CN105200467B - A kind of Gravure hard copper additive and plating solution - Google Patents
A kind of Gravure hard copper additive and plating solution Download PDFInfo
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- CN105200467B CN105200467B CN201510731166.5A CN201510731166A CN105200467B CN 105200467 B CN105200467 B CN 105200467B CN 201510731166 A CN201510731166 A CN 201510731166A CN 105200467 B CN105200467 B CN 105200467B
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- sodium
- deionized water
- sulfonate
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Abstract
The present invention relates to a kind of solution additive and plating solutions, especially a kind of Gravure hard copper additive and plating solution, Gravure hard copper additive includes hardness agent and brightener, hardness agent is composed of the following components: the poly- dithiopropane sodium sulfonate of benzothiazole or the thio propane sulfonic acid sodium of Anthelvet base two: 0.3-0.7%, ethylene thiourea: 0.4-0.8%, surplus is deionized water, the brightener is composed of the following components: 3- mercaptopropanesulfonic acid sodium or sodium polydithio-dipropyl sulfonate or phenyl sodium polydithio-dipropyl sulfonate: 1.0-2.0%, polyethyleneimine alkyl salt: 1.0-1.5%, sour copper walks by force agent: 0.3-1.0%, Macrogol 6000-10000:1.5-2.0%, surplus is deionized water.
Description
Technical field
The present invention relates to field of electroplating more particularly to a kind of Gravure hard copper additives and plating solution.
Background technique
Requirement of the electronic engraving printing notch board in engraving to layers of copper is high, and hardness control is in 190-230HV, copper ion row
Column will uniformly, and additive used at present is based on imported product, and domestic Gravure hard copper additive capability and performance is poor, therefore such as
What, which is developed, a kind of makes the Gravure hard copper additive that layers of copper hardness is big, brightener is good, performance is flexible, storage is long be to need
The technical issues of conscientiously solving.
Summary of the invention
For above situation, to overcome prior art defect, the purpose of the present invention is just to provide a kind of Gravure hard copper addition
Agent can effectively solve the problems, such as that hardness is big, brightness is good, performance is flexible, storage is long.
The technical solution that the present invention solves is,
A kind of Gravure hard copper additive, including hardness agent and brightener, which is characterized in that hardness agent is by following components group
At: the poly- dithiopropane sodium sulfonate of benzothiazole or the thio propane sulfonic acid sodium of Anthelvet base two: 0.3-0.7%, ethylene thiourea: 0.4-
0.8%, surplus is deionized water, and the brightener is composed of the following components: 3- mercaptopropanesulfonic acid sodium or polydithio-dipropyl
Sodium sulfonate or phenyl sodium polydithio-dipropyl sulfonate: 1.0-2.0%, polyethyleneimine alkyl salt: 1.0-1.5%, sour copper are walked by force
Position agent: 0.3-1.0%, Macrogol 6000-10000:1.5-2.0%, surplus are deionized water.
It further, further include plating solution, the plating solution includes following components and content: copper sulphate 200-280g/L；Sulphur
Sour 50-80g/L；Chloride ion 100-200mg/L；Hardness agent: 1-1.5ml/L, brightener: 2-6ml/L.
Further, the configuration method of Gravure hard copper additive is that first 30% deionized water is added in (1) in a reservoir, is added
Enter the ethylene thiourea of 0.4-0.8%, agitating and heating makes solution temperature to 60 DEG C or so, and stirring to ethylene thiourea is completely dissolved；
(2) plus the poly- dithiopropane sodium sulfonate of benzothiazole or the thio propane of Anthelvet base two is added in 20% deionized water immediately
Sodium sulfonate: 0.3-0.7%, the poly- dithiopropane sodium sulfonate of stirring benzothiazole or the thio propane sulfonic acid sodium of Anthelvet base two are completely molten
Solution；
(3) deionized water for supplying surplus, stirs evenly, and takes out；
(4) 30% deionized water is added in container, 1.0-2.0%3- mercaptopropanesulfonic acid sodium or polydithio-dipropyl is added
Sodium sulfonate or phenyl sodium polydithio-dipropyl sulfonate, -10000 agitating and heating of 1.5-2.0% Macrogol 6000 make solution temperature
To 40 DEG C or so, stirring to 3- mercaptopropanesulfonic acid sodium or sodium polydithio-dipropyl sulfonate or phenyl polydithio-dipropyl sulfonic acid
Sodium, Macrogol 6000-10000 are completely dissolved, and 40% deionized water, polyethyleneimine alkyl salt are added after being completely dissolved:
1.0-1.5%, sour copper walk by force agent: the deionized water of 0.3-1.0% and surplus stir evenly.
Instant component and dosage are scientific and reasonable, method is simple, easy to produce, easy to use, effect is good, are to Gravure hard copper
The improvement of additive novelty, it is on Gravure hard copper additive that hardness is big, brightness is good, planarization is good, effective storage period is long
Important breakthrough.
Specific embodiment
Below according to specific embodiment, the present invention will be further described.
