CN105603472B - Acid copper-plating series additive - Google Patents
Acid copper-plating series additive Download PDFInfo
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- CN105603472B CN105603472B CN201610013697.5A CN201610013697A CN105603472B CN 105603472 B CN105603472 B CN 105603472B CN 201610013697 A CN201610013697 A CN 201610013697A CN 105603472 B CN105603472 B CN 105603472B
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- leveling agent
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to acid copper-plating process sequence additive, belongs to circuit board liquid medicine additive technology field, described acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；The series additive is directed to the unique acid copper-plating series filled out designed by the HDI products of blind hole --- while filling perforation and conducting hole plating copper, coordinated using prepreg solution and fill out blind hole copper plating bath, use series additive provided by the invention, filling perforation effect can be increased and reduce the deposition of plate face copper, plating copper particle has the half bright, uniformity that crystallization is fine and closely woven, ductility is good and splendid.
Description
Technical field
The present invention relates to acid copper-plating process sequence additive, belongs to circuit board liquid medicine additive technology field.
Background technology
Circuit board (PCB) plating processed has very high requirement to the dispersibility and covering power of plating solution.Due to acid copper-plating
The copper deposits for selecting suitable additive to be obtained with, therefore, begin to be applied to PCB in the later stage sixties in last century
Plating.
As Electronic Design is while overall performance is improved constantly, also making great efforts to reduce its size.From mobile phone to intelligence
In the small portable product of weapon, " small " is forever constant pursuit.High Density Integration (HDI) technology can make end product
Design more minimizes, while meets Electronic Performance and the higher standard of efficiency.HDI is now widely used for mobile phone, number
(taking the photograph) camera, MP3, MP4, notebook computer, automotive electronics and other digital products etc., wherein the widest with the application of mobile phone
It is general.And the miniaturization of electronic product brings a series of challenge to component manufacture and printed board processing industry：Product is smaller, member
Device degree of integration is bigger.The high density brought to the manufacture of HDI plates, highly integrated, HDI manufactures is miniaturized to solve electronic product
Industry has started blind hole and has filled out process for copper.
The fast-developing sustainable growth for promoting HDI demands of consumer electronics, it is essential in HDI manufactures that blind hole is filled out in plating
One of process.It is that the electricity that rational additive changes blind hole plate diverse location is added in copper electroplating liquid that blind hole technology is filled out in plating
Flow distribution come realize blind hole fill.Additive master used in the electro-coppering formula for the copper sulphate system that PCB industries use at present
There are three kinds of accelerator, inhibitor and leveling agent.
CN200510106721.1 discloses a kind of electrolytic copper plating bath, and the electrolytic copper plating bath is used for the path to being formed on substrate
Hole carries out through hole filling plating, and it contains water-soluble mantoquita, sulfuric acid, chlorion and the plating agent as additive.It is above-mentioned to plate
Agent is polyvinyl imidazol quaternary ammonium compoundses or vinyl pyrrolidone and vinyl imidazole quaternary ammonium compoundses are total to
Polymers, therefore additive cost can be caused higher.
CN201410853598.9 discloses a kind of printed wiring board and its copper plating process, and the copper plating process includes
Pretreatment procedure, plating copper process and postprocessing working procedures, it is provided between pretreatment procedure and plating copper process and presoaks process, first
Brightener, inhibitor, leveling agent and the sulfuric acid of different component and different ratio are added in preimpregnation and the second preimpregnation respectively.It is but whole
Technique needs to be ultrasonically treated, and increases production process and cost；And fill out blind hole effect and be difficult to reach perfect condition.
With the rapid development of electronic technology, to meet the production requirement of HDI plates, to the need of high-quality plating copper additives
Ask increasing.Market has very big advantage to import additive at home, but price is high, and domestic autonomous production really is able to
Meet that the product of requirement is less.
The content of the invention
The problem of present invention exists for prior art, there is provided a kind of acid copper-plating process sequence additive, be directed to and fill out
Unique acid copper-plating series designed by the HDI products of blind hole --- while filling perforation and conducting hole plating copper, coordinated using prepreg solution
Blind hole copper plating bath is filled out, using series additive provided by the invention, filling perforation effect can be increased and reduce the deposition of plate face copper, plating
Copper particle has the half bright, uniformity that crystallization is fine and closely woven, ductility is good and splendid.
