JPS6324074A - Chemical conversion treatment bath composition for copper alloy - Google Patents
Chemical conversion treatment bath composition for copper alloyInfo
- Publication number
- JPS6324074A JPS6324074A JP16680686A JP16680686A JPS6324074A JP S6324074 A JPS6324074 A JP S6324074A JP 16680686 A JP16680686 A JP 16680686A JP 16680686 A JP16680686 A JP 16680686A JP S6324074 A JPS6324074 A JP S6324074A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- conversion treatment
- treatment bath
- copper
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims description 12
- 229910000881 Cu alloy Inorganic materials 0.000 title abstract 2
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 125000003277 amino group Chemical group 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 150000001413 amino acids Chemical class 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000004471 Glycine Substances 0.000 claims abstract description 5
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960002684 aminocaproic acid Drugs 0.000 claims abstract description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract 2
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- -1 nitrite ions Chemical class 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 238000007739 conversion coating Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000005772 leucine Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 235000014393 valine Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
- H01L23/49582—Metallic layers on lead frames
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、金属表面をリン酸塩浴中で化学的に処理して
、該金属表面にリン酸塩を主体とする不溶性化合物の被
膜を生成させ、金属表面に全屈の腐食防止、金属表面の
潤滑性向上、塗膜の密着性向上などを図る化合物処理に
関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention involves chemically treating a metal surface in a phosphate bath to form a coating of an insoluble compound mainly composed of phosphates on the metal surface. It relates to compound treatment that aims to prevent total corrosion on metal surfaces, improve the lubricity of metal surfaces, and improve the adhesion of paint films.
更に、詳しく述べるならば、本発明は、薄（かつ均一な
化成被膜を銅系金属表面に形成する銅系金属の化成処理
浴組成物に関するものである。More specifically, the present invention relates to a chemical conversion treatment bath composition for copper-based metals that forms a thin (and uniform) chemical conversion film on the surface of copper-based metals.
全屈の化成処理は従来鉄鋼を中心に検討され、防錆、密
着性向上、潤滑性付与などを目的としたリン酸塩処理お
よびクロメート処理が広範囲に行なわれ、工業的に重要
な技術になっている。Chemical conversion treatment for full bending has traditionally been studied mainly for steel, and phosphate treatment and chromate treatment have been widely used for the purposes of rust prevention, improved adhesion, and imparting lubricity, and it has become an industrially important technology. ing.
一方、銅は工業的に有用な金属材料であるが、酸に対し
て安定な金属であるため、酸への熔解反応で被膜形成反
応が進行する化成処理を工業的に安定して行なう方法の
開発は、鉄ｉｆＯ化成処理よりは遅れている。しかし、
リン酸被膜を銅系金属表面に形成する方法は今後工業的
に広〈実施される見込みがある。特に、リン酸イオン、
亜鉛イオン等、過酸化水素などの酸化剤などの鉄鋼で知
られている化成処理浴成分に、フン素を除くハロゲンイ
オンを添加した化成処理浴によれば、銅の表面に安定な
化成被膜を形成させることができることが公表され（特
開昭６１−２６７８３号）、今後、電線、ケーブルなど
の銅系金属部品４Ｅ’成処理の普及が期待される。On the other hand, copper is an industrially useful metal material, but since it is a metal that is stable against acids, it is difficult to carry out chemical conversion treatment in an industrially stable manner in which a film-forming reaction proceeds by dissolving it in an acid. Development is slower than iron ifO chemical conversion treatment. but,
The method of forming a phosphoric acid film on the surface of a copper-based metal is expected to be widely implemented industrially in the future. In particular, phosphate ion,
A chemical conversion bath in which halogen ions excluding fluorine are added to the chemical conversion bath components known for steel, such as zinc ions and oxidizing agents such as hydrogen peroxide, can form a stable chemical conversion film on the surface of copper. It has been published (Japanese Patent Laid-Open No. 61-26783) that it is possible to form 4E' copper-based metal parts such as electric wires and cables, and it is expected that the 4E' forming process will become widespread in the future.
本発明は、銅表面への化成被膜処理の効果の一つである
塗膜と銅との密着性の改善に関するものである。The present invention relates to improving the adhesion between a coating film and copper, which is one of the effects of chemical conversion coating treatment on a copper surface.
