CN104593751A - Ultralow-concentration ion palladium activation solution and process for chemical nickel-plating on copper surface - Google Patents
Ultralow-concentration ion palladium activation solution and process for chemical nickel-plating on copper surface Download PDFInfo
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- CN104593751A CN104593751A CN201410835759.1A CN201410835759A CN104593751A CN 104593751 A CN104593751 A CN 104593751A CN 201410835759 A CN201410835759 A CN 201410835759A CN 104593751 A CN104593751 A CN 104593751A
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Abstract
The invention discloses an ultralow-concentration ion palladium activation solution and a process for chemical nickel-plating on a copper surface. The ultralow-concentration ion palladium activation solution is characterized in that a plating solution comprises the following raw materials: 2-10ppm (palladium ion concentration) of a palladium salt, 0.5-10ml/L of sulfuric acid or hydrochloric acid, 0.01-4g/L of a surfactant, 0.1-10g/L of an accelerant and 1-50mg/L of a stabilizing agent. By using the accelerant, the concentration of palladium ions used by the activation solution can be significantly reduced under the condition that the chemical nickel-plating effect is not influenced, and a construction process is convenient and easy to implement.
Description
Technical field
The present invention relates to chemical conversion treatment technology, more specifically a kind of preprocessing activating liquid at copper surface chemical nickel plating and technique.
Background technology
Chemical Ni-plating layer has the comprehensive physical chemical properties such as outstanding homogeneity, hardness, wear-resisting and solidity to corrosion, this technology is used widely, and all has the application of different ratios in aerospace industry, automotive industry, electronic computer industry, foodstuffs industry, mechanical industry, petroleum industry, plastics industry, Printing industry and valve etc.For course of manufacturing printed circuit board in electronics, the surface treatment flow process of often application is ENIG process (chemical nickel plating leaching gold) and chemical nickel plating porpezite process.In the process of this two type, printed circuit board surface copper wire all needs through activation treatment, can carry out subsequent chemistry nickel deposited and plate palladium or gold-plated process.Because copper is the non-catalytic metal of Hypophosporous Acid, 50 chemical nickel plating.Equally, after ornamental copper piece and nonmetallic surface electroless copper, electro-coppering, need the material of chemical nickel plating process, all need can process through activation treatment.
In producing at present, utilizing ionic palladium to carry out activation is comparatively conveniently treatment process.Easily there is plating leakage or plating phenomenon of overflowing in ionic palladium activation treatment, patent EP2233609A1 and patent CN1222636C is by avoiding the method for carrying out aftertreatment after activation to overflow in nickel plating plating phenomenon in chemical nickel plating.Patent US005219815A describes a kind of low erosion containing ammonia activation solution, and its composition, based on halogenation ammonia and Palladous chloride, adds a small amount of ruthenium chloride and improves activation effect.Be characterized in that the ammonia salt that concentration is higher is that solution provides high stability, solution use temperature, acidity can adjust in a big way.But its precious metal concentration used is higher, improves production cost.In order to reduce production cost, in no-palladium activating, also there is many research in recent years, as patent CN102747345B provides a kind of by the method for leaching nickel activation at PCB copper circuit chemical nickel plating on surface, be characterized in using the method for displacement leaching nickel to come activated copper surface.But it adds temperature of reaction and production stage while the cost that economizes in raw materials.
Therefore, developing low-cost to the method that copper surface chemical nickel plating activates, there is urgent demand, significant to copper surface chemical nickel plating application industry.
Summary of the invention
Object of the present invention is exactly provide a kind of copper surface chemical nickel plating ultralow density ionic palladium activation solution to solve higher or that operation the is loaded down with trivial details drawback of existing copper chemical nickel plating on surface activating technology cost.
Another object of the present invention is to provide a kind of copper surface chemical nickel plating ultralow density ionic palladium activating process.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of copper surface chemical nickel plating ultralow density ionic palladium activation solution, is characterized in that, raw material composition comprises:
In palladium salt, palladium ion concentration controls at 2 ~ 10ppm.
Further illustrate such scheme, described palladium salt is: the one in palladous sulfate, Palladous chloride, dichloro four ammino palladium.