In order to solve the above problems, the technical solution adopted in the present invention is：
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：80~90 parts of deionized water, 3~6 parts of copper sulphate, polyethylene glycol 5
~10 parts, 2~5 parts of formaldehyde；
Described carrying agent, the parts by volume of each component are：80~85 parts of deionized water, 2~4 parts of sulfuric acid, copper sulphate 2~4
Part, 9~15 parts of polyethers, 1~3 part of formaldehyde；
Described brightener, the parts by volume of each component are：80~88 parts of deionized water, 1~3 part of sulfuric acid, copper sulphate 2~4
Part, 8~16 parts of polyethylene glycol, 1~5 part of formaldehyde；
Described leveling agent, the parts by volume of each component are：80~90 parts of deionized water, 4~5 parts of copper sulphate, polyethers 5~10
Part, 1~3 part of formaldehyde；
Described leveling agent replenishers, the parts by volume of each component are：85~90 parts of deionized water, 1~5 part of copper sulphate, gather
1~5 part of ethylene glycol, 1~5 part of formaldehyde；
Described formaldehyde, it is the formalin that volume fraction is 37%.
Described acid copper-plating series additive, its application method are that pre- 90~110mL/L of preserved material is added before electroplating, 20~
27 DEG C of 4~6min of immersion；In electroplate liquid addition carrying agent, brightener, leveling agent, volume ratio be respectively 10~20mL/L, 3~
6mL/L/, 10~20mL/L；Tank liquor composition, which is added, to be divided into for carrying 50~100ml/1000AH of agent, 200~400ml/ of brightener
1000AH, 200~300ml/1000AH of leveling agent replenishers.
The beneficial effects of the invention are as follows：
Using acid copper-plating process sequence additive provided by the invention, there is advantages below：
1st, plating solution performance is stable --- and splendid filling perforation effect and conducting hole depth plating power are good, filling perforation rate ＞ 85%；
2nd, electroplating copper particle has the bright, uniformity that crystallization is fine and closely woven, ductility is good and splendid；
3rd, direct current plating method and copper anode can be used to produce；
4th, additive is stable, stops bursting at the seams after line to be not required to the Dummy programs of complexity, can use Hou Shi grooves and CVS analysis and Controls；
5th, identical with general plating flow, without extra pre-treatment, decoction management is easy, can be done with existing legacy equipment
Simple modification uses；
6th, cost is cheap, available for industrial large-scale application.
7th, it is using rear electrodeposited coating feature：
Electroplate Rotating fields：Copper ion crystal is fine and closely woven
Density：8.9g/cm3；
Elongation：More than 15%；
Tensile strength：280-350N/mm2；
Thermal stress is tested：Qualified, 6 times floating tin is tested 288 DEG C/10 seconds.
Embodiment
The present invention is described in further details below by embodiment, these embodiments are only used for illustrating the present invention, and
Do not limit the scope of the invention.
Embodiment 1
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：80 parts of deionized water, 3 parts of copper sulphate, 5 parts of polyethylene glycol, formaldehyde
2 parts；
Described carrying agent, the parts by volume of each component are：80 parts of deionized water, 2 parts of sulfuric acid, 2 parts of copper sulphate, 9 parts of polyethers,
1 part of formaldehyde；
Described brightener, the parts by volume of each component are：80 parts of deionized water, 1 part of sulfuric acid, 2 parts of copper sulphate, polyethylene glycol
8 parts, 1 part of formaldehyde；
Described leveling agent, the parts by volume of each component are：80 parts of deionized water, 4 parts of copper sulphate, 5 parts of polyethers, formaldehyde 1~3
Part；
Described leveling agent replenishers, the parts by volume of each component are：Deionized water 85,1 part of copper sulphate, 1 part of polyethylene glycol,
1 part of formaldehyde；
Described acid copper-plating series additive, to add pre- preserved material 90mL/L before plating, 20 DEG C are soaked its application method
4min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 10mL/L, 3mL/L/, 10mL/L；Tank liquor
Composition, which is added, to be divided into for carrying agent 50ml/1000AH, brightener 200ml/1000AH, leveling agent replenishers 200ml/1000AH.