化成被膜を塗膜密着性向上の手段として使用する場合、
化成被膜の組織は微細でありまた摸厚２よ薄い方が望ま
しい。例えば、化成被膜の付着量がより多くなるに伴っ
て、塗膜に働く外力により塗膜が剥離する前に化成被膜
の部分で破壊が生じ、結果的に塗膜と銅との密着性が低
下する。例えば、前述の特開昭６１−２６７８３号の方
法を本発明者等がさらに研究したところ１０ｇ／ｒｒ？
以上の付着量では塗膜の密着性の劣化傾向が認められた
。また、化成被膜の組織が粗いと、その上に塗布した塗
、使の厚みが不均一ソなるので塗膜に亀裂を生じやすい
。When using chemical conversion coatings as a means of improving paint film adhesion,
The structure of the chemical conversion coating is fine, and it is preferable that the structure is thinner than the sample thickness of 2. For example, as the amount of chemical conversion coating increases, damage occurs in the chemical conversion coating before the coating peels off due to external force acting on the coating, resulting in a decrease in the adhesion between the coating and copper. do. For example, when the present inventors further researched the method of JP-A No. 61-26783 mentioned above, the result was 10 g/rr.
A tendency for the adhesion of the coating film to deteriorate was observed with the above amount of coating. In addition, if the structure of the chemical conversion coating is rough, the thickness of the coating applied on top of it will be uneven, making it easy for cracks to occur in the coating.
一般に、銅表面への化成被膜の付着量が少なくなると、
均一で細かい化成被膜の形成は困難になる。Generally, when the amount of chemical conversion coating deposited on the copper surface decreases,
It becomes difficult to form a uniform and fine chemical conversion coating.
即ち、薄い化成被膜を作成しようとすると、銅表面に部
分的に化成被膜のない部分を生じたり、あるいは結晶の
大きさが不均一となり、細かくならず、塗膜との密着性
が不十分になる。In other words, when trying to create a thin chemical conversion film, there may be some areas on the copper surface where there is no chemical conversion film, or the crystals will be uneven in size and not fine, resulting in insufficient adhesion to the paint film. Become.
本発明者らは銅表面に付着量が少なくても、均一で細か
い化成被膜の結晶を生成させることのできる化成処理浴
について鋭意検討の結果、本発明に到達したのである。The present inventors have arrived at the present invention as a result of intensive studies on a chemical conversion treatment bath that can generate uniform and fine crystals of a chemical conversion film even if the amount of deposition on the copper surface is small.
本発明は、リン酸イオン、金属イオン、酸性溶液中で銅
の／８解を促進する酸化剤を含んでなる化成処理浴中に
、カルボキシル基とアミノ基とを有する化合物をさらに
含有せしめてなる事を特徴とする銅系金属用の化成処理
浴組成物にある。In the present invention, a chemical conversion bath containing phosphate ions, metal ions, and an oxidizing agent that promotes the /8 decomposition of copper in an acidic solution further contains a compound having a carboxyl group and an amino group. The present invention provides a chemical conversion treatment bath composition for copper-based metals, which is characterized by the following.
本発明で使用されるカルボキシル基とアミノ基とを有す
る化合物は上記化成処理浴に溶解して、化成被膜を微細
、均一にし、また塗膜との密着性を向上させる成分であ
る。カルボキシル基とアミノ基とを有する化合物として
は、アントラニル酸、アミノサリチル酸、アミノ酸の殆
ど全部、特にグリシン、アミノカプロン酸、バリン、ロ
イシン、り゛ルタミン酸、アスパラギン酸などの分子中
にこれらの基を有する有機化合物を用いる。これらの中
では、特にグリシン、アミノカプロン酸が入手の容易さ
及び価格の点で好ましい。The compound having a carboxyl group and an amino group used in the present invention is a component that dissolves in the above-mentioned chemical conversion treatment bath, makes the chemical conversion film fine and uniform, and improves the adhesion to the coating film. Examples of compounds having a carboxyl group and an amino group include anthranilic acid, aminosalicylic acid, and almost all amino acids, especially glycine, aminocaproic acid, valine, leucine, glutamic acid, and aspartic acid, which have these groups in their molecules. Use organic compounds. Among these, glycine and aminocaproic acid are particularly preferred in terms of availability and price.
