 50 mm × 50 mm) and heat treated at 1000 ° C. in an Ar gas atmosphere to form a surface coating material made of Ni / SWCNT. . In Comparative Example 2, only Ni particles not containing SWCNTs were heat-treated and sintered under the same conditions to form a surface coating material on the same SPCC-SB iron plate as described above.
(2) Evaluation method About the obtained surface coating material, sliding property, corrosivity, and whisker generation | occurrence | production were evaluated. Note that the slidability is the same as the method described in Example 1, the corrosiveness is Example 2, and the evaluation of whisker generation is the same as the method described in Example 3.
（３）評価結果
評価結果をまとめて表６に示す。表６からＳＷＣＮＴ１０体積％含む表面被覆材は、摺動性、腐食性、及びウィスカー発生の抑制等に優れていることが確認できた。
(3) Evaluation results Table 6 summarizes the evaluation results. From Table 6, it was confirmed that the surface covering material containing 10% by volume of SWCNT was excellent in slidability, corrosivity, suppression of whisker generation, and the like.
Claims (8)
Ｎｉ、又はＳｎの金属のマトリックス相中に、
該炭素構造材料１〜３０体積％、及び該金属７０〜９９体積％の割合で分散している表面被覆材であって、
電気・電子部品の接点部品又はコネクター部品用表面被覆材。 One or more carbon structural materials selected from at least single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and a carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa.
In the matrix phase of the metal of Ni or Sn ,
A surface covering material dispersed in a proportion of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the metal ,
Surface coating material for contact parts or connector parts of electrical / electronic parts .
Ｎｉ、又はＳｎの合金で、Ｎｉ、Ｓｎのいずれかを１種のみを含み、さらに、前記Ｎｉ，Ｓｎのいずれか１種以外に、その他の元素としてＮｉ，Ｓｎ，Ｃｒ，Ａｕ，Ａｇ、Ｃｕ，Ｐｔ，Ｐｄ，Ｉｎ，Ｂｉ、及びＺｎから選択される１種以上を含む合金からなるマトリックス相中に、
該炭素構造材料１〜３０体積％、及び該合金７０〜９９体積％の割合で分散している表面被覆材であって、
電気・電子部品の接点部品又はコネクター部品用表面被覆材。 One or more carbon structural materials selected from at least single-walled carbon nanotubes, carbon nanohorns, and fullerenes, and a carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa.
An alloy of Ni or Sn, which contains only one of Ni and Sn, and in addition to any one of Ni and Sn, Ni, Sn, Cr, Au, Ag, Cu as other elements In a matrix phase made of an alloy containing one or more selected from Pt, Pt, Pd, In, Bi, and Zn,
A surface covering material dispersed in a proportion of 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of the alloy,
Surface coating material for contact parts or connector parts of electrical / electronic parts.
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