Embodiment 2
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：90 parts of deionized water, 6 parts of copper sulphate, 10 parts of polyethylene glycol, first
5 parts of aldehyde；
Described carrying agent, the parts by volume of each component are：85 parts of deionized water, 4 parts of sulfuric acid, 4 parts of copper sulphate, polyethers 15
Part, 3 parts of formaldehyde；
Described brightener, the parts by volume of each component are：88 parts of deionized water, 3 parts of sulfuric acid, 4 parts of copper sulphate, polyethylene glycol
16 parts, 5 parts of formaldehyde；
Described leveling agent, the parts by volume of each component are：90 parts of deionized water, 5 parts of copper sulphate, 10 parts of polyethers, formaldehyde 3
Part；
Described leveling agent replenishers, the parts by volume of each component are：90 parts of deionized water, 5 parts of copper sulphate, polyethylene glycol 5
Part, 5 parts of formaldehyde；
Described acid copper-plating series additive, to add pre- preserved material 110mL/L before plating, 27 DEG C are soaked its application method
6min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 20mL/L, 6mL/L/, 20mL/L；Tank liquor
Composition, which is added, to be divided into for carrying agent 100ml/1000AH, brightener 400ml/1000AH, leveling agent replenishers 300ml/1000AH.
Embodiment 3
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：85 parts of deionized water, 4.5 parts of copper sulphate, 8 parts of polyethylene glycol, first
3.55 parts of aldehyde；
Described carrying agent, the parts by volume of each component are：83 parts of deionized water, 3 parts of sulfuric acid, 3 parts of copper sulphate, polyethers 12
Part, 2 parts of formaldehyde；
Described brightener, the parts by volume of each component are：84 parts of deionized water, 2 parts of sulfuric acid, 3 parts of copper sulphate, polyethylene glycol
12 parts, 3 parts of formaldehyde；
Described leveling agent, the parts by volume of each component are：85 parts of deionized water, 4.5 parts of copper sulphate, 8 parts of polyethers, formaldehyde 2
Part；
Described leveling agent replenishers, the parts by volume of each component are：87 parts of deionized water, 3 parts of copper sulphate, polyethylene glycol 1
~5 parts, 3 parts of formaldehyde；
Described acid copper-plating series additive, to add pre- preserved material 100mL/L before plating, 23 DEG C are soaked its application method
5min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 15mL/L, 4.5mL/L/, 15mL/L；Groove
Liquid composition, which is added, to be divided into for carrying agent 75ml/1000AH, brightener 300ml/1000AH, leveling agent replenishers 250ml/
1000AH。
Embodiment 4
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：82 parts of deionized water, 4 parts of copper sulphate, 6 parts of polyethylene glycol, formaldehyde
3 parts；
Described carrying agent, the parts by volume of each component are：81 parts of deionized water, 2.5 parts of sulfuric acid, 2.5 parts of copper sulphate, polyethers
11 parts, 1.5 parts of formaldehyde；
Described brightener, the parts by volume of each component are：82 parts of deionized water, 1.5 parts of sulfuric acid, 2.5 parts of copper sulphate, poly- second
10 parts of glycol, 2 parts of formaldehyde；
Described leveling agent, the parts by volume of each component are：83 parts of deionized water, 4 parts of copper sulphate, 6 parts of polyethers, formaldehyde 1.5
Part；
Described leveling agent replenishers, the parts by volume of each component are：86 parts of deionized water, 2 parts of copper sulphate, polyethylene glycol 1
~5 parts, 2 parts of formaldehyde；
Described acid copper-plating series additive, to add pre- preserved material 95mL/L before plating, 21 DEG C are soaked its application method
4.5min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 13mL/L, 4mL/L/, 12mL/L；Groove
Liquid composition, which is added, to be divided into for carrying agent 58ml/1000AH, brightener 260ml/1000AH, leveling agent replenishers 210ml/
1000AH。
Embodiment 5
Acid copper-plating series additive, including pre- preserved material, carrying agent, brightener, leveling agent, leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：88 parts of deionized water, 5 parts of copper sulphate, 8 parts of polyethylene glycol, formaldehyde
4 parts；
Described carrying agent, the parts by volume of each component are：84 parts of deionized water, 3.5 parts of sulfuric acid, 3.5 parts of copper sulphate, polyethers