カルボキシル基とアミン基を有する化合物の添加量は化
成処理浴に対し２０〜２０００ ｐｐｍ （又は■／Ｌ
）添加すると効果が大である。添加量が２０ｐｐｍ以下
では、効果が顕著でなく、一方２０００ｐｐｍを越える
と化成処理浴の安定性が損なわれる傾向が生じる。The amount of the compound having a carboxyl group and an amine group added is 20 to 2000 ppm (or ■/L) to the chemical conversion treatment bath.
) has a great effect when added. If the amount added is less than 20 ppm, the effect will not be significant, while if it exceeds 2000 ppm, the stability of the chemical conversion bath will tend to be impaired.
リン酸イオン、金属イオン、酸性溶液中で銅の熔解を促
進する酸化剤を含む化成処理浴に浸漬された銅系金属の
表面では、銅溶解およびハロゲン化第１銅の析出を基本
とするアノード反応と、リン酸塩の沈殿を基本とするカ
ソード反応が進行し、化成被膜の形成が起こる。かかる
化成被膜形成過程に、カルボキシル基とアミノ基を有す
る化合物が及ぼす影響は明らかではないが、化成被膜を
構成している結晶の発生数が多くなり、結晶成長速度が
低下し結果として均一で細かい化成被膜が作成されるも
のと推察される。本発明の化成処理浴中の銅の溶解を促
進する酸化剤は、例えば過酸化水素または亜硝酸イオン
等である。上述の特開昭６１−２６７８３号にしたがっ
て、金属イオンとしては脱水素反応により溶解度が減少
する、亜鉛、マンガン、鉄、カルシウム、マグネシウム
などを使用することができる。On the surface of copper-based metals immersed in a chemical conversion bath containing phosphate ions, metal ions, and an oxidizing agent that promotes the dissolution of copper in acidic solutions, an anode based on copper dissolution and precipitation of cuprous halides The reaction and the cathodic reaction based on the precipitation of phosphate proceed, resulting in the formation of a conversion film. Although the influence of compounds having carboxyl groups and amino groups on the chemical conversion film formation process is not clear, the number of crystals that make up the chemical conversion film increases, and the crystal growth rate decreases, resulting in uniform and fine crystals. It is assumed that a chemical conversion film is created. The oxidizing agent that promotes dissolution of copper in the chemical conversion treatment bath of the present invention is, for example, hydrogen peroxide or nitrite ion. According to the above-mentioned Japanese Patent Application Laid-Open No. 61-26783, zinc, manganese, iron, calcium, magnesium, etc., whose solubility decreases due to dehydrogenation reaction, can be used as metal ions.
化成処理浴組成については、上述の特開昭６１−２６７
８３号にしたがって、塩素イオン、臭素イオンまたはヨ
ウ素イオンあるいはこれらの２種以上の混合イオンを浴
に添加することにより化成被膜形成反応を安定化させる
ことができる。化成被膜を円滑に生成させる好ましい浴
組成の一例は、化成処理浴ＩＬ中にリン酸イオン２ｇ、
亜鉛イオン２ｇ、フッ素を除くハロゲンイオンを１ｇ以
上含有させたものである。この特開昭６１−２６７８３
号の化成処理浴の場合でも、カルボキシル基とアミノ基
を有する化合物は反応安定性を損なわず、より均一で細
かい化成被膜の形成を可能にする。また、酸化剤につい
ては特開昭６１−２６７８３号にしたがって、化成処理
浴の酸化還元電位（ＡｇＣ１電極電位）の設定により酸
化剤の銅溶解促進作用を化成被膜安定形成に好ましいも
のに調節することができる。Regarding the chemical conversion bath composition, the above-mentioned Japanese Patent Application Laid-Open No. 61-267
According to No. 83, the chemical conversion film forming reaction can be stabilized by adding chloride ions, bromide ions, iodine ions, or a mixture of two or more of these ions to the bath. An example of a preferable bath composition for smoothly forming a chemical conversion film includes 2 g of phosphate ions,
It contains 2g of zinc ions and 1g or more of halogen ions excluding fluorine. This Japanese Patent Publication No. 61-26783
Even in the case of the chemical conversion treatment bath of No. 2, compounds having carboxyl groups and amino groups do not impair reaction stability and enable the formation of more uniform and finer chemical conversion coatings. Regarding the oxidizing agent, according to Japanese Patent Application Laid-Open No. 61-26783, the copper dissolution promoting effect of the oxidizing agent can be adjusted to a value favorable for stable formation of a chemical conversion film by setting the redox potential (AgC1 electrode potential) of the chemical conversion treatment bath. Can be done.
