CN103397316B - A kind of acidic chemical copper facing composite additive and preparation method thereof and using method - Google Patents
A kind of acidic chemical copper facing composite additive and preparation method thereof and using method Download PDFInfo
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- CN103397316B CN103397316B CN201310301873.1A CN201310301873A CN103397316B CN 103397316 B CN103397316 B CN 103397316B CN 201310301873 A CN201310301873 A CN 201310301873A CN 103397316 B CN103397316 B CN 103397316B
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Abstract
The invention discloses a kind of acidic chemical copper facing composite additive, with and preparation method thereof and use.Acidic chemical copper facing composite additive material composition and content are every volume is containing additive 1 0.2 ~ 1.2ml, additive 2 0.1 ~ 0.8g, additive 3 0.05 ~ 0.3g, the vitriol oil 0 ~ 1mL in the water of 1L; Additive 1 is castor oil polyoxyethylene ether; Additive 2 is 2-sulfydryl-acidum nicotinicum; Additive 3 is 2,2'-diquinolyl-4,4'-dioctyl phthalate disodium or 8-ethoxyquinoline-5-sodium sulfonate or both mixtures.Acidic chemical copper plating additive provided by the present invention has outstanding dispersive ability, leveling ability and covering power under sour 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 acidic chemical copper facing composite additive applied when electroless copper, also relate to preparation method and the using method of this acidic chemical copper facing composite additive.
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 acidic chemical copper facing composite additive applied when carrying out acidic chemical copper facing is provided, utilize this acidic chemical copper facing composite additive can improve copper plate quality when acidic chemical copper facing, 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 acidic chemical copper facing process, striated surface or pit, aperture.The preparation method that the present invention simultaneously also provides this acidic chemical copper facing compound a kind of to add and using method.
A kind of acidic chemical copper facing 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;
The vitriol oil 0 ~ 1mL;
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 described vitriol oil is the sulphuric acid soln that concentration is more than or equal to 70%.
The preparation method of above-mentioned acidic chemical copper facing composite additive, comprises the following steps:
(1) getting X(X is positive number) L water, add the vitriol oil of (0 ~ 1) XmL 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 acidic chemical copper facing composite additive.
The using method of acidic chemical copper facing composite additive of the present invention in electroless copper process is: in acid chemical plating copper process, according to the volume of chemical bronze plating liquid, adds the acidic chemical copper facing composite additive of chemical bronze plating liquid volume 2% ~ 3%.
Compared with prior art, beneficial effect of the present invention is as follows: acidic chemical copper facing 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 sour 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 acidic chemical copper facing scanning electron microscope (SEM) photograph (2000 times) not adding acidic chemical copper facing composite additive of the present invention.
Fig. 2 is the acidic chemical copper facing scanning electron microscope (SEM) photograph (2000 times) adding acidic chemical copper facing composite additive of the present invention.
Fig. 3 is the acidic chemical copper facing scanning electron microscope (SEM) photograph (10000 times) not adding acidic chemical copper facing composite additive of the present invention.