Described tensio-active agent is: stearic acid, the one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, glycerin fatty acid ester, diglycollic amide, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt.
Described accelerator comprises two classes: a class is one or more in the weak oxidants such as copper sulfate, ferric sulfate, sodium peroxide, hydrogen peroxide, persulphate, clorox; Another kind of is one or more in the weak reductants such as aldehyde, formic acid, formate, formic acid ester, glucose, sulfurous acid, sulphite, thiosulphate.
Described stablizer is: one or more in oxysuccinic acid, citric acid, lactic acid, propionic acid, oxyacetic acid, trolamine, glycine, thiocarbamide, potassiumiodide.
A kind of copper surface chemical nickel plating ultralow density ionic palladium activating process, it is characterized in that, it comprises the steps:
A, by described formulated ultralow density ionic palladium activation solution, in process for preparation, each solid ingredient is dissolved respectively, sulfuric acid, tensio-active agent, stablizer, palladium salt is added successively in deionized water, finally adds accelerator, and be diluted to prescribed concentration;
B, the activation solution prepared at room temperature use; By through oil removing, microetch copper piece or cover copper piece flood 30s ~ 3min in activation solution.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
The palladium ion concentration that the present invention uses is low, without the need to heating, without the need to carrying out conservation treatment to nonmetallic surface after activation, is applicable to various Copper base material chemical nickel plating or electroless nickel alloy.
Embodiment
A kind of copper surface chemical nickel plating of the present invention ultralow density ionic palladium activation solution, raw material composition comprises:
Activation solution forms described palladium salt and is water-soluble inorganic salt, and palladium salt consumption is directly connected to the stability of production cost and activation solution, and the too low part copper surface active that easily causes of palladium salt concn is not enough, occurs plating leakage phenomenon in Ni-Speed; The too high activation solution that easily makes of palladium salt concn is unstable, causes palladium ion in the adhesion of nonmetallic surface, just there will be overflow plating, bridging phenomenon in Ni-Speed.In the present invention, palladium ion concentration controls can meet application demand at 2 ~ 10ppm.
Described tensio-active agent is stearic acid, the one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, glycerin fatty acid ester, diglycollic amide, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt; The selection of tensio-active agent can affect activation effect to a certain extent and impact Ni-Speed, if tensio-active agent selection is improper, or consumption is excessive easily in nonmetallic surface absorption, and adheres to the excessive plating that palladium ion causes Ni-Speed.Also may form adsorption layer on copper surface, hinder the displacement of palladium ion and copper, and dosage of surfactant be very few, copper moistened surface may be caused not enough, and activation efficiency reduces even in the plating leakage of Ni-Speed.
Described accelerator is divided into two classes according to its action principle difference, and a class is one or more in the weak oxidants such as copper sulfate, ferric sulfate, sodium peroxide, hydrogen peroxide, persulphate, clorox; Another kind of is one or more in the weak reductants such as aldehyde, formic acid, formate, formic acid ester, glucose, sulfurous acid, sulphite, thiosulphate; Two class accelerators can not use simultaneously, use weak oxidant as accelerator, metallic copper can be made more easily oxidizing reaction to occur, become cupric ion, if use reductive agent palladium ion can be made more easily to reduce as accelerator, form the active site of palladium at copper; Because action principle is different, two class accelerators are in same solution and easily react to each other, therefore only select one when using.
Described stablizer is: one or more in oxysuccinic acid, citric acid, lactic acid, propionic acid, oxyacetic acid, trolamine, glycine, thiocarbamide, potassiumiodide; Stabilizing agent dosage is too much unsuitable, and excessive stablizer can have a strong impact on activation solution activity, hinders the displacement of palladium ion and copper, makes palladium ion at copper surface reduction, can not cause the problem of not plating in Ni-Speed.
Preparation and use: activation solution each solid ingredient in process for preparation is dissolved respectively, sulfuric acid, tensio-active agent, stablizer, palladium salt is added successively in deionized water, finally adds accelerator, and be diluted to prescribed concentration.The activation solution prepared at room temperature can use.By through oil removing, microetch copper piece or cover copper piece flood 30s ~ 3min in activation solution, can plating in chemical nickel-plating liquid through washing after taking-up.