本発明者等はカルボキシル基とアミノ基を有する化合物
を添加した場合に化成被膜安定形成が可能な酸化還元電
位の範囲を研究したところ、４００ｍ Ｖ、より望まし
くは５００…Ｖ以上が有効であることを見出した。特開
昭６１−２６７８３号の従来技術では均一な化成被膜を
得るためには、化成被膜の付着量は５〜Ｌｏｇ／ｎ？必
要であったが、本発明ではより緻密で均一な被膜を、被
膜付着ｆｆ１０．５〜５ ｇ／ ｌで得ることができる
。またこの従来技術では化成被膜はアモルファスないし
は結晶未発達状態であったが、本発明では結晶質もしく
はアモルファス混在結晶質であることが、電子顕微鏡観
察により認められた。The present inventors have studied the range of redox potential that allows stable formation of a chemical conversion film when a compound having a carboxyl group and an amino group is added, and found that 400 mV, more preferably 500...V or more is effective. I found out. In the conventional technique of JP-A No. 61-26783, in order to obtain a uniform chemical conversion film, the amount of chemical conversion film deposited must be 5 to Log/n? Although necessary, with the present invention denser and more uniform coatings can be obtained with a coating deposition ff of 10.5-5 g/l. Further, in this prior art, the chemical conversion coating was amorphous or in an undeveloped state of crystals, but in the present invention, it was confirmed by electron microscopy that it was crystalline or amorphous-crystalline.
次に、本発明の実施例と比較例を説明するが、本発明は
以下の実施例のみに限定されるものではない。Next, Examples and Comparative Examples of the present invention will be described, but the present invention is not limited to the following Examples.
比較例１ 亜鉛イオン３２．５ｇ／Ｌ、塩素イオン３０ｇ／Ｌ。Comparative example 1 Zinc ion 32.5g/L, chlorine ion 30g/L.
リン酸イオン１０ｇ／Ｌ、過酸化水素Ｌｏｇ／Ｌの濃度
となるような化成処理浴を作成した。２×５關の軟鋼平
角線をアセトン脱脂した後、ゆっくりと攪拌した上記処
理浴中に３分間浸漬した。この時の化成処理浴は温度２
０℃、ｐＨ１，７、酸化還元電位５５０ｍＶ （Ａｇ
Ｃ１電極）であった。得られた化成被膜の表面を走査型
電子顕微鏡で観察した４００倍の写真を第２図に示した
。次に化成処理した平角線を１規定＋１ｃｆに１時間浸
漬する事により化成被膜を溶解させ、１規定Ｉ１１に１
時間浸漬前後の重量変化を調べ化成被膜の付着量を調べ
その付着量を表１に示した。A chemical conversion bath was prepared with a concentration of 10 g/L of phosphate ions and Log/L of hydrogen peroxide. After degreasing a 2×5 rectangular mild steel wire with acetone, it was immersed in the slowly stirred treatment bath for 3 minutes. The temperature of the chemical conversion bath at this time is 2.
0°C, pH 1.7, redox potential 550mV (Ag
C1 electrode). FIG. 2 shows a photograph of the surface of the obtained chemical conversion coating observed with a scanning electron microscope at a magnification of 400 times. Next, the chemical conversion coating was dissolved by immersing the chemically treated flat wire in 1N + 1cf for 1 hour, and the chemical conversion film was dissolved in 1N I11.
The weight change before and after time immersion was examined to determine the amount of chemical conversion film adhered, and the amount adhered is shown in Table 1.
実施例１
比較例１で用いた化成処理浴ＩＬに対しグリシンを０．
５ｇ添加し、比較例１と同様の方法で化成処理を行なっ
た。得られた化成被膜の走査型電子顕微鏡写真を第１図
に、化成被膜付着量を表１に示した。Example 1 Glycine was added to the chemical conversion bath IL used in Comparative Example 1 by 0.
5g was added and chemical conversion treatment was performed in the same manner as in Comparative Example 1. A scanning electron micrograph of the obtained chemical conversion film is shown in FIG. 1, and the amount of the chemical conversion film deposited is shown in Table 1.