Fig. 4 is the acidic chemical copper facing scanning electron microscope (SEM) photograph (10000 times) adding acidic chemical copper facing 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:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add acidic chemical copper facing 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, vitriol oil 0.001ml(concentration are the sulphuric acid soln of 70%) and deionized water 1L volume fraction be the acidic chemical copper facing composite additive solution of chemical bronze plating liquid 2.5%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the acidic chemical copper facing 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 2:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add that acidic chemical copper facing composite additive of the present invention and adding consists of 0.8ml castor oil polyoxyethylene ether, 0.5g 2-sulfydryl-acidum nicotinicum, 0.3g 8-ethoxyquinoline-5-sodium sulfonate, vitriol oil 0.001ml(concentration is the sulphuric acid soln of 70%) and deionized water 1L volume fraction be the acidic chemical copper facing 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 acidic chemical copper facing 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 3:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add acidic chemical copper facing composite additive of the present invention and consists of 0.2ml castor oil polyoxyethylene ether, 0.1g2-sulfydryl-acidum nicotinicum, 0.01g2 with adding, 2'-diquinolyl-4,4'-dioctyl phthalate disodium, 0.05g 8-ethoxyquinoline-5-sodium sulfonate, vitriol oil 0.005ml(concentration are the sulphuric acid soln of 80%) and deionized water 1L volume fraction be the acidic chemical copper facing composite additive solution of chemical bronze plating liquid 3%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the acidic chemical copper facing 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 4:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add acidic chemical copper facing 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, vitriol oil 0.01ml(concentration are the sulphuric acid soln of 98%) and deionized water 1L volume fraction be the acidic chemical copper facing 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 acidic chemical copper facing 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 5:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add acidic chemical copper facing 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, vitriol oil 1ml(concentration are the sulphuric acid soln of 75%) and deionized water 1L volume fraction be the acidic chemical copper facing composite additive solution of chemical bronze plating liquid 2.2%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the acidic chemical copper facing 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 |
Embodiment 6:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add acidic chemical copper facing 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, vitriol oil 0.4ml(concentration are the sulphuric acid soln of 85%) and deionized water 1L volume fraction be the acidic chemical copper facing composite additive solution of chemical bronze plating liquid 2.8%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the acidic chemical copper facing 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 7:
Select the copper facing formula based on the cupric sulfate pentahydrate of 0.05mol/L, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, 0.35mol/L sodium hypophosphite, the pH value of solution is 4.5, and copper facing temperature is 40 DEG C.With the PET film through oil removing and roughening treatment for base material (aperture containing about 30um).Contrast does not add that acidic chemical copper facing composite additive of the present invention and adding consists of 1ml castor oil polyoxyethylene ether, 0.6g 2-sulfydryl-acidum nicotinicum, 0.4g 8-ethoxyquinoline-5-sodium sulfonate, vitriol oil 0.1ml(concentration is the sulphuric acid soln of 80%) and deionized water 1L volume fraction be the acidic chemical copper facing composite additive solution of chemical bronze plating liquid 2.5%, after electroless copper, obtain sample 1(respectively not additivated) and sample 2(be added with the acidic chemical copper facing 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 |
The electroless copper performance of above embodiment shows, utilize this acidic chemical copper facing composite additive can improve copper plate quality when acidic chemical copper facing, 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 acidic chemical copper facing 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 acidic chemical copper facing composite additive of the present invention, really can effectively improve electroless copper quality.
Claims (4)
1. an acidic chemical copper facing 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;
The vitriol oil 0 ~ 1mL, the described vitriol oil is the sulphuric acid soln that concentration is more than or equal to 70%;
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. acidic chemical copper facing composite additive as claimed in claim 1, is characterized in that: described water is deionized water.
3. the preparation method of acidic chemical copper facing composite additive as claimed in claim 1 or 2, is characterized in that comprising the following steps:
(1) get XL water, wherein X is positive number, adds the vitriol oil of 0 ~ 1 times of XmL and stirs, to be dissolved complete after be cooled to normal temperature stand-by;
(2) to add successively in additive 1,0.1 ~ 0.8 times of additive 2 described in Xg described in 0.2 ~ 1.2 times of XmL and the additive 3 described in 0.05 ~ 0.3 times of Xg to the solution of step (1) gained and to stir, i.e. obtained acidic chemical copper facing composite additive after all materials fully dissolve.
4. the using method of acidic chemical copper facing composite additive as claimed in claim 1 or 2, is characterized in that: in acid chemical plating copper process, according to the volume of chemical bronze plating liquid, adds the acidic chemical copper facing composite additive of chemical bronze plating liquid volume 2% ~ 3%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7335280B2 (en) | 2018-06-08 | 2023-08-29 | アトテック ドイチェランド ゲーエムベーハー ウント コ カーゲー | Electroless copper or copper alloy plating bath and plating method |
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| JPS4840543B1 (en) * | 1970-04-24 | 1973-12-01 | ||
| CN102731536A (en) * | 2012-06-29 | 2012-10-17 | 长沙铂鲨环保设备有限公司 | Anionic type gold complex and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7335280B2 (en) | 2018-06-08 | 2023-08-29 | アトテック ドイチェランド ゲーエムベーハー ウント コ カーゲー | Electroless copper or copper alloy plating bath and plating method |
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