CN110396706A - A kind of pcb board non-cyanide copper electroplating brightener and its application method - Google Patents
A kind of pcb board non-cyanide copper electroplating brightener and its application method Download PDFInfo
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- CN110396706A CN110396706A CN201910819193.6A CN201910819193A CN110396706A CN 110396706 A CN110396706 A CN 110396706A CN 201910819193 A CN201910819193 A CN 201910819193A CN 110396706 A CN110396706 A CN 110396706A
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- brightener
- pcb board
- plating
- copper
- pcb
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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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to a kind of pcb board cyanideless electro-plating copper electrolyte and method containing brightener, plating solution, includingIt is characterized in that the brightener preferably comprises the sulfur-containing compound of thienyl group, the sulfur-containing compound of more preferably following structural formula I
Description
Technical field
The present invention relates to printed circuit board (PCB) manufacturing fields, more particularly to a kind of pcb board non-cyanide copper electroplating brightener
And its application method.
Background technique
PCB acid copper is in PCB manufacture through common processing procedure, and in PCB electro-coppering, it is heavy to be occasionally found partial circuit plate
Phenomena such as lamination brightness irregularities, brightness shades, electric signal transmission performance is not only affected, is also unfavorable for party in request before examining goods
Audit requirement when order, is unfavorable for externally doing business.
Chinese invention patent application CN108286063A proposes a kind of PCB pattern electro-plating method, comprising the following steps:
(1) acidity is deoiled, and pcb board is put into the acidity that temperature is 35-45 DEG C and is gone in oil liquid, and maintains 3-5min, removal pcb board face oil
Rouge；(2) pcb board is put into the micro-corrosion liquid that temperature is 26-30 DEG C, and maintains 1-2min by microetch, removal plate face oxidation, and thick
Change plate face；(3) copper facing: pcb board is put into the copper plating bath that temperature is 22-28 DEG C, and with the electricity of 1-3A/dm2 by configuration copper plating bath
Current density copper facing thickeies the layers of copper in plate face and hole；(4) pure tin is plated: configuration tin plating electrolyte；It is 19-25 that pcb board, which is put into temperature,
DEG C tin plating electrolyte in, plate pure tin resist layer in route patterned surface, complete PCB pattern plating.Wherein it is in the publication
Overcome plate face coating specifically to use suitable copper brightener 125T without dim, coarse phenomenon, while realizing high potential area
Phenomena such as without plate is burnt.
Chinese invention patent application CN201610648970.1 discloses a kind of process for pcb board electro-coppering,
Process is largely divided into following steps: 1) deburring, including into plate, nog plate, high-pressure washing, drying ejecting plate again；2) heavy copper, packet
It includes upper plate, bulk, first wash, desmearing, second wash, preneutralization, third time washing, neutralization, ultrasonic wave water washing, remove
Oily, rear oil removing, the 4th washing, light erosion, the 5th washing, preimpregnation, activation, acceleration, the 6th washing, electroless copper plating, pickling,
7th washing；3) copper, including upper plate, oil removing, washing, acidleach, thickening plating, high-order washing, lower plate are thickeied.Wherein copper plating bath is adopted
It is PM-501 with brightener, one or both of perseverance emigrant's ST-2000 series.
Chinese invention patent application CN201310585204.1 discloses a kind of PCB blind hole copper electroplating solution and its preparation side
Method and electro-plating method, the copper electroplating solution each component and its content are as follows: cupric sulfate pentahydrate: 100~300g/L, sulfuric acid: 50~
200g/L, chloride ion: 30~100ppm, brightener: 5~50g/L, carrying agent: 3~30g/L, leveling agent: 2~20g/L, go from
Sub- water surplus；And the concentration of cupric sulfate pentahydrate and sulfuric acid ratio is 1.5~2: 1.Electro-plating method of the invention are as follows: will be with blind hole
Pcb board is put into the electroplating bath equipped with the copper electroplating solution and is electroplated under air stirring, obtains copper plate.
Aforementioned documents are that domestic brightener addition related for several documents only in PCB electroplating technology processing procedure uses
It records, wherein only have part is coarse to plate face dimness to be paid close attention to research, it is most of that brightener is all only generally added, although such as
This, such document is also very few.
However it is well known that brightening agent is a kind of widely used additive, and make extensively in copper facing
With such as:
Chinese invention patent application CN201710480380.7 discloses a kind of electro-coppering brightener.The brightener passes through
The raw material composition of following parts by weight: plating dyestuff 5-10 parts, 3.2-4 parts of disodium ethylene diamine tetraacetate, sodium thiosulfate 4.5-5.2
Part, 1.5-2 parts of polyethylene glycol, 5.6-6.3 parts of potassium dihydrogen phosphate, 11-16 parts of aminopyridine, 80-85 parts of water.
In addition, a kind of cyanide-free copper electroplating brightener, the brightener includes component A and B component, and wherein component A is 5,5- bis-
Methyl hydantoin and/or 5,5- Dimethyl Hydan derivative, B component are imidazoline pyridine diketone and/or imidazoline pyridine derovatives
Also as disclosed in Chinese invention patent application CN201810983278.3.
