JP5918537B2 - Manufacturing method of surface-treated steel sheet - Google Patents
Manufacturing method of surface-treated steel sheet Download PDFInfo
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- JP5918537B2 JP5918537B2 JP2011541799A JP2011541799A JP5918537B2 JP 5918537 B2 JP5918537 B2 JP 5918537B2 JP 2011541799 A JP2011541799 A JP 2011541799A JP 2011541799 A JP2011541799 A JP 2011541799A JP 5918537 B2 JP5918537 B2 JP 5918537B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 41
- 239000010959 steel Substances 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000007747 plating Methods 0.000 claims description 99
- 239000013078 crystal Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 45
- 239000011701 zinc Substances 0.000 description 44
- 229910052725 zinc Inorganic materials 0.000 description 44
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000010960 cold rolled steel Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 description 9
- 229960001763 zinc sulfate Drugs 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- -1 cyanide salt Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/10—Bearings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、５μｍを超えるウィスカの発生を抑制できる表面処理鋼板及びその表面処理鋼板を用いたカバー部材に関する。 The present invention relates to a surface-treated steel sheet capable of suppressing the generation of whiskers exceeding 5 μm and a cover member using the surface-treated steel sheet.
近年、ノートパソコン、携帯電話、カーナビゲーションなどに代表される電子機器製品は、小型化、高機能化の一途をたどっており、これに伴い電子機器の要となるプリント基板の配線も微細化・高集約化により、その配線幅や配線間隔が狭小となる一方である。例えば、２０１３年には最小８μｍになるとの報告もある「高木清；プリント配線板における表面処理の技術動向，表面技術，Ｖｏｌ．５９，ｐ．５７０（２００８）」。
これらのプリント基板や電子回路を組み込んだ電子機器製品においては、半導体や回路から発する電磁波の外部への漏れや隣接回路への漏れを遮断し、かつ、外部や隣接回路から発せられる電磁波の影響を受けないように、カバー部材、すなわち金属製のケースやカバー、フレーム、シート等が、回路、半導体、機構部品等の全体を覆うようにして用いられている。
上述のカバー部材には、洋白などの銅合金や表面処理鋼板等が多用されている。しかしながら、銅合金はその存在量が少ないため非常に高価であり、汎用性を求められる民生の電子機器製品での利用には向いていないため、表面処理鋼板が多用されることが多い。
表面処理鋼板としては、一般に、ぶりき（錫めっき鋼板）や錫合金めっき鋼板、亜鉛めっき鋼板等が広く用いられている。
亜鉛めっき鋼板は、ぶりきや錫合金めっき鋼板に比べ耐食性が高いため、金属ケース内の配置される電子部品の寿命が向上するという点、家電の一般的な使用温度条件下ではウィスカが発生しにくいという点、などが他の表面処理鋼板に比べて有利である。In recent years, electronic devices such as notebook PCs, mobile phones, car navigation systems, etc., have been steadily downsized and enhanced in functionality. With the high concentration, the wiring width and the wiring interval are becoming narrower. For example, there is a report that the minimum value will be 8 μm in 2013 “Kiyoshi Takagi; Surface treatment technology trends in printed wiring boards, surface technology, Vol. 59, p. 570 (2008)”.
In electronic equipment products incorporating these printed circuit boards and electronic circuits, the leakage of electromagnetic waves emitted from semiconductors and circuits to the outside and to adjacent circuits is blocked, and the effects of electromagnetic waves emitted from the outside and adjacent circuits are suppressed. A cover member, that is, a metal case or cover, a frame, a sheet, or the like is used so as to cover the entire circuit, semiconductor, mechanical component, or the like so as not to receive it.
For the above-described cover member, a copper alloy such as white or white, a surface-treated steel plate, and the like are frequently used. However, copper alloys are very expensive because of their small abundance, and are not suitable for use in consumer electronic products that require versatility, so surface-treated steel sheets are often used.
As surface-treated steel sheets, tinplate (tin-plated steel sheets), tin alloy-plated steel sheets, galvanized steel sheets, and the like are generally widely used.
Galvanized steel sheets have higher corrosion resistance than tinplate and tin alloy-plated steel sheets, which improves the life of electronic components placed in metal cases, and whiskers are generated under the general operating temperature conditions of home appliances. This is advantageous compared to other surface-treated steel sheets.
しかし、従来の亜鉛めっき鋼板を加工した製品、および亜鉛めっきされた製品は高温下において経時変化により、髭状のウィスカが発生しやすいという問題を有している。
このウィスカについては、耐食性目的の分野ではほとんど問題にならないが、電子機器、コンピュータ機器等の分野では、髭状のウィスカが亜鉛皮膜から脱落して浮遊し、回路中や端子間で、相手の部品と短絡してノイズや絶縁不良の原因になっており、電子機器の小型化やコンピュータ機器のコンタミネイション対策の観点から問題視されている。
特に、車両に組み込まれる電子機器のプリント配線基板などのカバー部材にウィスカが発生すると、振動によりウィスカが落下する機会が増えるため、その対策が求められていた。
本来、表面処理鋼板上にウィスカが発生しないことが望ましいことではあるが、ウィスカはその発生原因が種々様々であり一様でないことから、皆無にすることは事実上難しい状況にあり、できる限り抑制する方法が模索されている。
亜鉛ウィスカは、７５℃以上の雰囲気下にて急激に発生と成長が加速される傾向にあるが、逆にぶりきがウィスカを生じやすいとされる７５℃未満の雰囲気では発生ならびに成長しにくい。このため、一般的な家電の使用条件では、７５℃以上の高温下に曝される機会は皆無と言ってよいことから、表面処理鋼板の電子機器内部の部品への適用に当たっては、耐ウィスカ性の観点からのみみた場合、ぶりきよりも亜鉛めっき鋼板の使用が望ましい。However, a product obtained by processing a conventional galvanized steel sheet and a product that has been galvanized have a problem that wrinkle-like whiskers are likely to occur due to changes over time at high temperatures.
