CN105744753A - Method for forming oxidation-resistant protecting membrane on surfaces of copper and copper alloy on printed circuit board - Google Patents
Method for forming oxidation-resistant protecting membrane on surfaces of copper and copper alloy on printed circuit board Download PDFInfo
- Publication number
- CN105744753A CN105744753A CN201610295555.2A CN201610295555A CN105744753A CN 105744753 A CN105744753 A CN 105744753A CN 201610295555 A CN201610295555 A CN 201610295555A CN 105744753 A CN105744753 A CN 105744753A
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- CN
- China
- Prior art keywords
- wiring board
- printed wiring
- copper
- oxidation
- concentration
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/03—Metal processing
- H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
Abstract
The invention discloses a method for forming an oxidation-resistant protecting membrane on surfaces of copper and a copper alloy on a printed circuit board. The method comprises the following steps of: 1, oil removing; 2, micro-etching, 3, activation; 4, oxidation, and 5, cleaning. The invention aims to provide a method for forming the oxidation-resistant protecting membrane on surfaces of copper and the copper alloy on the printed circuit board. By adopting the method, the copper surface has a good oxidation-resistant capacity and is enabled to tolerate a plurality of times of high-temperature welding when the method is applied for surface processing.
Description
Technical field
The present invention relates to printed wiring board process field, on espespecially a kind of printed wiring board, copper and copper alloy surface form anti-oxidation protection epithelium method.
Background technology
Printed wiring board relates to repeatedly metallization processes in the fabrication process, such as electroless copper, electro-coppering, electronickelling gold, chemical plating stannum etc..Before printed wiring board does not complete final welding, its surface layers of copper is not if being protected by, very easily oxidized under the high humility of job shop, peracidity or alkali condition, affects subsequent diagram operation or the reliability of final welding.The surface treatment mode of printed wiring board finished product copper face protection has a variety of, such as chemical nickel plating gold, chemical plating stannum, chemical silvering, electronickelling gold, spray stannum etc..Early stage copper face antioxidant is made up of methanol and BTA, and health is brought very big threat by high volatility.In addition this organic protection leather film thickness is difficult to control to, and oxidation resistance is not enough.Development through several generations; current copper face anti-oxidation protection epithelium technique for applying is still difficult to high temperature resistant welding, the printed wiring board of selective chemical nickel plating gold easily produces copper deposition in gold face in the process forming protection epithelium; dredge the layer gold of permeability once occur Jafani effect will cause that nickel dam aoxidizes, and causes failure welding.
Summary of the invention
For solving the problems referred to above, the present invention provides copper and copper alloy surface on a kind of printed wiring board to form anti-oxidation protection epithelium method.
For achieving the above object, the present invention adopts the following technical scheme that and is: on a kind of printed wiring board, copper and copper alloy surface form anti-oxidation protection epithelium method, comprise the steps:
Step one: oil removing
Remove the greasy dirt on printed wiring board surface, prepare low bubble acid deoiling agent and add water with 20% volume ratio preparation oil removing solution, and to being immersed in by printed wiring board in oil removing solution after oil removing solution warms to 40 DEG C 60 seconds, remove the printed wiring board plate face development foreign material such as residue and finger-marks；
Step 2: microetch
Printed wiring board after step one cleans being entered micro-corrosion liquid process, remove copper face slight oxidation thing on printed wiring board, described micro-corrosion liquid is the sulfuric acid solution of sodium peroxydisulfate, Ammonium persulfate. or hydrogen peroxide；
Step 3: activation:
Copper face on the printed wiring board that step 2 microetch processes is obtained the roughness that can improve soldering reliability, then copper face needs sulfuric acid solution activates, described sulfuric acid solution is 5%v/v(5%v/v to be volume ratio be 5 percent the meaning) aqueous sulfuric acid, the temperature of aqueous sulfuric acid is 20～30 DEG C, being immersed by printed wiring board and treat the uniform bubble of piece surface in this solution after 3～5min, taking-up part is put in tap water rapidly and is cleaned up；
Step 4:
By after step 3 activates printed wiring board on copper face enter to be formed after anti-oxidation liquid and uniform be bonded anti-oxidation epithelium, described anti-oxidation liquid includes: concentration is formic acid or the glacial acetic acid of 5-30g/L, concentration is the alkyl imidazole of 0.001-1g/L, concentration is the copper ion of 0.1-1000ppm, surplus pH value regulator, wherein, described alkyl imidazole is benzimidazole, 2-tolimidazole, 2-ethyl benzo imidazole, 2-hexyl benzimidazole, one or more mixture in 2-heptyl benzimidazole, described pH adjusting agent is ammonia, the pH value of described anti-oxidation liquid is 2.85, the temperature of described anti-oxidation liquid is at 40 DEG C-46 DEG C, on printed wiring board, copper face is immersed in the time of anti-oxidation liquid is the 60-90 second;
Step 5: clean:
Printed wiring board after anti-oxidation liquid processes is washed twice post-drying and is preserved.