More suchlike brightening agent is related to one kind in addition, Chinese invention patent discloses CN108265317A
Compound copper facing uses up bright dose, belongs to electroplating additive technical field.The present invention passes through maleic anhydride, acrylic acid as former first
Material carries out polymerization and forms copolymer under the action of ammonium persulfate, in the course of the polymerization process, utilizes addition sodium vedproate, vinyl
Phosphonic acids is grafted in copolymer by the catalytic action of strongly acidic styrene type cation exchange resin, then again with N,
Dinethylformamide, methyl phenyl ethers anisole, glycidyl methacrylate etc. are polymerize as raw material, and two kinds of polymer has excellent
Good dispersion performance, can make copper ion be uniformly dispersed in matrix surface carry out copper facing, and be added benzalacetone,
Salicylide can slow down rate of crystal growth, accelerate nucleus formation speed, raising is the compactness of copper plate crystal grain, adds table
Face activating agent reduces the generation of pin hole under the action of auxiliary agent, while the knot of coating and matrix is strengthened using the effect of auxiliary agent
Close performance.
Document as above, although electro-coppering brightener is a very mature addition kind, as technological progress
It pursues in a steady stream, still there are many additive documents to emerge in large numbers, but say as discussed above and the adaptability of pcb board is not carried out
Enough concerns, therefore general plating copper additives often add in the plating solution in pcb board, for obtained coated metal
Connecting line is in frequent signal transmission in the future or plugs in micro- contact process, it is possible to create detrimental effect, not such as coating
There is the light of technical need needed for realizing, coating compound is micro- to be mingled with caused potential thermal decomposition.
Summary of the invention
The present invention is that the defect of solution aforementioned background art part proposes a kind of pcb board electro-coppering brightener containing Formulas I,
And its plating solution and application method, it is specific as follows:
A kind of pcb board cyanideless electro-plating copper electrolyte containing brightener, including
The brightener preferably comprises the sulfur-containing compound of thienyl group, the sulfur-bearing chemical combination of more preferably following structural formula I
Object
The brightener is the sulfur-containing compound for preferably comprising thienyl group.
The brightener is preferred compound of formula I.
The further technical solution of the present invention also resides in the compound of formula I and makees in pcb board cyanideless electro-plating copper electrolyte
For the purposes of brightener.
Further embodiment of the present invention is using a kind of aforementioned pcb board cyanideless electro-plating containing brightener
The copper plating process of copper electrolyte.
The technique uses the aforementioned preferred brightener.
Further, there are also the second element sulphur groups in addition to thienyl group for the brightener.
Further second element sulphur is close to thienyl group；
Specifically the second element sulphur group is thione group.
The present invention is further described in detail and is summarized as follows compared with prior art with remarkable advantage:
It is many for the research of brightener in the prior art, as the sulphur system brightener of brightener family, in the industry
Through being known as the general surface-active aromatic sulphonate with sulfurous acid key (=CH-SO3-) bonding, specific example is such as
Sulfimide class, sulfonamides, benzene sulfonyl class, sulfinic acid class, interior sulphonic acids, heterocyclic sulfonic acid class, but it is lasting as one
The light of technical need is benign, and above-mentioned brightener is far from satisfying demand, and it is special that the present inventor is found surprisingly that Formulas I chemical combination has
Bright performance, be not covered by above-mentioned generic concept consciousness brightener classification in, and by screening experiment find in PCB
There is good application in copper facing；In view of the structural complexity of above-mentioned substance, inventor infers its excellent bright performance not merely
It is due to possessed thienyl group, is the element knot that possible obtain bright performance with the adjacent thione group cooperation of thienyl group
Structure performance, the electron group in the amino fragment contained simultaneously in nitrogen-atoms advantageously form multivalent state coordination, and with branch
Phenyl ring advantageously form steric effect, be that may cause bright another factor, in any case, although can not be from scientific real
Testing angle completely proves that the above-mentioned inference of inventor is correct, but finally obtains in test the effect being confirmed in brightness effect
Fruit is objective to show, and provides a completely new thinking to provide the application of above-mentioned brightener and expanding bright research.
Specific embodiment
Embodiment 1:
According to the following formulation, copper plating bath is prepared,
Brightener is the sulfur-containing compound of following structural formula I
It is carried out by the technique of general electro-deposition substrate copper coating.
Comparative example 1:
Brightener is the thiophenic acid of thiophene carboxylic acid's class, remaining is same as Example 1；
Comparative example 2:
Brightener is that Ar-C (H)=C (H)-C (O)-CH3, Ar is thienyl, remaining is same as Example 1.
Embodiment 2:
Although aforementioned exemplary and it is of the invention focus on be compound of formula I bright property application, as in the industry
Personage is understood, and the purposes as primary brightener of compound of formula I and being used cooperatively for other second-class brighteners more can increase
Excellent performance, especially in terms of gloss imparting.It enumerates herein thus but not limited to this class is used cooperatively as with cumarin
It is used cooperatively, increases the cumarin of 0.8g/L on the basis of embodiment 1.
