JPS5953349B2 - Electroless copper plating solution - Google Patents
Electroless copper plating solutionInfo
- Publication number
- JPS5953349B2 JPS5953349B2 JP2758482A JP2758482A JPS5953349B2 JP S5953349 B2 JPS5953349 B2 JP S5953349B2 JP 2758482 A JP2758482 A JP 2758482A JP 2758482 A JP2758482 A JP 2758482A JP S5953349 B2 JPS5953349 B2 JP S5953349B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- electroless copper
- copper plating
- silver
- copper
- 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.)
- Expired
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 35
- 229910052802 copper Inorganic materials 0.000 title claims description 35
- 239000010949 copper Substances 0.000 title claims description 35
- 238000007747 plating Methods 0.000 title claims description 35
- 238000005452 bending Methods 0.000 claims description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 150000001414 amino alcohols Chemical class 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229940045105 silver iodide Drugs 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- HXJNJLSAZAGIBV-UHFFFAOYSA-M iodosilver silver Chemical compound [Ag].I[Ag] HXJNJLSAZAGIBV-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Description
【発明の詳細な説明】
本発明は無電解銅めつき液に関し、詳しくは高い引張り
強度とすぐれた耐折疲労強度とをもつめつき銅が得られ
る無電解銅めつき液に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electroless copper plating solution, and more particularly to an electroless copper plating solution that provides plating copper with high tensile strength and excellent bending fatigue strength.
無電解銅めつきから得られる銅の機械的特性を向上させ
るための研究開発は、これまでにも盛んに行なわれてき
ており、又現在でも盛んな理由の１つは、この無電解銅
めつき技術をプリント配線板の回路形成に応用すると大
きな効果が生まれる可能性があるためである。すなわち
、プリント配線板の回路は年々高密度化しており、違つ
た面の回路を導通させるためのスルーホール径は増々小
さくなつてきている。このような状況の中で、電気めつ
き方法に較べて平面部分とスルーホール内壁面のめつき
厚さに差の生じにくい無電解銅めつきが期待されている
わけである。また、電気めつきをおこない、回路以外の
銅をエッチング除去する方法（サブトラクト法）におい
ては、エッチングによりアンダーカット（銅の厚さ方向
において、表面部分はエッチングレジストの膜で寸法が
保持されるものの、基板近傍ではエッチングがより進行
するために回路断面が逆台形になる。）が生じるため細
線回路をつくるのは難しい。これに対して、無電解銅め
つき（アディティブ法）では回路部分だけをめつきで付
与するのでアンダーカットの問題がなく回路の細線化に
有利である。Research and development to improve the mechanical properties of copper obtained from electroless copper plating has been actively carried out, and one of the reasons why it is still active is that this electroless copper plating This is because the application of the mounting technology to circuit formation on printed wiring boards has the potential to produce great effects. That is, the circuit density of printed wiring boards is becoming higher and higher year by year, and the diameter of through holes for conducting circuits on different surfaces is becoming smaller and smaller. Under these circumstances, electroless copper plating is expected to produce less difference in the plating thickness between the flat surface and the inner wall surface of the through hole than electroplating methods. In addition, in the method of electroplating and etching away copper other than circuits (subtract method), etching creates undercuts (in the direction of the thickness of the copper, although the dimensions of the surface portion are maintained by an etching resist film). It is difficult to create thin wire circuits because etching progresses further near the substrate, resulting in an inverted trapezoidal cross-section of the circuit. On the other hand, in electroless copper plating (additive method), only the circuit portion is plated, so there is no undercut problem and it is advantageous for thinning the circuit.
しかし、これまでの多くの無電解銅めつきは、一般にプ
リント配線板の回路形成に用いられているピロリン酸電
気めつきから得られる銅（ピロ銅）の物性、すなわち引
張り強さ、および後で述べる方法で測定した耐折疲労強
度に比べて劣つているために、製品の信頼性があまり高
くない。However, many electroless copper plating methods to date have focused on the physical properties of copper (pyrocopper) obtained from pyrophosphate electroplating, which is commonly used to form circuits on printed wiring boards. The reliability of the product is not very high because it is inferior to the folding fatigue strength measured by the method described above.
