CN104593751B - Copper surface chemical nickel plating super low concentration ionic palladium activating solution and technique - Google Patents
Copper surface chemical nickel plating super low concentration ionic palladium activating solution and technique Download PDFInfo
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- CN104593751B CN104593751B CN201410835759.1A CN201410835759A CN104593751B CN 104593751 B CN104593751 B CN 104593751B CN 201410835759 A CN201410835759 A CN 201410835759A CN 104593751 B CN104593751 B CN 104593751B
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- palladium
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Abstract
The invention discloses a kind of copper surface chemical nickel plating super low concentration ionic palladium activating solution and technique, it is characterised in that plating solution raw materials composition includes：2~10ppm of palladium salt (palladium ion concentration), 0.5~10ml/L of sulfuric acid or hydrochloric acid, 0.01~4g/L of surfactant, 0.1~10g/L of accelerator, 1~50mg/L of stabilizer.By the present invention in that with accelerator, the palladium ion concentration that activating solution is used can be significantly reduced in the case where not influenceing chemical nickel plating effect, construction technology is convenient and easy.
Description
Technical field
The present invention relates to chemical surface treatment technology, more specifically a kind of preceding processing in copper surface chemical nickel plating is lived
Change liquid and technique.
Background technology
Chemical Ni-plating layer has the comprehensive physical chemical property such as outstanding uniformity, hardness, wear resisting and corrosion resistance, this skill
Art has been used widely, aerospace industry, auto industry, electronic computer industry, food industry, mechanical industry,
Petroleum industry, plastics industry, printing industry and valve etc. have the application of different proportion.To print electricity in electronic equipment
Exemplified by the board manufacturing process of road, the surface treatment flow often applied is ENIG processes (chemical nickel plating leaching gold) and chemical nickel plating porpezite
Process.During both types, printed circuit board surface copper wire is required to by activation process, after can carrying out
Continuous chemical deposited nickel and plating palladium or gold-plated process.Because copper is the non-catalytic metal of hypophosphorous acid chemical nickel plating.Equally,
Needed after ornamental copper piece and nonmetallic surface electroless copper, electro-coppering chemical nickel plating handle material, be required to by
Activation process can be processed.
In current production, it is more convenient efficiently processing method to carry out activation using ionic palladium.At ionic palladium activation
Easily there is plating leakage or plating phenomenon of overflowing in chemical nickel plating in reason, and patent EP2233609A1 and patent CN1222636C pass through living
The method post-processed after change plates phenomenon to avoid overflowing in nickel plating.Patent US005219815A describes a kind of low corrode and contains ammonia
Activating solution, it is constituted based on halogenation ammonia and palladium bichloride, is added a small amount of ruthenic chloride and is improved activation effect.It is characterized in that concentration is higher
Ammonia salt provide high stability for solution, solution temperature in use, acidity can be in interior adjustment in a big way.But its use it is expensive
Metal concentration is higher, improves production cost.In order to reduce production cost, in terms of no-palladium activating, also there is many grind in recent years
Study carefully, such as patent CN102747345B provides a kind of by soaking method of the nickel activation in PCB copper circuit chemical nickel plating on surface, its spy
Point is to activate copper surface using the method for displacement leaching nickel.But its save cost of material while add reaction temperature and
Production stage.
Therefore, developing low-cost has urgent demand to the method that copper surface chemical nickel plating is activated, to copper table
Face chemical nickel plating application industry is significant.
The content of the invention
The purpose of the present invention is exactly that existing copper chemical nickel plating on surface activating technology cost is higher or tedious process in order to solve
The drawbacks of a kind of copper surface chemical nickel plating super low concentration ionic palladium activating solution is provided.
It is a further object of the present invention to provide a kind of copper surface chemical nickel plating super low concentration ionic palladium activating process.
The present invention is to realize above-mentioned purpose using following technical solution：A kind of copper surface chemical nickel plating is with ultralow dense
Spend ionic palladium activating solution, it is characterised in that raw material composition includes：
Palladium ion concentration control is in 2~10ppm in palladium salt.
Such scheme is further illustrated, the palladium salt is：One kind in palladium sulfate, palladium bichloride, the ammino palladium of dichloro four.
The surfactant is：Stearic acid, neopelex, lauryl sodium sulfate, fatty glyceride,
One kind in diglycollic amide, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt.
The accelerator includes two classes：One class is copper sulphate, ferric sulfate, sodium peroxide, hydrogen peroxide, persulfate, secondary chlorine
One or more in the weak oxidants such as sour sodium；Another kind of is aldehyde, formic acid, formates, formic acid ester, glucose, sulfurous acid, Asia
One or more in the weak reductants such as sulfate, thiosulfate.
The stabilizer is：Malic acid, citric acid, lactic acid, propionic acid, hydroxyacetic acid, triethanolamine, glycine, thiocarbamide, iodine
Change the one or more in potassium.
