CN103397316A - Acidic chemical copper-plating composite additive as well as preparation method and use method thereof - Google Patents
Acidic chemical copper-plating composite additive as well as preparation method and use method thereof Download PDFInfo
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- CN103397316A CN103397316A CN2013103018731A CN201310301873A CN103397316A CN 103397316 A CN103397316 A CN 103397316A CN 2013103018731 A CN2013103018731 A CN 2013103018731A CN 201310301873 A CN201310301873 A CN 201310301873A CN 103397316 A CN103397316 A CN 103397316A
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Abstract
The invention discloses an acidic chemical copper-plating composite additive as well as a preparation method and use method thereof. The acidic chemical copper-plating composite additive comprises the following components in 1L of water: 0.2-1.2ml of additive 1, 0.1-0.8g of additive 2, 0.05-0.3g of additive 3 and 0-1mL of concentrated sulfuric acid, wherein the additive 1 is polyoxyethylene castor oil; the additive 2 is 2-mercapto-3-pyridine carboxylic acid; and the additive 3 is 2,2'-biquinoline-4,4'- disodium phthalate or 8-ethoxyquin-5-sodium sulfonate or the mixture of 2,2'-biquinoline-4,4'- dicarboxylic acid disodium and 8-ethoxyquin-5-sodium sulfonate. The acidic chemical copper-plating composite additive disclosed by the invention has excellent dispersing, leveling and deep-plating capacities and the characteristics of economy, practicability and obvious effect; and by utilizing the acidic chemical copper-plating composite additive, the problems of hydrogen brittleness, stripes, poor color and toughness and the like in a copper-plating process can be well solved, and the quality of chemical copper-plating solution and the copper-plating quality can be well improved.
Description
Technical field
The present invention relates to a kind of electroless copper technical field, relate in particular to a kind of acidic chemical copper facing composite additive of applying when electroless copper, also relate to preparation method and the using method of this acidic chemical copper facing composite additive.
Background technology
In the electroless copper process; particularly " additive process " in soft board electroless copper and plastic basis material Electroless copper process; often there will be in entrained air bubbles in coating, striated surface or blackspot, aperture the problems such as the weak and copper facing poor toughness of copper facing ability; cause fraction defective high, to enterprise, produce and bring very adverse influence.In the situation that the chemical fundamentals copper plating bath is definite, the quality of copper plate quality, largely depend on selecting of additive.Although the theory of China's electroless plating aspect, technology and relevant research had had larger progress in recent years, still existed many problems.Along with developing rapidly of science and technology, the miniaturization of electronic product is had higher requirement to precision and the stability of circuit card, and to realize wiring board high-accuracyly will solve well in aperture that (aperture is less than 50 μ m) copper facing and live width are less than the electroless copper quality of 30 μ m, this is just also more and more higher to the requirement of additive.Although China has developed some copper plating additives preferably, these additives still can not meet the production requirement of high degree of accuracy circuit card, and therefore developing novel electroless copper additive becomes extremely urgent.
Summary of the invention
The objective of the invention is the problem that exists for prior art, a kind of acidic chemical copper facing composite additive of applying when carrying out acidic chemical copper facing is provided, utilize this acidic chemical copper facing composite additive when acidic chemical copper facing, to improve the copper plate quality, can be good at solving in entrained air bubbles and cavity (hydrogen embrittlement), striated surface or pit in the coating that occurs in acidic chemical copper facing process, aperture the problems such as the weak and copper facing poor toughness of copper facing ability.The present invention simultaneously also provides preparation method and the using method of the compound interpolation of a kind of this acidic chemical copper facing.
A kind of acidic chemical copper facing composite additive, its material composition and content are: every volume is to 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;
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 concentration more than or equal to 70% sulphuric acid soln.
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, after to be dissolved completing, be cooled to normal temperature stand-by;
(2) add successively the described additive 1 of (0.2~1.2) XmL, the described additive 2 of (0.1~0.8) Xg and the described additive 3 of (0.05~0.3) Xg also to stir in the solution of step (1) gained, after all materials fully dissolve, namely make acidic chemical copper facing composite additive.
The using method of acidic chemical copper facing composite additive of the present invention in the electroless copper process is: in the acid chemical plating copper process, according to the volume of chemical bronze plating liquid, add 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 usingd castor oil polyoxyethylene ether as tensio-active agent, because it is a kind of nonionogenic tenside, so dispersion effect is preferably arranged under sour environment, can effectively reduce surface tension, the hydrogen that makes to be adsorbed on plating piece is overflowed fast, has avoided " hydrogen embrittlement " phenomenon.Selected additive 2 and additive 3, owing to all containing phenyl ring and heterocycle, have large π key, because the π key is delocalization, it has served as the bridge that electronics transmits, and is conducive to the reduce deposition of cupric ion and makes copper facing more smooth.And selected additive 2 and additive 3 are all the organism that contains lone electron pair, can the absorbing copper ion, and, due to the opposite charge between them, because electrostatic interaction makes the accumulation between heavy copper particle, become tightr.