線にエステルイミドワニス（口触スケネクタディ社製ア
イソミツドＲ）（）を膜厚５〜１０μｍになるように塗
布し、２００℃で２時間焼付した。次にエステルイミド
を塗布した平角線の害着性を、次に示す２つの方法で評
価した結果を表２に示した。Esterimide varnish (Isomid R, manufactured by Schenectady) () was applied to the wire to a thickness of 5 to 10 μm, and baked at 200° C. for 2 hours. Next, the adhesion properties of the rectangular wire coated with esterimide were evaluated using the following two methods, and the results are shown in Table 2.
方法１）・・・平角線上に塗布したエステルイミドに２
婁嘗角の切込みを５つ入れ、粘着テープをその上に付着
させた。粘着テープを剥離した時、切込みを入れたエス
テルイミド塗膜が平角線よりはがれた個数を調べた。Method 1)... Apply 2 to the esterimide coated on the flat wire.
Five square incisions were made and adhesive tape was adhered onto the incisions. When the adhesive tape was peeled off, the number of notched esterimide coatings that peeled off from the flat wire was determined.
方法２）・・・エステルイミドを塗布した平角線を切断
するまで伸長した時のエステルイミド塗膜の付着状態を
調べた。Method 2): The state of adhesion of the esterimide coating film was examined when a rectangular wire coated with esterimide was stretched until it was cut.
以下余白
ＬＬ−北減几 た・・ 百の±−゛、デー注） 密着
性の評価基準
○： 塗膜が剥離しない。Below is the margin LL - 100±-゛, day note) Evaluation criteria for adhesion: ○: The coating film does not peel off.
×： 塗膜の剥離が見られる。×: Peeling of the coating film is observed.
表１に示されているように、従来の化成処理浴、本発明
の化成処理浴とも得られた化成被膜の付着量は４〜５
ｇ／ｍの範囲にある。As shown in Table 1, the deposition amount of the chemical conversion coating obtained in both the conventional chemical conversion treatment bath and the chemical conversion treatment bath of the present invention was 4 to 5.
g/m range.
第２図の電子顕微鏡写真を見ると従来の化成処理浴を用
いたものは、部分的に化成被膜のないところがあり、結
晶の大きさも５〜１０μｍと大きい。Looking at the electron micrograph in FIG. 2, it can be seen that in the case of using a conventional chemical conversion treatment bath, there are parts where there is no chemical conversion coating, and the crystal size is large, 5 to 10 μm.
一方、第１図に示されている本発明の化成処理浴を用い
たものは、化成被膜のない部分はなく、結晶の大きさも
１〜３μｍ、：！：細かく均一であり、従来の化成処理
浴のものより化成被膜が細か（均一である事は明らかで
ある。表１に示されるように本発明の化成被膜は従来の
化成処理浴より密着性が優れている。このような優れた
密着性が得られたのは、細かく均一な化成被膜結晶が成
長したためと考えられる。On the other hand, in the chemical conversion treatment bath of the present invention shown in FIG. 1, there is no area without a chemical conversion coating, and the crystal size is 1 to 3 μm. : It is fine and uniform, and it is clear that the chemical conversion coating is finer (and more uniform) than that of conventional chemical conversion treatment baths.As shown in Table 1, the chemical conversion coating of the present invention has better adhesion than that of conventional chemical conversion treatment baths. The reason why such excellent adhesion was obtained is thought to be due to the growth of fine and uniform chemical conversion coating crystals.
比較例２
比較例１で用いた化成処理浴ＩＬに対し、カルボキシル
基を有するが、アミン基を有しない化合物として安息香
酸を、またアミノ基を有するが、カルボキシル基を有し
ない化合物としてアニリンを、それぞれ０．５ｇ添加し
て、比較例１と同様な化成処理を行なったところ、比較
例１と同様な結果が得られ、同じ化合物中にカルボキシ
ル基とアミノ基がないと、本発明の効果が達成されない
ことが確かめられた。Comparative Example 2 For the chemical conversion bath IL used in Comparative Example 1, benzoic acid was used as a compound having a carboxyl group but not having an amine group, and aniline was used as a compound having an amino group but not having a carboxyl group. When 0.5g of each was added and the same chemical conversion treatment as in Comparative Example 1 was performed, the same results as in Comparative Example 1 were obtained. It was confirmed that this was not achieved.