Preferably, the concentration of formic acid described in step 4 or glacial acetic acid is 10-25g/L.
Preferably, the concentration of alkyl imidazole described in step 4 is 0.01-0.5g/L.
Preferably, the concentration of copper ion described in step 4 is 0.5-200ppm.
The beneficial effects of the present invention is: the present invention can make copper and copper alloy surface on printed wiring board produce a kind of organic coating based on alkyl imidazole, copper face aoxidize inhibitory action, and this technique as copper face surface treatment time, resistant against high temperatures welding.Organic protection epithelium (or organic weldable protective agent) is a kind of fairly simple and economic mode; it makes copper face non-oxidizability significantly improve after processing; and protection leather film thickness is very thin, surface is smooth due to this, be particularly well-suited to thin wire, fine rule from printed wiring board surface treatment.
Detailed description of the invention
The present invention forms anti-oxidation protection epithelium method about copper on printed wiring board and copper alloy surface, comprises the steps:
Step one: oil removing
Remove the greasy dirt on printed wiring board surface, prepare low bubble acid deoiling agent and add water with 20% volume ratio preparation oil removing solution, and to being immersed in by printed wiring board in oil removing solution after oil removing solution warms to 40 DEG C 60 seconds, remove the printed wiring board plate face development foreign material such as residue and finger-marks；
Step 2: microetch
Printed wiring board after step one cleans being entered micro-corrosion liquid process, remove copper face slight oxidation thing on printed wiring board, described micro-corrosion liquid is the sulfuric acid solution of sodium peroxydisulfate, Ammonium persulfate. or hydrogen peroxide；
Step 3: activation:
Copper face on the printed wiring board that step 2 microetch processes is obtained the roughness that can improve soldering reliability, then copper face needs sulfuric acid solution activates, described sulfuric acid solution is 5%v/v(5%v/v to be volume ratio be 5 percent the meaning) aqueous sulfuric acid, the temperature of aqueous sulfuric acid is 20～30 DEG C, being immersed by printed wiring board and treat the uniform bubble of piece surface in this solution after 3～5min, taking-up part is put in tap water rapidly and is cleaned up；
Step 4:
By after step 3 activates printed wiring board on copper face enter to be formed after anti-oxidation liquid and uniform be bonded anti-oxidation epithelium, described anti-oxidation liquid includes: concentration is formic acid or the glacial acetic acid of 5-30g/L, concentration is the alkyl imidazole of 0.001-1g/L, concentration is the copper ion of 0.1-1000ppm, surplus pH value regulator, wherein, described alkyl imidazole is benzimidazole, 2-tolimidazole, 2-ethyl benzo imidazole, 2-hexyl benzimidazole, one or more mixture in 2-heptyl benzimidazole, described pH adjusting agent is ammonia, the pH value of described anti-oxidation liquid is 2.85, the temperature of described anti-oxidation liquid is at 40 DEG C-46 DEG C, on printed wiring board, copper face is immersed in the time of anti-oxidation liquid is the 60-90 second;
Step 5: clean:
Printed wiring board after anti-oxidation liquid processes is washed twice post-drying and is preserved.
Preferably, the concentration of formic acid described in step 4 or glacial acetic acid is 10-25g/L.
Preferably, the concentration of alkyl imidazole described in step 4 is 0.01-0.5g/L.
Preferably, the concentration of copper ion described in step 4 is 0.5-200ppm.
Embodiment 1:
Step one: printed wiring board is first through the low bubble acid deoiling technique cleaner plate face development foreign material such as residue and finger-marks, and described low bubble acid deoiling agent prepares oil removing solution with 20% volume ratio, is immersed in by printed wiring board in oil removing solution 60 seconds after being warming up to 40 DEG C；
Step 2: cleaning the printed wiring board after oil removing through step one and enter micro-corrosion liquid process, remove copper face slight oxidation thing on printed wiring board, described micro-corrosion liquid is the sulfuric acid solution of sodium peroxydisulfate, Ammonium persulfate. or hydrogen peroxide；
Step 3: copper face obtains the roughness that can improve soldering reliability on the printed wiring board that step 2 microetch processes, and then copper face needs sulfuric acid solution activates, and described sulfuric acid solution is the aqueous sulfuric acid of 5%v/v；
Step 4: on the printed wiring board after step 3 activates, copper face can form the anti-oxidation epithelium of uniform bonding under the process conditions after entering anti-oxidation liquid, concentration is the formic acid of 15g/L or glacial acetic acid, concentration be the 2-hexyl benzimidazole of 0.1g/L, concentration is the copper ion of 20ppm, surplus pH value regulator, on described printed wiring board, copper face is at the anti-oxidation liquid that temperature is 42 DEG C, and pH value processes 60 seconds for 2.85 times.
