CN103556139B - A kind of alkaline chemical copper plating composite additive and preparation method thereof and using method - Google Patents
A kind of alkaline chemical copper plating composite additive and preparation method thereof and using method Download PDFInfo
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- CN103556139B CN103556139B CN201310301889.2A CN201310301889A CN103556139B CN 103556139 B CN103556139 B CN 103556139B CN 201310301889 A CN201310301889 A CN 201310301889A CN 103556139 B CN103556139 B CN 103556139B
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Abstract
The invention discloses a kind of alkaline chemical copper plating composite additive, with and preparation method thereof and using method.Does is acidic chemical copper facing composite additive material composition and content are every volume containing additive 1 in the water of 1L? 0.2 ~ 1.2ml, additive 2? 0.1 ~ 0.8g, additive 3? 0.05 ~ 0.3g, sodium hydroxide 0 ~ 30g; Additive 1 is castor oil polyoxyethylene ether; Additive 2 is 2-sulfydryl-acidum nicotinicum; Additive 3 is 2,2 ˊ-diquinolyl-4,4 ˊ-dioctyl phthalate disodium or 8-ethoxyquinoline-5-sodium sulfonate or both mixtures.Alkaline electroless plating copper additives provided by the present invention has outstanding dispersive ability, leveling ability and covering power under alkaline environment, the problems such as hydrogen embrittlement, striped, shade deviation and the poor toughness occurred in copper facing process can be solved very well, have economical and practical, the feature of successful, can promote the quality of chemical bronze plating liquid and copper-plated quality very well.
Description
Technical field
The present invention relates to a kind of electroless copper technical field, particularly relate to a kind of alkaline chemical copper plating composite additive applied when electroless copper, also relate to preparation method and the using method of this alkaline chemical copper plating compound interpolation.
Background technology
In electroless copper process; particularly " additive process " in soft board electroless copper and plastic basis material Electroless copper process; the problems such as the weak and copper facing poor toughness of the copper facing ability in entrained air bubbles in coating, striated surface or blackspot, aperture that often there will be; cause fraction defective to remain high, produce to enterprise and bring very adverse influence.When chemical fundamentals copper plating bath is determined, the quality of copper plate quality, largely depends on selecting of additive.Although the theory of China's electroless plating aspect, technology and relevant research have had larger progress in recent years, many problems are still there is.Along with developing rapidly of science and technology, the miniaturization of electronic product is had higher requirement to the precision of circuit card and stability, and to realize wiring board high-accuracyly well will solve the electroless copper quality that in aperture, (aperture is less than 50 μm) copper facing and live width are less than 30 μm, this is also just more and more higher to the requirement of additive.Although China have developed some good copper plating additives, these additives still can not meet the production requirement of high degree of accuracy circuit card, therefore develop novel electroless copper additive and become extremely urgent.
Summary of the invention
The object of the invention is for prior art Problems existing, a kind of alkaline chemical copper plating composite additive of the application when carrying out alkaline chemical copper plating is provided, utilize this alkaline chemical copper plating composite additive can improve copper plate quality when alkaline chemical copper plating, can be good at solving the problems such as the weak and copper facing poor toughness of copper facing ability in entrained air bubbles and cavity (hydrogen embrittlement) in the coating occurred in alkaline chemical copper plating process, striated surface or pit, aperture.The preparation method that the present invention simultaneously also provides this alkaline chemical copper plating compound a kind of to add and using method.
A kind of alkaline chemical copper plating composite additive, its material composition and content are that every volume is contain following material in the water of 1L:
Additive 1 0.2 ~ 1.2ml;
Additive 2 0.1 ~ 0.8g;
Additive 3 0.05 ~ 0.3g;
Sodium hydroxide 0 ~ 30g;
Described additive 1 is castor oil polyoxyethylene ether.
Described additive 2 is 2-sulfydryl-acidum nicotinicum.
Described additive 3 is 2,2'-diquinolyl-4,4'-dioctyl phthalate disodium or 8-ethoxyquinoline-5-sodium sulfonate or both mixtures.
Described water is deionized water.
The preparation method of above-mentioned alkaline chemical copper plating composite additive, is characterized in that, comprise the following steps:
(1) getting X(X is positive number) L deionized water, add (0 ~ 30) Xg sodium hydroxide) and to stir, to be dissolved complete after be cooled to normal temperature stand-by;
(2) adding the additive 1 described in (0.2 ~ 1.2) XmL, additive described in (0.1 ~ 0.8) Xg 2 and the additive 3 described in (0.05 ~ 0.3) Xg successively to the solution of step (1) gained in stirs, after all materials fully dissolve, namely obtain alkaline chemical copper plating composite additive;
The using method of alkaline chemical copper plating composite additive of the present invention in electroless copper process is: in alkaline electroless plating copper process, according to the volume of chemical bronze plating liquid, adds the alkaline chemical copper plating composite additive of chemical bronze plating liquid volume 1% ~ 2%.