すなわち、プリント配線板に部品搭載後の半田あげによ
る加熱などで回路が切断しやすいなどの欠点がある。ピ
ロ銅の引張り強度は５０〜６０ｋｇ／一、また耐折疲労
強度は２５μｍの厚さで２、０００〜３、０００回であ
る。これに対して、工業的なレベルで使用されている無
電解銅めつきから得られる銅の引張り強度は、約３０ｋ
ｇ／一、また耐折疲労強度は８００〜１，１００回（２
５μｍ）である。配線回路が高密度な配線板では、同時
に高い接続信頼性が要求されるので、無電解銅めつきは
前記した理由で配線の高密度化には有利であつても、ほ
とんど使用されていないのが現状である。したがつて、
無電解銅めつきで得られる銅の物性が改善され、たとえ
ば、ピロ銅のそれに近づけば新しい道が開けるのである
。本発明はこのような点に鑑みてなされたもので、銅塩
、錯化剤、還元剤およびＰＨ調整剤を含む無電解銅めつ
き液に、銀イオン供給源とアミノアルコールを添加した
ことを特徴とする。That is, there is a drawback that circuits are easily broken due to heating caused by soldering after components are mounted on a printed wiring board. The tensile strength of pyrocopper is 50 to 60 kg/1, and the folding fatigue strength is 2,000 to 3,000 times at a thickness of 25 μm. In contrast, the tensile strength of copper obtained from electroless copper plating, which is used on an industrial level, is approximately 30k.
g/1, and the folding fatigue strength is 800 to 1,100 times (2
5 μm). Wiring boards with high-density wiring circuits also require high connection reliability, so electroless copper plating is rarely used, even though it is advantageous for increasing wiring density for the reasons mentioned above. is the current situation. Therefore,
If the physical properties of copper obtained by electroless copper plating can be improved and become closer to those of, for example, pyro-copper, new avenues will open up. The present invention has been made in view of these points, and is based on the addition of a silver ion source and an amino alcohol to an electroless copper plating solution containing a copper salt, a complexing agent, a reducing agent, and a pH adjuster. Features.
銀イオン供給源としては、金属銀、ヨウ化銀、臭化銀、
塩化銀、硝酸銀、硫酸銀、シアン化銀、酢酸銀、炭酸銀
等の銀化合物の少なくとも一種が使用される。Silver ion sources include metallic silver, silver iodide, silver bromide,
At least one of silver compounds such as silver chloride, silver nitrate, silver sulfate, silver cyanide, silver acetate, and silver carbonate is used.
銀イオンは得られるめつき銅の機械強度、特に引張り強
度および耐折疲労強度を向上させる。Silver ions improve the mechanical strength of the plated copper obtained, especially the tensile strength and bending fatigue strength.
銀イオン供給源として、金属銀、ヨウ化銀を使用する場
合はその添加量は１１ｎｇ／１もあれば充分で▲▲叔こ
れよりじくてもめつぎ液が不安定になり分解するという
とはない。これ１ま金属銀ミヨウ化銀の溶解度が極めて
小さいためである。水に対する溶解度は、金属銀の場合
、２５℃で２．８×１０−５ｇ／ｌ（２．６×１０−J
ャｃ求^ｌ）、ヨウ化銀の場合、２０℃で３．４Ｘ１０
−５ｇ／ｌ（１．４×１０−Jャｃ求^１）である。これ
に対して、その他の銀の化合物（たとえば硝酸銀など）
の場合には、一般に溶解度が高いのである一定量以上加
えるとめつき液が不安定になり分解しやす〈なる。If metallic silver or silver iodide is used as a silver ion source, an addition amount of 11 ng/1 is enough. do not have. This is because the solubility of metallic silver silver iodide is extremely low. In the case of metallic silver, the solubility in water is 2.8 x 10-5 g/l (2.6 x 10-J
In the case of silver iodide, 3.4X10 at 20℃
-5 g/l (1.4 x 10-Jc^1). In contrast, other silver compounds (such as silver nitrate)
In the case of , the solubility is generally high, so if more than a certain amount is added, the plating solution becomes unstable and easily decomposes.
これはめつき液中の韻イオン濃度が高くＺ′ｉる一ため
である冫ごめ場合、安定剤を多く添加すればある程度分
解を抑えられるが、その場合においても限度がある。溶
解度の高い銀イオン供給源を使用する場合、それらの化
合物はめつき液中の銀イオン濃度が得られためつきの機
械強度の向上すなわち引張り強度および耐折疲労強度が
認められ、かつめつき液が不安定になり分解しない濃度
となるような量供給される。This is due to the high ion concentration in the plating solution.In the case of decomposition, adding a large amount of stabilizer can suppress the decomposition to some extent, but even in that case there is a limit. When a highly soluble silver ion source is used, these compounds increase the silver ion concentration in the plating solution, resulting in improved mechanical strength of the plating, i.e., tensile strength and bending fatigue strength; It is supplied in such an amount that the concentration is stable and does not decompose.
一般にはめつき液中の銀イオンの濃度は１０−１〜１０
−３モル／１が好ましい。Generally, the concentration of silver ions in the plating solution is 10-1 to 10
-3 mol/1 is preferred.