Below in conjunction with specific embodiment, present invention process is described in detail.
Embodiment 1
The glass-fiber-plate (copper-clad plate of PCB glass) being printed on different size and spacing copper cash and copper face is adopted to carry out example test, to facilitate observation with or without plating leakage excessive plating phenomenon.
Activation solution forms:
Operating process:
Sheet material → oil removing → washing → microetch → washing → activation → washing → plating.
Degreasing fluid used is acid deoiling liquid, and reactivation process condition controls: room temperature, nothing stirring, time are 90s.Without plating plating leakage phenomenon of overflowing after sample nickel plating.
Embodiment 2
Activation solution liquid forms:
Condition controls:
Room temperature, soak time 2min, alr mode: test piece is moved.
Operating process is with embodiment 1.Nickel plating is without excessive plating plating leakage phenomenon
Embodiment 3
Activation solution forms:
Condition controls:
Room temperature, without stirring, activation 1min;
Operating process is with embodiment 1, and nickel plating is without excessive plating plating leakage phenomenon.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (7)
1. a copper surface chemical nickel plating ultralow density ionic palladium activation solution, is characterized in that, raw material composition comprises:
Palladium salt,
Sulfuric acid 0.5 ~ 10ml/L, tensio-active agent 0.01 ~ 4g/L,
Accelerator 0.1 ~ 10g/L, stablizer 1 ~ 50mg/L,
In palladium salt, palladium ion concentration controls at 2 ~ 10ppm.
2. copper surface chemical nickel plating ultralow density ionic palladium activation solution according to claim 1, is characterized in that, described palladium salt is the one in palladous sulfate, Palladous chloride, dichloro four ammino palladium.
3. copper surface chemical nickel plating ultralow density ionic palladium activation solution according to claim 1, it is characterized in that, described tensio-active agent is: stearic acid, the one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, glycerin fatty acid ester, diglycollic amide, alkylsulfonate, alkyl, polyether, alkyl ether carboxy acid salt.
4. copper surface chemical nickel plating ultralow density ionic palladium activation solution according to claim 1, is characterized in that, described accelerator is one or more in the weak oxidants such as copper sulfate, ferric sulfate, sodium peroxide, hydrogen peroxide, persulphate, clorox.
5. copper surface chemical nickel plating ultralow density ionic palladium activation solution according to claim 1, it is characterized in that, described accelerator is one or more in the weak reductants such as aldehyde, formic acid, formate, formic acid ester, glucose, sulfurous acid, sulphite, thiosulphate.
6. copper surface chemical nickel plating ultralow density ionic palladium activation solution according to claim 1, it is characterized in that, described stablizer is: one or more in oxysuccinic acid, citric acid, lactic acid, propionic acid, oxyacetic acid, trolamine, glycine, thiocarbamide, potassiumiodide.
7. the ultralow density ionic palladium activating process of the copper surface chemical nickel plating as described in claim 1-6 any one, it is characterized in that, it comprises the steps:
A, by described formulated ultralow density ionic palladium activation solution, in process for preparation, each solid ingredient is dissolved respectively, sulfuric acid, tensio-active agent, stablizer, palladium salt is added successively in deionized water, finally adds accelerator, and be diluted to prescribed concentration;
B, the activation solution prepared at room temperature use; By through oil removing, microetch copper piece or cover copper piece flood 30s ~ 3min in activation solution.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| CN112609172A (en) * | 2020-11-30 | 2021-04-06 | 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 |
| CN114411126A (en) * | 2022-01-26 | 2022-04-29 | 南雄市溢诚化工有限公司 | Ruthenium system-based activation solution 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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| 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 |
| CN112609172A (en) * | 2020-11-30 | 2021-04-06 | 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 |
| CN114411126A (en) * | 2022-01-26 | 2022-04-29 | 南雄市溢诚化工有限公司 | Ruthenium system-based activation solution before chemical nickel plating and preparation method 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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