Technical effect of the invention is recorded as shown in table 1 below:
The technical test data for the present invention of table 1
| Embodiment 1 | Comparative example 1 | Comparative example 2 | Embodiment 2 | |
| Glossiness | ★★★★ | ★★ | ★★ | ★★★★★ |
| Stress characteristics | ▲▲ | ▲▲▲▲ | ▲▲▲▲ | ▲ |
Glossiness is measured as ocular estimate, and ★ ★ ★ ★ ★ is bright in mirror surface, and ★ ★ ★ ★ is light, and ★ ★ ★ is relatively light
Bright, ★ ★ half is bright, and ★ is without light.
Stress characteristics are measured as bending experiment, ▲ fall off for 180 ° without coating, ▲ ▲ being 120 ° is that no coating falls off, ▲ ▲
▲ fall off for 90 ° without coating, ▲ ▲ ▲ ▲ it falls off for 60 ° without coating.
Finally, it should be noted that embodiment described above, the only specific embodiment of the application, to illustrate the application
Technical solution, rather than its limitations, the protection scope of the application is not limited thereto, although with reference to the foregoing embodiments to this Shen
It please be described in detail, those skilled in the art should understand that: anyone skilled in the art
Within the technical scope of the present application, it can still modify to technical solution documented by previous embodiment or can be light
It is readily conceivable that variation or equivalent replacement of some of the technical features；And these modifications, variation or replacement, do not make
The essence of corresponding technical solution is detached from the spirit and scope of the embodiment of the present application technical solution.The protection in the application should all be covered
Within the scope of.Therefore, the protection scope of the application should be based on the protection scope of the described claims.
Claims (9)
1. a kind of pcb board cyanideless electro-plating copper electrolyte containing brightener, including
It is characterized in that the brightener preferably comprises the sulfur-containing compound of thienyl group, more preferably following structural formula I's contains
Sulphur compound
2. a kind of pcb board cyanideless electro-plating copper electrolyte containing brightener according to claim 1, it is characterised in that the light
Bright dose is the sulfur-containing compound for preferably comprising thienyl group.
3. a kind of pcb board cyanideless electro-plating copper electrolyte containing brightener according to claim 1 to 2, it is characterised in that described
Brightener is preferred compound of formula I.
4. purposes of the compound of formula I according to claim 1 in pcb board cyanideless electro-plating copper electrolyte as brightener.
5. a kind of PCB copper plating process, it is characterised in that using a kind of containing brightener described according to claim 1-5
Pcb board cyanideless electro-plating copper electrolyte.
6. a kind of PCB copper plating process, it is characterised in that use brightener as claimed in claim 4.
7. theme according to any claim from 1 to 6, which is characterized in that there are also remove thiophene for the brightener
The second element sulphur except group.
8. the second element sulphur according to claim 7 is close to thienyl group.
9. the second element sulphur according to claim 6-8 is thione group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910819193.6A CN110396706B (en) | 2019-08-31 | 2019-08-31 | PCB cyanide-free copper electroplating brightener and use method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910819193.6A CN110396706B (en) | 2019-08-31 | 2019-08-31 | PCB cyanide-free copper electroplating brightener and use method thereof |
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| CN110396706A true CN110396706A (en) | 2019-11-01 |
| CN110396706B CN110396706B (en) | 2021-04-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1897974A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN107217283A (en) * | 2017-07-25 | 2017-09-29 | 上海新阳半导体材料股份有限公司 | Leveling agent, the metal plating compositions containing it, preparation method and application |
-
2019
- 2019-08-31 CN CN201910819193.6A patent/CN110396706B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1897974A1 (en) * | 2006-09-07 | 2008-03-12 | Enthone Inc. | Deposition of conductive polymer and metallization of non-conductive substrates |
| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN107217283A (en) * | 2017-07-25 | 2017-09-29 | 上海新阳半导体材料股份有限公司 | Leveling agent, the metal plating compositions containing it, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| XIAOYUE LI ET AL.: "Bluish-Green Cu(I) Dimers Chelated with Thiophene Ring-Introduced Diphosphine Ligands for Both Singlet and Triplet Harvesting in OLEDs", 《ACS APPL. MATER. INTERFACES》 * |
| 刘志江 等: "电镀液添加剂的定性分析", 《当代化工》 * |
| 李玖娟 等: "环氧树脂表面生成聚噻吩的研究及直接电镀应用", 《电镀与精饰》 * |
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Effective date of registration: 20210312 Address after: Room 2407, 2067 Yan'an west road, Changning District, Shanghai 200050 Applicant after: Shanghai Linghe Chemical Technology Co.,Ltd. Address before: 519031 room 105-44336, No.6 Baohua Road, Hengqin New District, Zhuhai City, Guangdong Province (centralized office area) Applicant before: ZHUHAI WANSHUN RUITONG TECHNOLOGY Co.,Ltd. |
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