This whisker is hardly a problem in the field of corrosion resistance, but in the field of electronic equipment, computer equipment, etc., the bowl-shaped whisker falls off the zinc film and floats, and the other part in the circuit or between terminals It is a cause of noise and insulation failure due to short circuit, and is regarded as a problem from the viewpoint of miniaturization of electronic equipment and countermeasures against contamination of computer equipment.
In particular, when a whisker is generated in a cover member such as a printed wiring board of an electronic device incorporated in a vehicle, an opportunity for the whisker to drop due to vibration is increased.
Originally, it is desirable that whiskers do not occur on the surface-treated steel sheet. However, whiskers have various causes and are not uniform. How to do is being sought.
Zinc whiskers tend to be rapidly generated and grown under an atmosphere of 75 ° C. or higher, but conversely, generation and growth are difficult in an atmosphere of less than 75 ° C. where tin whisker is likely to cause whiskers. For this reason, it can be said that there is no opportunity to be exposed to a high temperature of 75 ° C. or higher under the general usage conditions of home appliances. From the viewpoint of the above, it is preferable to use a galvanized steel sheet rather than tinplate.
しかし、カーナビゲーションなどの車載で用いられる電子機器製品については、車の内部が密閉空間となることから、内部温度が６０℃を優に超え、亜鉛ウィスカの発生と成長が促進される温度雰囲気下にあることから、亜鉛めっき製品においても例外なく発生しやすいことが知られており、亜鉛めっき品の耐ウィスカ性を確認する方法として、１００℃雰囲気下に亜鉛めっき品を長時間さらすことが提案されている。 However, for electronic equipment products used in vehicles such as car navigation systems, the interior of the car is a sealed space, so the internal temperature is well above 60 ° C, and the temperature and atmosphere of zinc whisker generation and growth are promoted. Therefore, it is known that galvanized products are likely to occur without exception, and as a method for confirming the whisker resistance of galvanized products, it is proposed to expose galvanized products to a 100 ° C atmosphere for a long time. Has been.
なお、ここでいうウィスカとは、JEITA ET-7410「電気・電子部品のウィスカ確認試験方法」のウィスカに関する記述に準拠して述べている。
また、亜鉛と錫のウィスカの発生のしやすい温度が異なる点については、文献「山本正和; 錫ウィスカ成長プロセスの解明と対策 (R＆Dプランニング, 2006)」」に記載されている。
また、ウィスカは、加工時の応力、光沢剤等の種々の要因が相俟って発生するものと考えられ、数週間経過して発生する場合や、数年たってから発生する場合もある。The whisker here is described in accordance with the description about whiskers in JEITA ET-7410 “Whisker Confirmation Test Method for Electric and Electronic Components”.
Also, the difference in the temperature at which zinc and tin whiskers are likely to occur is described in the document “Yamamoto Masakazu; Elucidation and Countermeasures for Tin Whisker Growth Process (R & D Planning, 2006)”.
In addition, whiskers are considered to occur due to various factors such as stress during processing and brightener, and may occur after several weeks or after several years.
亜鉛ウィスカの防止法に関する先行技術としては、
・亜鉛めっき後に不活性ガス、還元性ガス等で熱処理する、
・めっき皮膜中の内部応力を低く押える光沢剤を使用する、
などの方法があり、特許文献１、特許文献２には、使用するシアン浴（アルカリ）の組成を限定すること、めっき皮膜中に共析するＣ量、めっき皮膜の歪みの量を規定することによりウィスカの発生を抑制できることが記載されている。特許文献３には、無機系光沢剤を使用することによってシアン浴（アルカリ）におけるウィスカ発生をなくすことができる旨が記載されている。特許文献４、特許文献５には、ウィスカを抑制する方法として、シアン浴（アルカリ）からの亜鉛めっき作製時に逆電流を周期的に流しながら行うことが記載されている。As prior art regarding the prevention method of zinc whiskers,
・ After galvanization, heat treatment with inert gas, reducing gas, etc.
・ Use a brightening agent that keeps the internal stress in the plating film low.
In Patent Document 1 and Patent Document 2, the composition of the cyan bath (alkali) to be used is limited, the amount of C that is co-deposited in the plating film, and the amount of distortion of the plating film. Describes that the generation of whiskers can be suppressed. Patent Document 3 describes that whisker generation in a cyan bath (alkali) can be eliminated by using an inorganic brightener. Patent Documents 4 and 5 describe, as a method for suppressing whiskers, performing a reverse current periodically while producing zinc plating from a cyan bath (alkali).