The accompanying drawing explanation
Fig. 1 is the acidic chemical copper facing scanning electron microscope (SEM) photograph (2000 times) that does not add 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) that adds 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) that does not add 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) that adds acidic chemical copper facing composite additive of the present invention.
Embodiment
For the ease of it will be appreciated by those skilled in the art that below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail: embodiment 1:
Select cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).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 70% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).Contrast does not add acidic chemical copper facing composite additive of the present invention and adding, and to consist 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 be 70% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).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 80% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).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 98% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).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 75% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).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 85% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 cupric sulfate pentahydrate, 0.07mol/L iminodiethanoic acid, 0.2mol/L sodium-acetate, the 0.35mol/L sodium hypophosphite of 0.05mol/L to be basic copper facing formula, the pH value of solution is 4.5, and the copper facing temperature is 40 ℃.Take the PET film through oil removing and roughening treatment as base material (aperture that contains the 30um left and right).Contrast does not add acidic chemical copper facing composite additive of the present invention and adding, and to consist of 1ml castor oil polyoxyethylene ether, 0.6g 2-sulfydryl-acidum nicotinicum, 0.4g 8-ethoxyquinoline-5-sodium sulfonate, vitriol oil 0.1ml(concentration be 80% sulphuric acid soln) 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 respectively sample 1(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 | Have or not bubble | Have or not striped | Have or not pit | Copper facing in hole | The 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 when acidic chemical copper facing, to improve the copper plate quality, can be good at solving in entrained air bubbles and cavity (hydrogen embrittlement), striated surface or pit in the coating that occurs in acidic chemical copper facing process, aperture the problems such as the weak and copper facing poor toughness of copper facing ability.The contriver carries out respectively 2000 times and 10000 times of electroless copper electron-microscope scannings 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 the electroless copper quality.
Claims (5)
1. acidic chemical copper facing composite additive, its material composition and content are: every volume is to 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;
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.
2. acidic chemical copper facing composite additive as claimed in claim 1, it is characterized in that: described water is deionized water.
3. acidic chemical copper facing composite additive as claimed in claim 1 is characterized in that: the described vitriol oil is concentration more than or equal to 70% sulphuric acid soln.
4. as the preparation method of acidic chemical copper facing composite additive as described in claim 1 or 2 or 3, it is characterized in that comprising the following steps:
(1) getting X(X is positive number) L water, add the vitriol oil of (0~1) XmL and stir, after to be dissolved completing, be cooled to normal temperature stand-by;
(2) add successively the described additive 1 of (0.2~1.2) XmL, the described additive 2 of (0.1~0.8) Xg and the described additive 3 of (0.05~0.3) Xg also to stir in the solution of step (1) gained, after all materials fully dissolve, namely make acidic chemical copper facing composite additive.
5. as the using method of acidic chemical copper facing composite additive as described in claim 1 or 2 or 3, it is characterized in that: in the acid chemical plating copper process, according to the volume of chemical bronze plating liquid, add the acidic chemical copper facing composite additive of chemical bronze plating liquid volume 2%~3%.
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Cited By (1)
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CN112400036A (en) * | 2018-06-08 | 2021-02-23 | 德国艾托特克公司 | Electroless copper or copper alloy plating bath and method for plating |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
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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- 2013-07-18 CN CN201310301873.1A patent/CN103397316B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3787296A (en) * | 1970-04-24 | 1974-01-22 | H Hayashida | Non-poisonous zinc plating baths |
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 |
Non-Patent Citations (1)
Title |
---|
王晓波等: "电镀添加剂的研究概况", 《宁波化工》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112400036A (en) * | 2018-06-08 | 2021-02-23 | 德国艾托特克公司 | Electroless copper or copper alloy plating bath and method for plating |
JP2021527166A (en) * | 2018-06-08 | 2021-10-11 | アトテック ドイチェランド ゲーエムベーハー | Electroless copper or copper alloy plating bath and plating method |
US11396706B2 (en) * | 2018-06-08 | 2022-07-26 | Atotech Deutschland Gmbh | Electroless copper or copper alloy plating bath and method for plating |
CN112400036B (en) * | 2018-06-08 | 2023-02-21 | 德国艾托特克公司 | Electroless copper or copper alloy plating bath and method for plating |
TWI814822B (en) * | 2018-06-08 | 2023-09-11 | 德商德國艾托特克公司 | Electroless copper or copper alloy plating bath and method for plating |
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