Embodiment 1
Plating piece is added in Gravure hard copper plating solution, plating solution composition is copper sulphate 240g/L；Sulfuric acid 60g/L；Chloride ion
150mg/L；Hardness agent: 1ml/L, brightener: 3ml/L, wherein hardness agent is the poly- dithiopropane sodium sulfonate of benzothiazole: 0.7%,
Ethylene thiourea: 0.4%, surplus is deionized water, brightener are as follows: 3- mercaptopropanesulfonic acid sodium: 15%, polyethyleneimine alkyl
Salt: 1%, sour copper walks by force agent: 0.3%, Macrogol 6000-10000:1.5%, surplus are deionized water, bath temperature 38
DEG C, cathode-current density 15A/dm2, anode and cathode area ratio 1:4, the mobile linear velocity 1m/s of anode and cathode.
Embodiment 2
Plating piece is added in Gravure hard copper plating solution, plating solution composition is copper sulphate 200g/L；Sulfuric acid 50g/L；Chloride ion
100mg/L；Hardness agent: 1ml/L, brightener: 2ml/L, wherein hardness agent is the thio propane sulfonic acid sodium of Anthelvet base two: 0.5%,
Tetrahydro-thiazoles thioketones: 0.6%, surplus is deionized water, brightener are as follows: sodium polydithio-dipropyl sulfonate: 2%, polyethyleneimine
Alkyl salt: 1.5%, sour copper walks by force agent: 1%, Macrogol 6000-10000:2%, surplus are deionized water, bath temperature
38 DEG C, cathode-current density 15A/dm2, anode and cathode area ratio 1:4, the mobile linear velocity 1m/s of anode and cathode.
Embodiment 3
Plating piece is added in Gravure hard copper plating solution, plating solution composition is copper sulphate 240g/L；Sulfuric acid 60g/L；Chloride ion
150mg/L；Hardness agent: 3ml/L, brightener: 3ml/L, wherein hardness agent is the poly- dithiopropane sodium sulfonate of benzothiazole: 0.7%,
Ethylene thiourea: 0.4%, surplus is deionized water, brightener are as follows: phenyl sodium polydithio-dipropyl sulfonate: 15%, polyethyleneimine
Alkyl salt: 1%, sour copper walks by force agent: 0.3%, Macrogol 6000-10000:1.5%, surplus are deionized water, plating bath temperature
38 DEG C of degree, cathode-current density 15A/dm2, anode and cathode area ratio 1:4, the mobile linear velocity 1m/s of anode and cathode.
1 embodiment coating Contrast on effect table of table
| Embodiment | Embodiment one | Embodiment two | Embodiment three |
| Coating effect | Bright in mirror surface | Bright in mirror surface | It is bright |
| Hardness | 24OHV | 220HV | 260HV |
| Flatness | It is good | It is good | Generally |
The existing induration of curing agent, and have bright effect.Cathodic polarization can be effectively improved in the plating process, make nucleus
Formation speed be much larger than the speed of nucleus growth, it is careful to make to crystallize, and layers of copper is bright；Microcosmic point of coating can be effectively improved simultaneously
The ability of dissipating makes to be flattened at the subtle injustice of electrode surface, can also effectively improve the brightness of coating.On the one hand due to improving yin
Pole polarization can be such that the interaction force after ion reduction in crystallization process increases, and improve the hardness of layers of copper, on the other hand this kind of
Certain ingredients of curing agent can be mixed in the lattice of layers of copper, the more uniform internal stress for improving layers of copper, to make coating
Hardness improve.Content is very few in the plating solution for curing agent, and the layers of copper hardness decline just plated is not too big, but when hardness holding
Between can be obviously shortened, brightness will not be ideal, and low current density area is especially serious.Curing agent too high levels can inhibit leveling agent
Effect, the probability for surface defect occur increases, and high current density region has focal spot generation, and layers of copper internal stress can also become larger, firmly
Degree increases, unfavorable to electronic engraving, therefore the proportion content of curing agent is critically important, is compared by embodiment it can be found that using this
The coating effect of the Gravure hard copper additive of formula is very ideal.
Although technical solution of the present invention is described in detail above-described embodiment, technical solution of the present invention
Above embodiments are not limited to, in the case where not departing from thought and objective of the invention, technical solution of the present invention is done
Any change fall within claims of the present invention limited range.
Claims (3)
1. a kind of Gravure hard copper additive, including hardness agent and brightener, which is characterized in that hardness agent is composed of the following components:
The poly- dithiopropane sodium sulfonate of benzothiazole or the thio propane sulfonic acid sodium of Anthelvet base two: 0.3-0.7%, ethylene thiourea: 0.4-
0.8%, surplus is deionized water, and the brightener is composed of the following components: 3- mercaptopropanesulfonic acid sodium or polydithio-dipropyl
Sodium sulfonate or phenyl sodium polydithio-dipropyl sulfonate: 1.0-2.0%, polyethyleneimine alkyl salt: 1.0-1.5%, sour copper are walked by force
Position agent: 0.3-1.0%, Macrogol 6000-10000:1.5-2.0%, surplus are deionized water.