以上に示されるように本発明の化成処理浴を用いれば、
化成被膜の付着量が少なくても、細かく均一な化成被膜
を銅系材料に生成させる事が出来、その工業的価値は大
きい。As shown above, if the chemical conversion treatment bath of the present invention is used,
Even if the amount of chemical conversion film deposited is small, a fine and uniform chemical conversion film can be formed on copper-based materials, and its industrial value is great.
【図面の簡単な説明】
第１図は本発明の実施例により生成された化成被膜の走
査型電子顕微鏡組織を示す写真、第２図は従来例につい
て第１図と同様の組織を示す写真である。[Brief Description of the Drawings] Fig. 1 is a photograph showing a scanning electron microscope structure of a chemical conversion film produced according to an embodiment of the present invention, and Fig. 2 is a photograph showing a structure similar to Fig. 1 of a conventional example. be.
Claims (1)
の溶解を促進する酸化剤を含んでなる化成処理浴中に、
カルボキシル基とアミノ基を有する化合物を含有せしめ
てなることを特徴とする銅系金属の化成処理浴組成物。 ２、前記カルボキシル基とアミノ基を有する化合物を化
成処理浴中に１０〜５０００ｐｐｍ含有せしめてなる特
許請求の範囲第１項記載の銅系金属の化成処理浴組成物
。 ３、前記カルボキシル基とアミノ基を有する化合物がア
ミノ酸である特許請求の範囲第１項記載の銅系金属の化
成処理浴組成物。 ４、アミノ酸がグリシンである特許請求の範囲第３項記
載の銅系金属の化成処理浴組成物。 ５、アミノ酸がアミノカプロン酸である特許請求の範囲
第３項記載の銅系金属の化成処理浴組成物。 ６、化成処理浴のｐＨが０．５〜３．５であり、また酸
化還元電位（ＡｇＣｌ電極）が４００ｍＶ以上である特
許請求の範囲第１項記載の銅系金属の化成処理浴組成物
。[Claims] 1. In a chemical conversion bath comprising phosphate ions, metal ions, and an oxidizing agent that promotes dissolution of copper in an acidic solution,
1. A chemical conversion treatment bath composition for copper-based metals, comprising a compound having a carboxyl group and an amino group. 2. The chemical conversion treatment bath composition for copper-based metals according to claim 1, wherein the chemical conversion treatment bath contains 10 to 5000 ppm of the compound having a carboxyl group and an amino group. 3. The chemical conversion treatment bath composition for copper-based metals according to claim 1, wherein the compound having a carboxyl group and an amino group is an amino acid. 4. The chemical conversion treatment bath composition for copper-based metals according to claim 3, wherein the amino acid is glycine. 5. The chemical conversion treatment bath composition for copper-based metals according to claim 3, wherein the amino acid is aminocaproic acid. 6. The chemical conversion treatment bath composition for copper-based metals according to claim 1, wherein the chemical conversion treatment bath has a pH of 0.5 to 3.5 and an oxidation-reduction potential (AgCl electrode) of 400 mV or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16680686A JPS6324074A (en) | 1986-07-17 | 1986-07-17 | Chemical conversion treatment bath composition for copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16680686A JPS6324074A (en) | 1986-07-17 | 1986-07-17 | Chemical conversion treatment bath composition for copper alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6324074A true JPS6324074A (en) | 1988-02-01 |
Family
ID=15838023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16680686A Pending JPS6324074A (en) | 1986-07-17 | 1986-07-17 | Chemical conversion treatment bath composition for copper alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6324074A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676023A (en) * | 1995-08-31 | 1997-10-14 | Otsuka Koki Kabushiki Kaisha | Cane type emergency brake |
| WO2004024987A1 (en) * | 2002-08-30 | 2004-03-25 | Toto Ltd. | Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy |
| JP2014520955A (en) * | 2011-07-07 | 2014-08-25 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Method for providing adhesion of organic resist to copper or copper alloy surface |
-
1986
- 1986-07-17 JP JP16680686A patent/JPS6324074A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5676023A (en) * | 1995-08-31 | 1997-10-14 | Otsuka Koki Kabushiki Kaisha | Cane type emergency brake |
| WO2004024987A1 (en) * | 2002-08-30 | 2004-03-25 | Toto Ltd. | Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy |
| JP2014520955A (en) * | 2011-07-07 | 2014-08-25 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Method for providing adhesion of organic resist to copper or copper alloy surface |
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