しかしながらこれらの先行技術では小型化の進む電子機器のカバー部材やプリント配線基板のカバー部材といった用途を想定しておらず、そのため、ウィスカの発生を防止するとの記載はあっても、数μｍのウィスカが発生しないことは明らかになっていない。また、ウィスカの発生に関して結晶配向性の制御に着目した技術もない。
そこで、本発明は、亜鉛皮膜の結晶配向性を制御することで５μｍを超えるウィスカの発生を抑制できる亜鉛皮膜を有する表面処理鋼板、その表面処理鋼板を用いて加工形成された電子機器及びプリント配線基板のカバー部材を提供することを課題とする。However, these prior arts do not assume uses such as a cover member of an electronic device whose size is being reduced and a cover member of a printed wiring board. It is not clear that this will not occur. In addition, there is no technique that focuses on controlling crystal orientation with respect to whisker generation.
Accordingly, the present invention provides a surface-treated steel sheet having a zinc film that can suppress the generation of whiskers exceeding 5 μm by controlling the crystal orientation of the zinc film, an electronic device and a printed wiring formed by using the surface-treated steel sheet It is an object to provide a cover member for a substrate.
（１）本発明の電子機器またはプリント配線基板のカバー部材用表面処理鋼板の製造方法は、鋼板上にめっき電流密度５Ａ／ｄｍ２〜４０Ａ／ｄｍ２で亜鉛めっきを施し、（０００２）面の結晶配向性指数が２．５〜５．３である亜鉛めっき皮膜を形成し、前記亜鉛めっきを施すめっき浴には有機系光沢剤が添加されず、前記めっき浴の浴温が３０〜６０℃に調整され、前記めっき浴のｐＨが０．５〜３．０に調整され、且つ、前記めっき浴は、ＺｎＳＯ ４ ・７Ｈ ２ ０が１５０〜３００ｇ／Ｌ、Ｎａ ２ ＳＯ ４ が２０〜１００ｇ／Ｌ、およびＨ ２ ＳＯ ４ が５〜７０ｇ／Ｌ含まれる酸性のめっき浴であることを特徴とする。 ( 1 ) The manufacturing method of the surface-treated steel sheet for the cover member of the electronic device or printed wiring board according to the present invention is such that galvanizing is performed on the steel sheet at a plating current density of 5 A / dm 2 to 40 A / dm 2 , A zinc plating film having a crystal orientation index of 2.5 to 5.3 is formed, and an organic brightener is not added to the plating bath to which the zinc plating is applied, and the bath temperature of the plating bath is 30 to 60 ° C. , adjusted to the pH of the plating bath is adjusted to 0.5 to 3.0, and the plating bath, ZnSO 4 · 7H 2 0 is 150~300g / L, Na 2 SO 4 is 20 to 100 g / It is an acidic plating bath containing 5 to 70 g / L of L and H 2 SO 4 .
請求項１に記載の亜鉛皮膜を有する表面処理鋼板は、亜鉛皮膜の（０００２）面の配向性指数を２．５以上とすることで５μｍを超えるウィスカの発生を防止した表面処理鋼板とすることができる。
また、請求項４、５に記載の亜鉛皮膜を有する表面処理鋼板を用いて加工形成された電子機器及びプリント配線基板のカバー部材は、経時変化で発生したウィスカがカバー部材から脱落することにより回路中や端子間で、相手の部品と短絡してノイズや絶縁不良の原因となることがない。特に、車両に組み込まれる電子機器のプリント配線基板などのカバー部材において、振動によるウィスカ落下が原因で発生する故障を減少させることができる。The surface-treated steel sheet having a zinc coating according to claim 1 is a surface-treated steel sheet in which the orientation index of the (0002) plane of the zinc coating is 2.5 or more to prevent the generation of whiskers exceeding 5 μm. Can do.
In addition, the electronic device formed using the surface-treated steel sheet having the zinc coating according to claims 4 and 5 and the cover member of the printed wiring board are configured such that whiskers generated with the passage of time fall off from the cover member. There is no short circuit with the other parts in the middle or between terminals, causing noise or insulation failure. In particular, in a cover member such as a printed wiring board of an electronic device incorporated in a vehicle, it is possible to reduce a failure that occurs due to whisker dropping due to vibration.
以下に、本発明の実施形態につき詳細に説明する。
＜基板＞
本発明に使用される亜鉛皮膜を有する表面処理鋼板は、電子機器、コンピュータ機器などのケースやカバーなどの素材として用いられる表面処理鋼板が挙げられる。表面処理鋼板の基板としては、０．１０〜１．２０ｍｍ程度の厚さの普通鋼冷延鋼板が好ましい。中でも、０．１〜０．５ｍｍ程度の厚さの普通鋼冷延鋼板が好ましい。冷延鋼板の中でも低炭素または極低炭素アルミキルド鋼板が、加工性などの観点から好ましく基板として使用される。Hereinafter, embodiments of the present invention will be described in detail.
<Board>
Examples of the surface-treated steel sheet having a zinc coating used in the present invention include surface-treated steel sheets used as materials for cases and covers of electronic devices and computer devices. As the substrate of the surface-treated steel sheet, a plain steel cold-rolled steel sheet having a thickness of about 0.10 to 1.20 mm is preferable. Among these, a plain steel cold-rolled steel sheet having a thickness of about 0.1 to 0.5 mm is preferable. Among the cold-rolled steel plates, a low carbon or extremely low carbon aluminum killed steel plate is preferably used as a substrate from the viewpoint of workability.
＜表面処理＞
本発明の表面処理鋼板の亜鉛皮膜としては、例えば、基板上に湿式めっき法によって形成される、亜鉛めっきが挙げられる。<Surface treatment>
Examples of the zinc film of the surface-treated steel sheet of the present invention include galvanizing formed on a substrate by a wet plating method.