Compared with prior art, beneficial effect of the present invention is as follows: alkaline chemical copper plating composite additive of the present invention is using castor oil polyoxyethylene ether as tensio-active agent, because it is a kind of nonionogenic tenside, so have good dispersion effect under alkaline environment, effectively can reduce surface tension, the hydrogen be adsorbed on plating piece is overflowed fast, avoids " hydrogen embrittlement " phenomenon.Selected additive 2 and additive 3 are owing to all containing phenyl ring and heterocycle, and have large π key, because π key is delocalization, it acts as the bridge of electron transmission, the reduction being conducive to cupric ion deposits and makes copper facing more smooth.And selected additive 2 and additive 3 are all the organism containing lone electron pair, can absorbing copper ion, and due to the electric charge between them contrary, because electrostatic interaction makes the accumulation between heavy copper particle become tightr.
Accompanying drawing explanation
Fig. 1 is the alkaline chemical copper plating scanning electron microscope (SEM) photograph (2000 times) not adding alkaline chemical copper plating composite additive of the present invention.
Fig. 2 is the alkaline chemical copper plating scanning electron microscope (SEM) photograph (2000 times) adding alkaline chemical copper plating composite additive of the present invention.
Fig. 3 is the alkaline chemical copper plating scanning electron microscope (SEM) photograph (20000 times) not adding alkaline chemical copper plating composite additive of the present invention.
Fig. 4 is the alkaline chemical copper plating scanning electron microscope (SEM) photograph (20000 times) adding alkaline chemical copper plating composite additive of the present invention.
Embodiment
The present invention to be described in further detail below in conjunction with embodiment and accompanying drawing for the ease of it will be appreciated by those skilled in the art that: embodiment 1:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of 0.9ml castor oil polyoxyethylene ether, 0.5g 2-sulfydryl-acidum nicotinicum, 0.3g 2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, sodium hydroxide 14.5g and deionized water 1L volume fraction are the alkaline chemical copper plating composite additive solution of chemical bronze plating liquid 1.6%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | Few | Nothing | Few | On a small quantity | Reddish black | 8 |
| Sample 2 | Nothing | Nothing | Nothing | A lot | Pink | 10 |
Embodiment 2:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of with adding the alkaline chemical copper plating composite additive solution that 1ml castor oil polyoxyethylene ether, 0.6g 2-sulfydryl-acidum nicotinicum, 0.4g 8-ethoxyquinoline-5-sodium sulfonate, sodium hydroxide 14.5g and deionized water 1L volume fraction are chemical bronze plating liquid 1.3%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | Few | Nothing | Few | On a small quantity | Reddish black | 7 |
| Sample 2 | Nothing | Nothing | Nothing | A lot | Pink | 9.5 |
Embodiment 3:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of 0.5ml castor oil polyoxyethylene ether, 0.6g 2-sulfydryl-acidum nicotinicum, 0.2g 2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, sodium hydroxide 5g and deionized water 1L volume fraction are the alkaline chemical copper plating composite additive solution of chemical bronze plating liquid 1%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | A lot | On a small quantity | A lot | On a small quantity | Reddish black | 7 |
| Sample 2 | Nothing | Nothing | Minute quantity | A lot | Pink | 9.5 |
Embodiment 4:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of with adding the alkaline chemical copper plating composite additive solution that 0.8ml castor oil polyoxyethylene ether, 0.5g 2-sulfydryl-acidum nicotinicum, 0.3g 8-ethoxyquinoline-5-sodium sulfonate, sodium hydroxide 25g and deionized water 1L volume fraction are chemical bronze plating liquid 1.5%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | More | Nothing | A lot | On a small quantity | Black | 7.5 |
| Sample 2 | Nothing | Nothing | No | A lot | Brick-red | 10 |
Embodiment 5:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of 0.2ml castor oil polyoxyethylene ether, 0.1g 2-sulfydryl-acidum nicotinicum, 0.01g 2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, 0.05g 8-ethoxyquinoline-5-sodium sulfonate, sodium hydroxide 1g and deionized water 1L volume fraction are the alkaline chemical copper plating composite additive solution of chemical bronze plating liquid 1.8%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | More | Nothing | A lot | On a small quantity | Black | 7.5 |
| Sample 2 | Nothing | Nothing | No | A lot | Brick-red | 9 |
Embodiment 6:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of 1ml castor oil polyoxyethylene ether, 0.7g 2-sulfydryl-acidum nicotinicum, 0.2g 2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, 0.05g 8-ethoxyquinoline-5-sodium sulfonate, sodium hydroxide 30g and deionized water 1L volume fraction are the alkaline chemical copper plating composite additive solution of chemical bronze plating liquid 2%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | A lot | On a small quantity | A lot | On a small quantity | Reddish black | 7 |
| Sample 2 | Nothing | Nothing | Minute quantity | A lot | Pink | 9.5 |
Embodiment 7:
Copper facing formula based on the formaldehyde selecting the disodium ethylene diamine tetraacetate of the Seignette salt of the cupric sulfate pentahydrate of 16g/L, 14g/L, 19.5g/L, the sodium hydroxide of 14.5g/L and 10 ~ 12mL/L, the pH value of solution is 12 ~ 13, and copper facing temperature is 30 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add alkaline chemical copper plating composite additive of the present invention and consists of 1.2ml castor oil polyoxyethylene ether, 0.8g 2-sulfydryl-acidum nicotinicum, 0.3g 2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, sodium hydroxide 10g and deionized water 1L volume fraction are the alkaline chemical copper plating composite additive solution of chemical bronze plating liquid 1.2%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the alkaline chemical copper plating composite additive of above-mentioned concentration).The electroless copper performance of contrast gained:
| Title | There is bubble-free | With or without striped | With or without pit | Copper facing in hole | Copper facing color | Backlight level |
| Sample 1 | A lot | On a small quantity | A lot | On a small quantity | Reddish black | 7 |
| Sample 2 | Nothing | Nothing | Minute quantity | A lot | Pink | 10 |
The electroless copper performance of above embodiment shows, utilize this alkaline chemical copper plating composite additive can improve copper plate quality when alkaline chemical copper plating, can be good at solving the problems such as the weak and copper facing poor toughness of copper facing ability in entrained air bubbles and cavity (hydrogen embrittlement) in the coating occurred in alkaline chemical copper plating process, striated surface or pit, aperture.Contriver carries out 2000 times and 10000 times of electroless copper electron-microscope scannings respectively to the sample 1 in embodiment 1 and sample 2, as shown in Figures 1 to 4, scanning electron microscope (SEM) photograph shows, after adding alkaline chemical copper plating composite additive of the present invention, really can effectively improve electroless copper quality.