13 parts, 2.5 parts of formaldehyde；
Described brightener, the parts by volume of each component are：87 parts of deionized water, 2.5 parts of sulfuric acid, 3.5 parts of copper sulphate, poly- second
13 parts of glycol, 4 parts of formaldehyde；
Described leveling agent, the parts by volume of each component are：87 parts of deionized water, 5 parts of copper sulphate, 8 parts of polyethers, formaldehyde 2.5
Part；
Described leveling agent replenishers, the parts by volume of each component are：88 parts of deionized water, 4 parts of copper sulphate, polyethylene glycol 4
Part, 4 parts of formaldehyde；
Described acid copper-plating series additive, to add pre- preserved material 105mL/L before plating, 26 DEG C are soaked its application method
5.5min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 17mL/L, 5mL/L/, 18mL/L；Groove
Liquid composition, which is added, to be divided into for carrying agent 85ml/1000AH, brightener 350ml/1000AH, leveling agent replenishers 270ml/
1000AH。
Claims (1)
1. acid copper-plating series additive, it is characterised in that：The additive include pre- preserved material, carrying agent, brightener, leveling agent,
Leveling agent replenishers；
Described pre- preserved material, the parts by volume of each component are：80~90 parts of deionized water, 3~6 parts of copper sulphate, polyethylene glycol 5~10
Part, 2~5 parts of formaldehyde；
Described carrying agent, the parts by volume of each component are：It is 80~85 parts of deionized water, 2~4 parts of sulfuric acid, 2~4 parts of copper sulphate, poly-
9~15 parts of ether, 1~3 part of formaldehyde；
Described brightener, the parts by volume of each component are：It is 80~88 parts of deionized water, 1~3 part of sulfuric acid, 2~4 parts of copper sulphate, poly-
8~16 parts of ethylene glycol, 1~5 part of formaldehyde；
Described leveling agent, the parts by volume of each component are：80~90 parts of deionized water, 4~5 parts of copper sulphate, 5~10 parts of polyethers,
1~3 part of formaldehyde；
Described leveling agent replenishers, the parts by volume of each component are：85~90 parts of deionized water, 1~5 part of copper sulphate, poly- second two
1~5 part of alcohol, 1~5 part of formaldehyde；
Described acid copper-plating series additive, its application method are that pre- 90~110mL/L of preserved material is added before electroplating, 20~27 DEG C
Soak 4~6min；Addition carrying agent, brightener, leveling agent in electroplate liquid, volume ratio is respectively 10~20mL/L, 3~6mL/
L, 10~20mL/L；Tank liquor composition add part for carrying agent 50~100mL/1000AH, 200~400mL of brightener/
1000AH, 200~300mL of leveling agent replenishers/1000AH；
Described formaldehyde is the formalin of volume fraction 37%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610013697.5A CN105603472B (en) | 2016-01-05 | 2016-01-05 | Acid copper-plating series additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610013697.5A CN105603472B (en) | 2016-01-05 | 2016-01-05 | Acid copper-plating series additive |
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| CN105603472A CN105603472A (en) | 2016-05-25 |
| CN105603472B true CN105603472B (en) | 2018-03-20 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203836B (en) * | 2016-12-19 | 2021-12-17 | 艾威尔电路（深圳）有限公司 | Method for improving deep plating capacity of electroplated copper |
| CN107385487B (en) * | 2017-07-24 | 2019-05-10 | 电子科技大学 | Tetra- oxa- -3,9- of 2,4,8,10-, two phospha spiro-compound is in the application of HDI plate copper plating rapidly pretreatment solution and its pre-treating technology |
| CN110241445B (en) * | 2019-06-26 | 2021-06-08 | 北京化工大学 | High-efficiency pore-filling acidic copper plating solution and electronic chemical additive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| CN102912395A (en) * | 2012-11-15 | 2013-02-06 | 苏州正信电子科技有限公司 | Method for filling blind-buried holes through electro-coppering |
-
2016
- 2016-01-05 CN CN201610013697.5A patent/CN105603472B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| CN102912395A (en) * | 2012-11-15 | 2013-02-06 | 苏州正信电子科技有限公司 | Method for filling blind-buried holes through electro-coppering |
Non-Patent Citations (3)
| Title |
|---|
| PCB盲孔填孔电镀中光泽剂及工艺条件的影响研究;伊洪坤等;《印制电路信息》;20140310(第3期);第50-53页 * |
| VF添加剂在电镀填孔中的应用;程军;《印制电路信息》;20130310(第3期);第36页表1 * |
| 一种快速填盲孔的工艺及原理研究;朱凯等;《印制电路信息》;20150310(第3期);第112-116页 * |
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