＜めっき浴＞
亜鉛皮膜を形成させるための一例として基板上に亜鉛めっきを施すが、亜鉛めっきに用いるめっき浴としては、亜鉛イオンの供給源として硫酸塩を用い、これにめっき液の導電性を高めるため硫酸アンモニウム、硫酸ナトリウム、硫酸などの導電補助塩を適宜添加した浴を用いる。
めっき浴の組成の一例として下記のものが挙げられる。
ＺｎＳＯ４・７Ｈ２Ｏ：１５０〜３００ｇ／Ｌ
Ｎａ２ＳＯ４：２０〜１００ｇ／Ｌ
Ｈ２ＳＯ４：５〜７０ｇ／Ｌ
有機系添加剤：０（添加無し）<Plating bath>
As an example for forming a zinc film, zinc plating is performed on a substrate. As a plating bath used for zinc plating, sulfate is used as a source of zinc ions, and ammonium sulfate is used to increase the conductivity of the plating solution. A bath to which a conductive auxiliary salt such as sodium sulfate or sulfuric acid is appropriately added is used.
Examples of the composition of the plating bath include the following.
ZnSO 4 · 7H 2 O: 150 to 300 g / L
Na 2 SO 4: 20~100g / L
H 2 SO 4: 5~70g / L
Organic additive: 0 (no addition)
＜めっき条件＞
上記のめっき浴に、酸またはアルカリを添加して、ｐＨを０．５〜３．０、浴温を３０〜６０℃に調節する。
陽極（アノード）としては、可溶性陽極として亜鉛板を用いるか、不溶性陽極として白金を表面にコーティングしたチタン板などを用いる。
めっき電流密度は５Ａ／ｄｍ２〜２００Ａ／ｄｍ２（直流電解）とする。５Ａ／ｄｍ２未満では亜鉛めっき皮膜が形成しづらく、２００Ａ／ｄｍ２超えると亜鉛めっき皮膜が粉末状となるため外観性に劣り、また密着性も悪くなる。<Plating conditions>
Acid or alkali is added to the above plating bath to adjust the pH to 0.5 to 3.0 and the bath temperature to 30 to 60 ° C.
As the anode (anode), a zinc plate is used as a soluble anode, or a titanium plate with platinum coated on the surface is used as an insoluble anode.
The plating current density is 5 A / dm 2 to 200 A / dm 2 (DC electrolysis). If it is less than 5 A / dm 2, it is difficult to form a galvanized film, and if it exceeds 200 A / dm 2 , the galvanized film becomes powdery, resulting in poor appearance and poor adhesion.
亜鉛めっきにより鋼板上に形成させる亜鉛めっきの皮膜厚みは、０．５〜５．０μｍが好ましい。皮膜厚みが０．５μｍ未満であると耐食性が悪く、また５．０μｍを超える皮膜厚みは電気めっきにより得るには操業性が低下するためコストが大幅に増加する。よって、耐食性とコストのバランスの調整から上記範囲が好ましい。 As for the film thickness of the zinc plating formed on a steel plate by galvanization, 0.5-5.0 micrometers is preferable. When the film thickness is less than 0.5 μm, the corrosion resistance is poor, and when the film thickness exceeds 5.0 μm, the operability is lowered to obtain by electroplating, and the cost is greatly increased. Therefore, the said range is preferable from adjustment of the balance of corrosion resistance and cost.
なお、従来の亜鉛めっき処理においては、めっき浴の攪拌速度、浴温を高めて、めっき時の電流密度を出来る限り高く（たとえば１００Ａ／ｄｍ２以上）することでめっき時間の短縮を図り、生産性を向上させる方法がとられることが一般的であり、めっき皮膜の結晶構造は、めっき浴の種類（硫酸塩、塩化物塩、シアン化塩）、組成（光沢剤などの添加剤の添加）、めっき条件（電流密度、浴温、攪拌速度など）に大きく依存していた。
このような従来技術については、めっき時の電流密度の上昇やめっき浴への添加材の添加によって結晶粒が微細になり、結晶の配向性が全体的に低下する、または（０００２）面の結晶配向性が低下する傾向があり、亜鉛めっき皮膜の配向性と外観（白色度）との関連について、文献「中野博昭、電気亜鉛めっき皮膜の結晶形態制御に関する研究、九州大学博士論文、１９９９」にも記載されているが、めっき皮膜の結晶配向性とウィスカの発生状況についてはなんら触れられていない。
なお、亜鉛皮膜の耐食性をさらに向上させるため、亜鉛皮膜の配向性に影響を与えない範囲で、亜鉛皮膜の下層に、ニッケルもしくは錫を含有する金属層を形成することもできる。In the conventional galvanizing treatment, the plating time is shortened by increasing the stirring speed of the plating bath and the bath temperature to increase the current density during plating as much as possible (for example, 100 A / dm 2 or more). In general, the crystal structure of the plating film depends on the type of plating bath (sulfate, chloride salt, cyanide salt) and composition (addition of additives such as brighteners). , Greatly dependent on plating conditions (current density, bath temperature, stirring speed, etc.).
With respect to such a conventional technique, crystal grains become finer due to an increase in current density during plating or addition of an additive to a plating bath, and the crystal orientation is entirely reduced, or crystals on a (0002) plane The relationship between the orientation of zinc-plated films and the appearance (whiteness) tends to decrease, and the literature "Hiroaki Nakano, Research on Crystal Morphology Control of Electro-galvanized Films, Kyushu University Doctoral Dissertation, 1999" However, no mention is made of the crystal orientation of the plating film and the occurrence of whiskers.