2. a kind of Gravure hard copper additive as described in claim 1, it is characterised in that: it further include plating solution, the plating solution packet
Containing following components and content: copper sulphate 200-280g/L；Sulfuric acid 50-80g/L；Chloride ion 100-200mg/L；Hardness agent: 1-
1.5ml/L, brightener: 2-6ml/L.
3. a kind of Gravure hard copper additive as described in claim 1, which is characterized in that preparation method are as follows:
(1) 30% deionized water is first added in a reservoir, the ethylene thiourea of 0.4-0.8% is added, agitating and heating makes solution temperature
To 60 DEG C or so, stirring to ethylene thiourea is completely dissolved；
(2) plus the poly- dithiopropane sodium sulfonate of benzothiazole or the thio propane sulfonic acid of Anthelvet base two is added in 20% deionized water immediately
Sodium: 0.3-0.7%, the poly- dithiopropane sodium sulfonate of stirring benzothiazole or the thio propane sulfonic acid sodium of Anthelvet base two are completely dissolved；
(3) deionized water for supplying surplus, stirs evenly, and takes out；
(4) 30% deionized water is added in container, 1.0-2.0%3- mercaptopropanesulfonic acid sodium or polydithio-dipropyl sulfonic acid is added
Sodium or phenyl sodium polydithio-dipropyl sulfonate, -10000 agitating and heating of 1.5-2.0% Macrogol 6000 make solution temperature to 40
DEG C or so, stirring to 3- mercaptopropanesulfonic acid sodium or sodium polydithio-dipropyl sulfonate or phenyl sodium polydithio-dipropyl sulfonate gather
Ethylene glycol 6000-10000 is completely dissolved, and 40% deionized water, polyethyleneimine alkyl salt: 1.0- are added after being completely dissolved
1.5%, sour copper walks by force agent: the deionized water of 0.3-1.0% and surplus stir evenly.
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| CN201510731166.5A CN105200467B (en) | 2015-11-02 | 2015-11-02 | A kind of Gravure hard copper additive and plating solution |
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| CN201510731166.5A CN105200467B (en) | 2015-11-02 | 2015-11-02 | A kind of Gravure hard copper additive and plating solution |
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| CN105200467B true CN105200467B (en) | 2019-01-29 |
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| CN106637312A (en) * | 2017-03-07 | 2017-05-10 | 龙游运申制版有限公司 | Copper plating solution for plate roller and preparation method of copper plating solution |
| CN107268042B (en) * | 2017-06-02 | 2018-07-10 | 吕艺璇 | A kind of electronic engraving printing gravure hard copper additive |
| CN107740146A (en) * | 2017-10-27 | 2018-02-27 | 桐城运城制版有限公司 | A kind of intaglio plate copper plating additive |
| CN107723750A (en) * | 2017-11-17 | 2018-02-23 | 灵宝华鑫铜箔有限责任公司 | A kind of additive and the method using 6 microns of high rigidity electrolytic copper foils of Additive Production |
| CN109371437B (en) * | 2018-12-04 | 2021-03-30 | 东莞市同欣表面处理科技有限公司 | Gravure acid electroplating hard copper additive and preparation method thereof |
| CN110453254A (en) * | 2019-08-30 | 2019-11-15 | 广州皓悦新材料科技有限公司 | A kind of pulse plating brightener and preparation method thereof |
| CN111575753A (en) * | 2020-04-09 | 2020-08-25 | 杭州运城制版有限公司 | Processing technology of primary copper printing roller |
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| JP2001073182A (en) * | 1999-07-15 | 2001-03-21 | Boc Group Inc:The | Improved acidic copper electroplating solution |
| CN102703938B (en) * | 2012-06-07 | 2015-04-22 | 上海交通大学 | Stress relieving agent for copper sulfate electroplate liquid |
| CN102912388A (en) * | 2012-10-11 | 2013-02-06 | 郑州市大有制版有限公司 | Gravure hard copper additive |
| CN103060860B (en) * | 2013-01-22 | 2016-01-20 | 中南大学 | A kind of printed circuit board acid copper-plating electroplate liquid and methods for making and using same thereof |
| CN103103586B (en) * | 2013-02-22 | 2016-05-04 | 陕西师范大学 | The copper electroplating solution that contains thiazole compound |
| CN103572336B (en) * | 2013-11-20 | 2016-06-22 | 东莞市富默克化工有限公司 | A kind of PCB blind hole copper electroplating solution and preparation method thereof and electro-plating method |
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Address after: 212300 Zhenjiang city of Jiangsu province Danyang Yanling Town South Applicant after: JIANGSU MENGDE NEW MATERIALS TECHNOLOGY CO., LTD. Address before: 212300 Zhenjiang city of Jiangsu province Danyang Yanling Town South Applicant before: JIANGSU MENGDE PLATING CHEMICALS CO., LTD. |
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