１０−３〜１０−５モル／１が更に好ましい。More preferably 10-3 to 10-5 mol/1.
アミノアルコールは無電解めつき液の安定性を向上させ
る。Amino alcohol improves the stability of electroless plating solutions.
アミノアルコールは
一般式
Ｈ２Ｎ−Ｒ−０Ｈ
で表わされる化合物で、例えば、エタノールアミン、３
−アミノ−１−プロパノール、５−アミノ−１−ペンタ
ノール、６−アミノ−１−ヘキサノール、１−アミノ−
２−プロパノール、２−アミノ−１−ブタノール、２−
アミノ−１−プロパノール、１−アミノ−２−ブタノー
ル等がある。Amino alcohol is a compound represented by the general formula H2N-R-0H, such as ethanolamine, 3
-amino-1-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 1-amino-
2-propanol, 2-amino-1-butanol, 2-
Examples include amino-1-propanol and 1-amino-2-butanol.
アミノアルコールの添加量は０．００１ｇ／１以上、好
ましくは０．０１〜１０ｇ／１．最も好ましくは０．５
〜５ｇハである。添加量が０．００１ｇハ未満の場合は
めつき液の安定性が低下し、めつき銅の物性、すなわち
、引張り強度および耐折疲労強度が低下する添加量が多
くても悪影響は与えないが、一般に１０ｇハを超える添
加は不必要である。The amount of amino alcohol added is 0.001 g/1 or more, preferably 0.01 to 10 g/1. Most preferably 0.5
~5g Ha. If the amount added is less than 0.001 g, the stability of the plating solution decreases, and the physical properties of the plated copper, that is, the tensile strength and bending fatigue strength, decrease. Generally, it is unnecessary to add more than 10 g.
ジオール、ヒドロキシカルボン酸、ジカノレボン酸、ジ
アミン、シアンヒドリン、エチレングリコールのモノあ
るいはジアルキルエーテル、ヒドロキシ基をもつ脂肪族
第二あるいは第三アミン、Ｄ−メチル−エタノールアミ
ン、Ｐ−ジオキサン、モルホリン、ピペラジンの少なく
とも一種を０．００１ｇハ以上、好ましくは０．０１〜
１０ｇ／１．最も好ましくは０．５〜５ｇハ更に添加す
ることが出来る。At least one of diols, hydroxycarboxylic acids, dicanolebonic acids, diamines, cyanohydrins, mono- or dialkyl ethers of ethylene glycol, aliphatic secondary or tertiary amines with hydroxy groups, D-methyl-ethanolamine, P-dioxane, morpholine, piperazine 0.001g or more of one kind, preferably 0.01~
10g/1. Most preferably, 0.5 to 5 g can be further added.
本発明においてベースとなる無電解銅めつき液はとくに
特殊な配合のものではない。The electroless copper plating solution that is the base of the present invention is not particularly formulated.
銅塩、錯化剤、還元剤およびＰＨ調整剤とから成る一般
の無電解銅めつき液が用いられる。銅塩としては、硫酸
銅、ハロゲン化銅、硝酸銅、酢酸銅等が、錯化剤として
は、エチレンジアミン四酢酸、ロツシエル塩等が還元剤
としてはホルマリン、パラホルムアルデヒド等が、ＰＨ
調整剤としては水酸化ナトリウム等が使用される。代表
的な無電解めつき液としては、硫酸銅３〜２０ｇ／１．
エチレンジアミン四酢酸、銅塩濃度の１．２〜３倍モル
濃度量、３７％のホルマリン水溶液２〜２５ｍ１／１．
ＰＨｌｌ．５〜１３．０のものが好ましい。温度は９０
℃以下で行うのが良い。以上説明したように本発明の無
電解めつき液により引張り強度、耐折疲労強度に優れた
めつき銅が得られた。A common electroless copper plating solution consisting of a copper salt, a complexing agent, a reducing agent and a PH adjuster is used. Copper salts include copper sulfate, copper halides, copper nitrate, copper acetate, etc. Complexing agents include ethylenediaminetetraacetic acid and Rothsiel's salt; reducing agents include formalin, paraformaldehyde, etc.
Sodium hydroxide or the like is used as a regulator. A typical electroless plating solution is copper sulfate 3 to 20 g/1.
Ethylenediaminetetraacetic acid, 1.2 to 3 times molar concentration of copper salt concentration, 2 to 25 ml of 37% formalin aqueous solution 1/1.
PHll. 5 to 13.0 is preferred. The temperature is 90
It is best to do this at temperatures below ℃. As explained above, by using the electroless plating solution of the present invention, a plating copper having excellent tensile strength and bending fatigue strength was obtained.