A kind of copper surface chemical nickel plating super low concentration ionic palladium activating process, it is characterised in that it comprises the following steps：
A, by it is described formula prepare super low concentration ionic palladium activating solution, each solid constituent dissolves respectively in process for preparation,
Sulfuric acid, surfactant, stabilizer, palladium salt are sequentially added in deionized water, accelerator is eventually adding, and be diluted to specified dense
Degree；
The activating solution that b, preparation are completed is used at room temperature；By the copper piece Jing Guo oil removing, microetch or copper piece is covered in activating solution
Middle dipping 30s~3min.
The beneficial effect that the present invention can be reached using above-mentioned technical solution is：
The palladium ion concentration that the present invention is used is low, without heating, without being carried out after activation to nonmetallic surface at protection
Reason, it is adaptable to various Copper base material chemical nickel platings or electroless nickel alloy.
Embodiment
A kind of copper surface chemical nickel plating super low concentration ionic palladium activating solution of the present invention, raw material composition includes：
It is water-soluble inorganic salt that activating solution, which constitutes the palladium salt, and palladium salt consumption is directly connected to cost and the activation of production
The stability of liquid, the too low part copper surface active that easily causes of palladium salt concentration is not enough, occurs plating leakage phenomenon in Ni-Speed；Palladium
Salinity is too high easily to make activating solution unstable, causes palladium ion in the adhesion of nonmetallic surface, will go out in Ni-Speed
Now overflow plating, bridging phenomenon.Palladium ion concentration control can meet application demand in 2~10ppm in the present invention.
The surfactant be stearic acid, neopelex, lauryl sodium sulfate, fatty glyceride,
One kind in diglycollic amide, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt；The selection of surfactant can be certain
Activation effect is influenceed in degree and Ni-Speed is impacted, if surfactant selection is improper, or consumption is excessive easily
In nonmetallic surface absorption, and adhere to the excessive plating that palladium ion causes Ni-Speed.Adsorption layer, resistance may also can be formed on copper surface
Hinder the displacement of palladium ion and copper, and dosage of surfactant is very few, is likely to result in copper moistened surface deficiency, activation efficiency reduction
Even in the plating leakage of Ni-Speed.
The accelerator is divided into two classes according to its action principle difference, and a class is copper sulphate, ferric sulfate, sodium peroxide, double
One or more in the weak oxidants such as oxygen water, persulfate, sodium hypochlorite；Another kind of is aldehyde, formic acid, formates, formic acid
One or more in the weak reductants such as ester, glucose, sulfurous acid, sulphite, thiosulfate；Two class accelerators can not be same
When use, using weak oxidant as accelerator, can make metallic copper be easier occur oxidation reaction, be changed into copper ion, use
If reducing agent can make palladium ion be more easy to reduction as accelerator, in the active site of copper formation palladium；Because action principle is different, two
Class accelerator is in same solution and easily reacted to each other, therefore one is only selected when using.
The stabilizer is：Malic acid, citric acid, lactic acid, propionic acid, hydroxyacetic acid, triethanolamine, glycine, thiocarbamide, iodine
Change the one or more in potassium；Stabilizing agent dosage should not be excessive, and excessive stabilizer can have a strong impact on activating solution activity, hinder palladium
The displacement of ion and copper, prevents palladium ion from copper surface reduction, the problem of causing not plating in Ni-Speed.
Prepare and use：Activating solution each solid constituent in process for preparation dissolves respectively, by sulfuric acid, surfactant, steady
Determine agent, palladium salt to sequentially add in deionized water, be eventually adding accelerator, and be diluted to prescribed concentration.Prepare the activating solution completed
It can be used at room temperature.By the copper piece Jing Guo oil removing, microetch or cover copper piece 30s~3min is impregnated in activating solution, after taking-up
Can the plating in chemical nickel-plating liquid by washing.
Present invention process is described in detail with reference to specific embodiment.
Embodiment 1
Example test is carried out using the glass-fiber-plate (copper-clad plate of PCB glasses) for being printed on different size and spacing copper cash and copper face,
To facilitate observation whether there is the excessive plating phenomenon of plating leakage.
Activating solution is constituted：
Operating process：
Sheet material → oil removing → washing → microetch → washing → activation → washing → plating.
Degreasing fluid used is acid deoiling liquid, the control of activation process condition：Room temperature, without stirring, the time be 90s.Sample is plated
Without plating plating leakage phenomenon of overflowing after nickel.
Embodiment 2
Activating solution liquid is constituted：
Condition is controlled：
Room temperature, soak time 2min, agitating mode：Test piece is moved.
Operating process be the same as Example 1.Nickel plating is without excessive plating plating leakage phenomenon
Embodiment 3
Activating solution is constituted：
Condition is controlled：
Room temperature, no stirring activates 1min；
Operating process be the same as Example 1, nickel plating is without excessive plating plating leakage phenomenon.
Above-described is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection domain.