In order to further improve the corrosion resistance of the zinc coating, a metal layer containing nickel or tin can be formed under the zinc coating as long as the orientation of the zinc coating is not affected.
＜結晶配向性の制御＞
亜鉛めっき時の電析過電圧により、亜鉛めっき皮膜の結晶配向性を制御する。ここでいう電析過電圧とは、理論析出電圧と実際の電析時に必要な電圧の差であり、この電析過電圧が低いほど（０００２）面の結晶配向性が高くなる。電析過電圧を低くするためには、電流密度を低くする、攪拌速度を小さくする、浴温を高くする、ｐＨを高くすることが有効である。<Control of crystal orientation>
The crystal orientation of the galvanized film is controlled by the electrodeposition overvoltage during galvanization. The electrodeposition overvoltage here is the difference between the theoretical precipitation voltage and the voltage required during actual electrodeposition. The lower the electrodeposition overvoltage, the higher the crystal orientation of the (0002) plane. In order to reduce the electrodeposition overvoltage, it is effective to reduce the current density, decrease the stirring speed, increase the bath temperature, and increase the pH.
＜保護層＞
本実施形態に係る表面処理鋼板では、めっきのままで使用することも可能であるが、亜鉛皮膜の耐食性，耐酸化性，耐指紋性，耐疵付き性、放熱性などの特性を向上させるために、亜鉛めっきの上に化成処理皮膜や有機樹脂を主体とする皮膜、もしくは無機物を主体とする皮膜などの保護層を形成することも好ましい。
化成処理皮膜としては、例えば電解法や浸積法などを用いて、表面処理鋼板の表面に、クロム量として１〜４０ｍｇ／ｍ２程度のクロム水和酸化物皮膜を付着させることが挙げられる。
また、バナジウム酸、ケイ酸塩、リチウム塩、リン酸塩を主体とする無機系処理液への浸漬または塗布、電解による皮膜形成等が挙げられる。
有機樹脂を主体とする皮膜としては、アクリル系，ポリエステル系，ウレタン系の水系樹脂等が挙げられ、耐食性，潤滑性，耐疵付き性，加工性，溶接性，電着塗装性，塗膜密着性等の品質を向上させるため、必要によりシリカ等の各種酸化物粒子や各種りん酸塩等の無機顔料、ワックス粒子，有機シラン化合物，フッ素樹脂の水分散体塩等を含有させてもよい。
無機物を主体とする皮膜としては、バナジウム酸、ケイ酸塩、リチウム塩、リン酸塩を主体とする無機系処理液への浸漬または塗布、電解による皮膜形成等が挙げられる。<Protective layer>
The surface-treated steel sheet according to the present embodiment can be used as it is, but in order to improve the properties of the zinc film such as corrosion resistance, oxidation resistance, fingerprint resistance, scratch resistance, and heat dissipation. In addition, it is also preferable to form a protective layer such as a chemical conversion treatment film, a film mainly composed of an organic resin, or a film mainly composed of an inorganic substance on the galvanizing.
An example of the chemical conversion treatment film is to deposit a chromium hydrated oxide film having a chromium content of about 1 to 40 mg / m 2 on the surface of the surface-treated steel sheet using, for example, an electrolytic method or a dipping method.
In addition, examples include immersion or coating in an inorganic treatment liquid mainly composed of vanadate, silicate, lithium salt, and phosphate, and film formation by electrolysis.
Films mainly composed of organic resins include acrylic, polyester, and urethane water-based resins. Corrosion resistance, lubricity, scratch resistance, workability, weldability, electrodeposition coating properties, and coating adhesion In order to improve quality such as property, various oxide particles such as silica, inorganic pigments such as various phosphates, wax particles, an organic silane compound, an aqueous dispersion salt of a fluororesin, and the like may be included as necessary.
Examples of the film mainly composed of an inorganic substance include immersion or coating in an inorganic treatment liquid mainly composed of vanadate, silicate, lithium salt and phosphate, and film formation by electrolysis.
＜結晶配向性指数＞
上記の表面処理によって、基板上に亜鉛皮膜が形成され、その亜鉛皮膜の（０００２）面の結晶配向性指数を、２．５以上とすることができる。亜鉛皮膜の結晶配向性指数は、Ｘ線回折装置により各結晶面の回折強度を測定した後、得られた亜鉛皮膜の回折ピークと標準粉末の回折ピークを利用して、
WillsonとRogersの方法「文献K. S. Willson and J. A. Rogers; Tech. Proceeding Amer. Electroplaters Soc., 51, 92 (1964)」にて、以下のようにして算出した。
回折強度のデータとしては、Ｘ線源の管球がＣｕ（Ｋα）の場合、回折角度（２θ）が３０〜１００°の範囲内で出現されるとされる、（０００２）面から（２０２２）面までのものを用いた。
（０００２）面の結晶配向性指数＝ＩＦ（０００２）／ＩＦＲ（０００２）
上記式中、ＩＦ（０００２）は、（０００２）面からのＸ線回折相対強度であり、
ＩＦＲ（０００２）は、配向性のない標準亜鉛（粉末亜鉛）のＸ線回折相対強度（ＪＣＰＤＳカードＮｏ．０４−０８３１記載）である。
ＩＦ（０００２）＝Ｉ（０００２）／［Ｉ（０００２）＋Ｉ（１０１０）＋・・・・＋Ｉ（２０２２）］
ＩＦＲ（０００２）＝ＩＲ（０００２）／［ＩＲ（０００２）＋ＩＲ（１０１０）＋・・・・＋ＩＲ（２０２２）］
上記式中、
Ｉ（ｈｋｉｌ）は、（ｈｋｉｌ）面からのＸ線回折強度であり、
ＩＲ（ｈｋｉｌ）は、標準亜鉛粉末のＪＣＰＤＳカード（Ｎｏ．０４−０８３１）に記載されている（ｈｋｉｌ）面からのＸ線回折強度である。
なお、Ｘ線回折に関しては公知の方法を用いれば良く、線源としてもＣｕＫα線の他、ＣｏＫα線等を使用してもよい<Crystal orientation index>
By the above surface treatment, a zinc film is formed on the substrate, and the crystal orientation index of the (0002) plane of the zinc film can be 2.5 or more. The crystal orientation index of the zinc film is measured using the diffraction peak of the obtained zinc film and the diffraction peak of the standard powder after measuring the diffraction intensity of each crystal plane with an X-ray diffractometer.