実施例 １〜５
硫酸銅０．０４モル／１、エチレンジアミン四酢酸０．
０５モル／ｌ、ホルムアルデヒド０．０３モル／ｌ、Ｐ
Ｈｌｌ．８の溶液に次表の添加物を添加して無電解銅め
つき液を作成した。Examples 1 to 5 Copper sulfate 0.04 mol/1, ethylenediaminetetraacetic acid 0.
05 mol/l, formaldehyde 0.03 mol/l, P
Hll. An electroless copper plating solution was prepared by adding the additives shown in the following table to the solution of No. 8.
これらのめつき液に活性化処理したステンレス板を浸漬
して７０℃で無電解めつきをおこない、めつき膜厚２５
〜３５μｍの銅箔を得た。An activated stainless steel plate was immersed in these plating solutions and subjected to electroless plating at 70°C, resulting in a plating film thickness of 25%.
A copper foil of ~35 μm was obtained.
めつきの析出速度、得られた銅箔の引張り強度耐折疲労
強度は，次表のとうりである。尚、引張り強度は１０ｍ
ｍ×７０ｍｍの試験片を用い東洋測器製のテンシロン形
万能試験機を用い、つかみ間隔１５ｍｍ引張り速度１ｍ
ｍ／分で測定した。The plating precipitation rate, tensile strength and bending fatigue strength of the resulting copper foil are as shown in the following table. In addition, the tensile strength is 10m
Using a tensilon type universal testing machine made by Toyo Sokki, using a test piece of m x 70 mm, the grip interval was 15 mm and the tensile speed was 1 m.
Measured in m/min.
又、耐折疲労強度の測定はＪＩＳＰ８ｌｌ５に準じた耐
折疲労試験器でおこなつた。折り曲げ点の曲率は半径２
ｍｍのものを使用した。この試験器によれば耐折疲労強
度が試料破断までの折り曲げ回数で示される。比較例
１〜３
硫酸銅０．０４モル／ｌ、エチレンジアミン四酢酸０．
０５モル／ｌ、ホルムアルデヒド０．０３モル／１、Ｐ
Ｈｌｌ．８の溶液に次表の添加物を添加して無電解銅め
つき液を作成し、実施例同様に特性の測定を行なつた。Further, the bending fatigue strength was measured using a bending fatigue tester conforming to JISP8115. The curvature of the bending point is radius 2
mm was used. According to this tester, the bending fatigue strength is indicated by the number of times the sample is bent until it breaks. Comparative example
1-3 Copper sulfate 0.04 mol/l, ethylenediaminetetraacetic acid 0.
05 mol/l, formaldehyde 0.03 mol/1, P
Hll. Additives shown in the following table were added to the solution of No. 8 to prepare an electroless copper plating solution, and the properties were measured in the same manner as in the examples.
Claims (1)
解銅めつき液に、銀イオン供給源とアミノアルコールを
添加したことを特徴とする無電解銅めつき液。 ２ 銀イオン供給源を無電解銅めつき液中の銀イオンの
濃度が、得られためつき銅の引張り強度および耐折疲労
強度の向上が認められかつめつき液が分解しない濃度と
なるように添加するとともに、アミノアルコールを０．
００１ｇ／ｌ以上添加する特許請求の範囲第１項記載の
無電解銅めつき液。 ３ 銀イオン供給源が金属銀、ヨウ化銀である特許請求
の範囲第１項又は第２項記載の無電解銅めつき液。[Claims] 1. Electroless copper plating characterized by adding a silver ion source and an amino alcohol to an electroless copper plating solution containing a copper salt, a complexing agent, a reducing agent, and a pH adjuster. liquid. 2. The silver ion supply source is adjusted so that the concentration of silver ions in the electroless copper plating solution is such that the tensile strength and bending fatigue strength of the resulting matted copper are improved and the plating solution does not decompose. At the same time, 0.0% of amino alcohol was added.
The electroless copper plating solution according to claim 1, wherein the electroless copper plating solution is added in an amount of 0.001 g/l or more. 3. The electroless copper plating solution according to claim 1 or 2, wherein the silver ion source is metallic silver or silver iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2758482A JPS5953349B2 (en) | 1982-02-22 | 1982-02-22 | Electroless copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2758482A JPS5953349B2 (en) | 1982-02-22 | 1982-02-22 | Electroless copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58144465A JPS58144465A (en) | 1983-08-27 |
| JPS5953349B2 true JPS5953349B2 (en) | 1984-12-24 |
Family
ID=12225002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2758482A Expired JPS5953349B2 (en) | 1982-02-22 | 1982-02-22 | Electroless copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5953349B2 (en) |
-
1982
- 1982-02-22 JP JP2758482A patent/JPS5953349B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58144465A (en) | 1983-08-27 |
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