Claims (4)
1. an alkaline chemical copper plating composite additive, its material composition and content are: every volume is containing following material in the water of 1L,
Additive 1 0.2 ~ 1.2ml;
Additive 2 0.1 ~ 0.8g;
Additive 3 0.05 ~ 0.3g;
Sodium hydroxide 0 ~ 30g;
Described additive 1 is castor oil polyoxyethylene ether;
Described additive 2 is 2-sulfydryl-acidum nicotinicum;
Described additive 3 is 2,2'-diquinolyl-4,4'-dioctyl phthalate disodium or 8-ethoxyquinoline-5-sodium sulfonate or both mixtures.
2. alkaline chemical copper plating composite additive as claimed in claim 1, is characterized in that: described water is deionized water.
3. the preparation method of alkaline chemical copper plating composite additive as claimed in claim 1 or 2, is characterized in that comprising the following steps:
(1) getting X(X is positive number) L deionized water, add (0 ~ 30) Xg sodium hydroxide and stir, to be dissolved complete after be cooled to normal temperature stand-by;
(2) adding the additive 1 described in (0.2 ~ 1.2) XmL, additive described in (0.1 ~ 0.8) Xg 2 and the additive 3 described in (0.05 ~ 0.3) Xg successively to the solution of step (1) gained in stirs, after all materials fully dissolve, namely obtain alkaline chemical copper plating composite additive.
4. the using method of alkaline chemical copper plating composite additive as claimed in claim 1 or 2, is characterized in that: in alkaline electroless plating copper process, according to the volume of chemical bronze plating liquid, adds the alkaline chemical copper plating composite additive of chemical bronze plating liquid volume 1% ~ 2%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377174A (en) * | 1963-10-24 | 1968-04-09 | Torigai Eiichi | Method and bath for chemically plating copper |
| US3708329A (en) * | 1971-09-10 | 1973-01-02 | Bell Telephone Labor Inc | Electroless copper plating |
| US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
| US4371397A (en) * | 1980-05-08 | 1983-02-01 | Tokyo Shibaura Denki Kabushiki Kaisha | Chemical copper-plating bath |
| CN102677027A (en) * | 2012-05-25 | 2012-09-19 | 广州市天承化工有限公司 | Activating solution composition for nonmetallic material electroless plating |
| CN103014682A (en) * | 2012-12-05 | 2013-04-03 | 陕西师范大学 | Low-temperature low-stress electroless copper plating solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5217335A (en) * | 1975-08-01 | 1977-02-09 | Hitachi Ltd | Chemical copper plating solution |
| JP2006316350A (en) * | 2005-04-13 | 2006-11-24 | Hitachi Chem Co Ltd | Pretreatment liquid for electroless nickel plating, and pretreatment method to electroless nickel plating |
-
2013
- 2013-07-18 CN CN201310301889.2A patent/CN103556139B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377174A (en) * | 1963-10-24 | 1968-04-09 | Torigai Eiichi | Method and bath for chemically plating copper |
| US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
| US3708329A (en) * | 1971-09-10 | 1973-01-02 | Bell Telephone Labor Inc | Electroless copper plating |
| US4371397A (en) * | 1980-05-08 | 1983-02-01 | Tokyo Shibaura Denki Kabushiki Kaisha | Chemical copper-plating bath |
| CN102677027A (en) * | 2012-05-25 | 2012-09-19 | 广州市天承化工有限公司 | Activating solution composition for nonmetallic material electroless plating |
| CN103014682A (en) * | 2012-12-05 | 2013-04-03 | 陕西师范大学 | Low-temperature low-stress electroless copper plating solution |
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