The calculation was performed as follows using the method of Willson and Rogers, “Literature KS Willson and JA Rogers; Tech. Proceeding Amer. Electroplaters Soc., 51, 92 (1964)”.
As diffraction intensity data, when the tube of the X-ray source is Cu (Kα), the diffraction angle (2θ) appears to be within the range of 30 to 100 °, from the (0002) plane (2022). The one up to the surface was used.
Crystal orientation index of (0002) plane = IF (0002) / IFR (0002)
In the above formula, IF (0002) is the X-ray diffraction relative intensity from the (0002) plane,
IFR (0002) is an X-ray diffraction relative intensity of standard zinc (powder zinc) having no orientation (described in JCPDS card No. 04-0831).
IF (0002) = I (0002) / [I (0002) + I (1010) +... + I (2022)]
IFR (0002) = IR (0002) / [IR (0002) + IR (1010) +... + IR (2022)]
In the above formula,
I (hkil) is the X-ray diffraction intensity from the (hkil) plane,
IR (hkil) is the X-ray diffraction intensity from the (hkil) plane described in the JCPDS card (No. 04-0831) of standard zinc powder.
Note that a known method may be used for X-ray diffraction, and a CoKα ray or the like may be used as a radiation source in addition to a CuKα ray.
＜ウィスカ発生の観察＞
上記亜鉛皮膜が形成された表面処理鋼板から、幅２ｍｍ×長さ２０ｍｍに切り出し、その中央１０ｍｍのところで９０度曲げしたものを試料として（図１参照）、亜鉛めっきのウィスカ発生が促進されるとされる温度１００℃の雰囲気に保った大気オーブンに投入し、１０００時間後の表面を電子顕微鏡にて観察した。
このウィスカ発生の条件は、「山本正和：錫ウィスカ成長プロセスの解明と対策（Ｒ＆Ｄプランイング、２００６）」の記載によった。
なお、ウィスカの観察方法については、ＪＥＩＴＡ ＥＴ−７４１０に記載の観察方法（走査型電子顕微鏡（ＳＥＭ））を用いた。
上記処理後の試料表面において、長手方向の長さが５μｍを超えるウィスカ発生の有無を確認した。<Observation of whisker generation>
When the surface-treated steel sheet on which the zinc coating is formed is cut into a width of 2 mm and a length of 20 mm and bent 90 degrees at the center of 10 mm (see FIG. 1), the generation of whisker in galvanization is promoted. Then, it was put into an atmospheric oven maintained in an atmosphere at a temperature of 100 ° C., and the surface after 1000 hours was observed with an electron microscope.
The conditions for this whisker generation were as described in “Yamamoto Masakazu: Elucidation of Tin Whisker Growth Process and Countermeasures (R & D Planning, 2006)”.
In addition, about the observation method of a whisker, the observation method (scanning electron microscope (SEM)) as described in JEITA ET-7410 was used.
On the surface of the sample after the above treatment, the presence or absence of whisker generation having a length in the longitudinal direction exceeding 5 μm was confirmed.
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：５Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：２４Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜の結晶配向性指数を、Ｘ線回折装置を用いて、WillsonとRogersの方法を用いて算出した結果、（０００２）面の結晶配向性指数は５．３であった。
さらに、表面処理鋼板から、ウィスカ発生観察用として、幅２ｍｍ×長さ２０ｍｍの試料に切り出し、その中央１０ｍｍのところで９０度曲げを行った後、１００℃の大気オーブンに投入して１０００ｈｒ経時させて、走査型電子顕微鏡（ＳＥＭ）により表面観察を行った。
ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカは認められなかった。On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 5 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath agitation speed (circulation pump liquid feed speed): 24 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of calculating the crystal orientation index of the zinc coating of the obtained surface-treated steel sheet using the method of Willson and Rogers using an X-ray diffractometer, the crystal orientation index of the (0002) plane was 5.3. there were.
Further, for observation of whisker generation from a surface-treated steel plate, a sample having a width of 2 mm and a length of 20 mm was cut out, bent 90 degrees at the center of 10 mm, and then placed in an air oven at 100 ° C. for 1000 hours. The surface was observed with a scanning electron microscope (SEM).
As a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, no whisker having a length in the longitudinal direction exceeding 5 μm was observed.