Claims (3)
1. a kind of copper surface chemical nickel plating super low concentration ionic palladium activating solution, it is characterised in that raw material composition includes：
Palladium salt,
The ml/L of sulfuric acid 0.5 ~ 10, the g/L of surfactant 0.01 ~ 4,
The g/L of accelerator 0.1~10, the mg/L of stabilizer 1~50,
Palladium ion concentration control is in 2~10 ppm in activating solution；
The accelerator is one kind or many in copper sulphate, ferric sulfate, sodium peroxide, hydrogen peroxide, persulfate, sodium hypochlorite
Kind, or, it is one kind or many in aldehyde, formic acid, formates, formic acid esters, glucose, sulfurous acid, sulphite, thiosulfate
Kind；The surfactant is：Stearic acid, neopelex, lauryl sodium sulfate, fatty glyceride, diethyl
One kind in alkylolamides, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt；The stabilizer is：Malic acid, citric acid,
One or more in lactic acid, propionic acid, hydroxyacetic acid, triethanolamine, glycine, thiocarbamide, KI.
2. copper surface chemical nickel plating according to claim 1 super low concentration ionic palladium activating solution, it is characterised in that described
Palladium salt is one kind in palladium sulfate, palladium bichloride, the ammino palladium of dichloro four.
3. a kind of copper surface chemical nickel plating with described in claim 1-2 any one is corresponding with super low concentration ionic palladium activating solution
Copper surface chemical nickel plating super low concentration ionic palladium activating process, it is characterised in that it comprises the following steps：
A, by the raw material composition prepare super low concentration ionic palladium activating solution, each solid constituent dissolves respectively in process for preparation,
Sulfuric acid, surfactant, stabilizer, palladium salt are sequentially added in deionized water, accelerator is eventually adding, and be diluted to specified dense
Degree；
The activating solution that b, preparation are completed is used at room temperature；By the copper piece Jing Guo oil removing, microetch or cover copper piece and soaked in activating solution
Stain 30s ~ 3min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106282978A (en) * | 2016-08-31 | 2017-01-04 | 上海芮远化学科技有限公司 | For ionic palladium activating solution making conductor line on pottery and preparation method thereof |
| CN109837532A (en) * | 2017-11-24 | 2019-06-04 | 天津环鑫科技发展有限公司 | A kind of nickel plating activating solution, configuration method, application, silicon wafer activation method and nickel plating process |
| CN108728830A (en) * | 2018-07-12 | 2018-11-02 | 深圳市化讯半导体材料有限公司 | A kind of ionic palladium activator and its preparation method and application |
| CN109136887A (en) * | 2018-10-10 | 2019-01-04 | 深圳市互连微电子材料有限公司 | A kind of copper surface chemical nickel plating ionic palladium activating solution and preparation method |
| CN110643982A (en) * | 2019-11-14 | 2020-01-03 | 苏州天承化工有限公司 | Ionic palladium activation solution and preparation method and application thereof |
| CN111455360A (en) * | 2020-05-06 | 2020-07-28 | 广东工业大学 | Chemical palladium plating reducing agent and chemical palladium plating solution |
| CN112609172B (en) * | 2020-11-30 | 2021-09-28 | 江苏矽智半导体科技有限公司 | Chemical palladium plating solution for wafer packaging field and preparation method thereof |
| CN114086160A (en) * | 2021-11-10 | 2022-02-25 | 江苏艾森半导体材料股份有限公司 | Copper surface chemical plating palladium activating solution and application thereof |
| CN114411126B (en) * | 2022-01-26 | 2023-09-05 | 南雄市溢诚化工有限公司 | Activating solution based on ruthenium system and used before chemical nickel plating and preparation method thereof |
| CN115404468A (en) * | 2022-08-24 | 2022-11-29 | 广东致卓环保科技有限公司 | Active colloidal palladium for chemical nickel plating of ABS alloy and preparation process thereof |
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| EP0109402B1 (en) * | 1982-05-26 | 1988-06-01 | Macdermid, Incorporated | Catalyst solutions for activating non-conductive substrates and electroless plating process |
| US20020062760A1 (en) * | 2000-11-06 | 2002-05-30 | Ronald Redline | Catalyst solutions useful in activating substrates for subsequent plating |
| CN102677027B (en) * | 2012-05-25 | 2013-10-30 | 广州市天承化工有限公司 | Activating solution composition for nonmetallic material electroless plating |
| CN104178752B (en) * | 2013-05-23 | 2017-09-26 | 中国科学院大连化学物理研究所 | A kind of chemical palladium-plating or its alloy film carry out the activation method before chemical plating |
| CN103556134B (en) * | 2013-11-13 | 2015-11-25 | 湖南省化讯应用材料有限公司 | The pretreatment process of process for electroless nickel plating |
| CN103981514A (en) * | 2014-06-11 | 2014-08-13 | 深圳市兴经纬科技开发有限公司 | Circuit board chemical nickel plating activation fluid and activation method |
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