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：２０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：３６Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は３．６であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカは認められなかった。On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 20 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath stirring speed (circulation pump liquid feed speed): 36 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 3.6.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, no whisker having a length in the longitudinal direction exceeding 5 μm was observed.
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：２０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：４８Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は３．２であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカは認められなかった。On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 20 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath stirring speed (circulation pump liquid feed speed): 48 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 3.2.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, no whisker having a length in the longitudinal direction exceeding 5 μm was observed.
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：４０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：７２Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は２．５であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカは認められなかった（図２参照）。
On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 40 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath agitation speed (circulation pump liquid feed speed): 72 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 2.5.
Moreover, as a result of observing the surface of whisker generation with a scanning electron microscope, no whisker having a length in the longitudinal direction exceeding 5 μm was observed (see FIG. 2).
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、ニッケルめっきを下地めっきとして施した後、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
＜ニッケルめっき条件＞
＜めっき浴＞
硫酸ニッケル ： 200ｇ／Ｌ
塩化ニッケル ： 40ｇ／Ｌ
ホウ酸 ： 40ｇ／Ｌ
＜めっき条件＞
ｐＨ ： ４．０
浴温 ： 40℃
電流密度 ： １０Ａ／ｄｍ２
陽極 ： ニッケル板
ニッケル下地めっき皮膜の厚み：約0.7μｍ（6ｇ／ｍ２）
＜亜鉛めっき条件＞
めっき電流密度：２０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：Ｐｔ蒸着Ｔｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：３６Ｌ／ｍｉｎ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、
（０００２）面の面配向指数は5.2であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカは認められなかった。
［比較例１］On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, nickel plating was applied as a base plating, and then zinc plating was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
<Nickel plating conditions>
<Plating bath>
Nickel sulfate: 200g / L
Nickel chloride: 40 g / L
Boric acid: 40 g / L
<Plating conditions>
pH: 4.0
Bath temperature: 40 ℃
Current density: 10 A / dm 2
Anode: Nickel plate Nickel undercoat thickness: approx. 0.7 μm (6 g / m 2 )
<Zinc plating conditions>
Plating current density: 20 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-deposited Ti plate plating bath stirring speed (circulation pump liquid feed speed): 36 L / min
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1,
The plane orientation index of the (0002) plane was 5.2.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, no whisker having a length in the longitudinal direction exceeding 5 μm was observed.
[Comparative Example 1]
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：１００Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：７２Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は１．９であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカが認められた（図３参照）。
比較例１のめっき条件は、めっき電流密度が高く、ウィスカ発生を促進させた結果、大きなウィスカが形成された。
［比較例２］On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 100 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath agitation speed (circulation pump liquid feed speed): 72 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc coating of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 1.9.
Further, as a result of observing the presence or absence of whisker generation with a scanning electron microscope, whiskers having a length in the longitudinal direction exceeding 5 μm were observed (see FIG. 3).
The plating conditions of Comparative Example 1 were high in plating current density, and as a result of promoting the generation of whiskers, large whiskers were formed.
[Comparative Example 2]
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：１５０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：７２Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：なし
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は１．４であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカが認められた。
比較例２のめっき条件は、めっき電流密度が高く、ウィスカ発生を促進させた結果、大きなウィスカが形成された。
［比較例３］On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 150 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath agitation speed (circulation pump liquid feed speed): 72 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic substance: None Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 1.4.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, whiskers having a length in the longitudinal direction exceeding 5 μm were observed.
The plating conditions of Comparative Example 2 were high in plating current density, and as a result of promoting the generation of whiskers, large whiskers were formed.
[Comparative Example 3]
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：２０Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：３６Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：４ｍｇ／Ｌ
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は０．２であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカが認められた（図４参照）。図５は図４の拡大写真である。
比較例３のめっき条件は、めっき電流密度は低く、めっき浴の撹拌速度も低いが、有機添加剤を使用したため、ウィスカ発生を促進させた結果、大きなウィスカが形成された。
［比較例４］On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 20 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath stirring speed (circulation pump liquid feed speed): 36 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic matter: 4 mg / L
Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 0.2.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, whiskers having a length in the longitudinal direction exceeding 5 μm were observed (see FIG. 4). FIG. 5 is an enlarged photograph of FIG.
As for the plating conditions of Comparative Example 3, the plating current density was low and the stirring rate of the plating bath was low. However, since organic additives were used, the generation of whiskers was promoted, resulting in the formation of large whiskers.
[Comparative Example 4]
定法により脱脂、酸洗を行ったＡｌキルド冷延鋼板上に、硫酸亜鉛を主体とする酸性のめっき浴を用いて以下の条件で亜鉛めっきを施した。
めっき電流密度：１００Ａ／ｄｍ２
めっき浴温度 ：４５±５℃
陽極（アノード）：ＰｔコーティングＴｉ板
めっき浴の撹拌速度（循環ポンプの送液速度）：３６Ｌ／ｍｉｎ
めっき浴の組成
ＺｎＳＯ４・７Ｈ２Ｏ：２２０ｇ／Ｌ
Ｎａ２ＳＯ４：５０ｇ／Ｌ
Ｈ２ＳＯ４：１０ｇ／Ｌ
有機物の添加：４ｍｇ／Ｌ
亜鉛めっき皮膜の厚み：約３μｍ（２０ｇ／ｍ２）
得られた表面処理鋼板の亜鉛皮膜を実施例１と同様にして評価した結果、（０００２）面の結晶配向性指数は０．１であった。
また、ウィスカ発生の有無を走査型電子顕微鏡にて表面観測した結果、長手方向の長さが５μｍを超えるウィスカが認められた。
比較例４のめっき条件は、めっき電流密度が高く、めっき浴の撹拌速度は低いが、有機添加剤を使用したため、ウィスカ発生を促進させた結果、大きなウィスカが形成された。
On an Al killed cold-rolled steel sheet that had been degreased and pickled by a conventional method, galvanization was performed under the following conditions using an acidic plating bath mainly composed of zinc sulfate.
Plating current density: 100 A / dm 2
Plating bath temperature: 45 ± 5 ° C
Anode (anode): Pt-coated Ti plate plating bath stirring speed (circulation pump liquid feed speed): 36 L / min
Composition of plating bath ZnSO 4 · 7H 2 O: 220 g / L
Na 2 SO 4 : 50 g / L
H 2 SO 4 : 10 g / L
Addition of organic matter: 4 mg / L
Thickness of galvanized film: about 3 μm (20 g / m 2 )
As a result of evaluating the zinc film of the obtained surface-treated steel sheet in the same manner as in Example 1, the crystal orientation index of the (0002) plane was 0.1.
Further, as a result of surface observation with a scanning electron microscope for the presence or absence of whisker generation, whiskers having a length in the longitudinal direction exceeding 5 μm were observed.
The plating conditions of Comparative Example 4 were high plating current density and low plating bath agitation speed, but because organic additives were used, whisker generation was promoted, resulting in the formation of large whiskers.
以上の実施例、比較例をまとめたものを表１に示す。
本発明の亜鉛皮膜を有する表面処理鋼板は、亜鉛皮膜の（０００２）面の結晶配向性指数を制御することで５μｍを超えるウィスカの発生を抑制した表面処理鋼板とすることができ、この表面処理鋼板を用いて加工形成された電子機器及びプリント配線基板のカバー部材は、経時変化で発生したウィスカがカバー部材から脱落して回路中や端子間で、相手の部品と短絡してノイズや絶縁不良の原因となることがない。
特に、車両に組み込まれる電子機器のプリント配線基板などのカバー部材において、振動によるウィスカ落下が原因で発生する故障を減少させることができ、産業上の利用可能性が極めて高い。The surface-treated steel sheet having a zinc coating according to the present invention can be a surface-treated steel sheet in which the generation of whiskers exceeding 5 μm is suppressed by controlling the crystal orientation index of the (0002) plane of the zinc coating. Covers of electronic devices and printed wiring boards that are processed and formed using steel sheets have whiskers that have occurred over time and fall off the cover member, causing short circuits with other parts in the circuit and between terminals, resulting in noise and poor insulation. It will not cause
In particular, in a cover member such as a printed wiring board of an electronic device incorporated in a vehicle, failures caused by whisker dropping due to vibration can be reduced, and industrial applicability is extremely high.
Claims (1)
前記亜鉛めっきを施すめっき浴には有機系光沢剤が添加されず、
前記めっき浴の浴温が３０〜６０℃に調整され、
前記めっき浴のｐＨが０．５〜３．０に調整され、且つ、
前記めっき浴は、ＺｎＳＯ ４ ・７Ｈ ２ ０が１５０〜３００ｇ／Ｌ、Ｎａ ２ ＳＯ ４ が２０〜１００ｇ／Ｌ、およびＨ ２ ＳＯ ４ が５〜７０ｇ／Ｌ含まれる酸性のめっき浴であることを特徴とする、電子機器またはプリント配線基板のカバー部材用表面処理鋼板の製造方法。 On the steel sheet, galvanization is performed at a plating current density of 5 A / dm 2 to 40 A / dm 2 to form a galvanized film having a (0002) plane crystal orientation index of 2.5 to 5.3 ,
No organic brightener is added to the plating bath for galvanization,
The bath temperature of the plating bath is adjusted to 30 to 60 ° C.,
The pH of the plating bath is adjusted to 0.5-3.0, and
Said plating bath is a plating bath of acid ZnSO 4 · 7H 2 0 is 150~300g / L, Na 2 SO 4 is 20 to 100 g / L, where and H 2 SO 4 is contained 5 to 70 g / L A method for producing a surface-treated steel sheet for a cover member of an electronic device or a printed wiring board.
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| PCT/JP2010/006535 WO2011061901A1 (en) | 2009-11-20 | 2010-11-08 | Surface-treated steel sheet and cover member using steel sheet |
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| CN102534700B (en) * | 2012-02-29 | 2014-10-22 | 山东恒达精密薄板科技有限公司 | Technique for continuously producing nickel-zinc electroplated anti-fingerprint plate |
| KR102274990B1 (en) * | 2015-06-09 | 2021-07-09 | 닛폰세이테츠 가부시키가이샤 | surface treatment steel plate |
| JP7183266B2 (en) * | 2018-06-12 | 2022-12-05 | 株式会社ブリヂストン | Metal cords, metal cord-rubber composites and conveyor belts |
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| KR20180055927A (en) | 2018-05-25 |
| JPWO2011061901A1 (en) | 2013-04-04 |
| KR101860071B1 (en) | 2018-06-27 |
| JP6223482B2 (en) | 2017-11-01 |
| CN102666936A (en) | 2012-09-12 |
| KR20170087545A (en) | 2017-07-28 |
| KR20120101395A (en) | 2012-09-13 |
| KR101956723B1 (en) | 2019-06-19 |
| JP2016106178A (en) | 2016-06-16 |
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