Step 5: the printed wiring board after anti-oxidation liquid processes is washed twice post-drying and preserved.
Embodiment 2:
Embodiment 2 and embodiment 1 are distinctive in that, described anti-oxidation liquid is the 2-hexyl benzimidazole of 0.1g/L, concentration containing the formic acid that concentration is 20g/L or glacial acetic acid, concentration is the copper ion of 20ppm, surplus pH value regulator, on described printed wiring board, copper face is at the anti-oxidation liquid that temperature is 40 DEG C, and pH value processes 90 seconds for 2.85 times.
Embodiment 3:
Embodiment 3 and embodiment 1 are distinctive in that, on described printed wiring board, copper face is at the anti-oxidation liquid that temperature is 46 DEG C, and pH value processes 30 seconds for 2.85 times.
Embodiment of above is only that the preferred embodiment of the present invention is described; not the scope of the present invention is defined; under the premise designing spirit without departing from the present invention; various deformation that technical scheme is made by this area ordinary skill technical staff and improvement, all should fall in the protection domain that claims of the present invention are determined.
Claims (4)
1. on a printed wiring board, copper and copper alloy surface form anti-oxidation protection epithelium method, it is characterised in that: comprise the steps:
Step one: oil removing
Remove the greasy dirt on printed wiring board surface, prepare low bubble acid deoiling agent and add water with 20% volume ratio preparation oil removing solution, and to being immersed in by printed wiring board in oil removing solution after oil removing solution warms to 40 DEG C 60 seconds, remove the printed wiring board plate face development foreign material such as residue and finger-marks；
Step 2: microetch
Printed wiring board after step one cleans being entered micro-corrosion liquid process, remove copper face slight oxidation thing on printed wiring board, described micro-corrosion liquid is the sulfuric acid solution of sodium peroxydisulfate, Ammonium persulfate. or hydrogen peroxide；
Step 3: activation:
Copper face on the printed wiring board that step 2 microetch processes is obtained the roughness that can improve soldering reliability, then copper face needs sulfuric acid solution activates, described sulfuric acid solution is 5%v/v(5%v/v to be volume ratio be 5 percent the meaning) aqueous sulfuric acid, the temperature of aqueous sulfuric acid is 20～30 DEG C, being immersed by printed wiring board and treat the uniform bubble of piece surface in this solution after 3～5min, taking-up part is put in tap water rapidly and is cleaned up；
Step 4:
By after step 3 activates printed wiring board on copper face enter to be formed after anti-oxidation liquid and uniform be bonded anti-oxidation epithelium, described anti-oxidation liquid includes: concentration is formic acid or the glacial acetic acid of 5-30g/L, concentration is the alkyl imidazole of 0.001-1g/L, concentration is the copper ion of 0.1-1000ppm, surplus pH value regulator, wherein, described alkyl imidazole is benzimidazole, 2-tolimidazole, 2-ethyl benzo imidazole, 2-hexyl benzimidazole, one or more mixture in 2-heptyl benzimidazole, described pH adjusting agent is ammonia, the pH value of described anti-oxidation liquid is 2.85, the temperature of described anti-oxidation liquid is at 40 DEG C-46 DEG C, on printed wiring board, copper face is immersed in the time of anti-oxidation liquid is the 60-90 second;
Step 5: clean:
Printed wiring board after anti-oxidation liquid processes is washed twice post-drying and is preserved.
2. on printed wiring board according to claim 1, copper and copper alloy surface form anti-oxidation protection epithelium method, it is characterised in that: the concentration of formic acid described in step 4 or glacial acetic acid is 10-25g/L.
3. on printed wiring board according to claim 1, copper and copper alloy surface form anti-oxidation protection epithelium method, it is characterised in that: the concentration of alkyl imidazole described in step 4 is 0.01-0.5g/L.
4. on printed wiring board according to claim 1, copper and copper alloy surface form anti-oxidation protection epithelium method, it is characterised in that: the concentration of copper ion described in step 4 is 0.5-200ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610295555.2A CN105744753B (en) | 2016-05-06 | 2016-05-06 | Copper and copper alloy surface form anti-oxidation protection epithelium method on printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610295555.2A CN105744753B (en) | 2016-05-06 | 2016-05-06 | Copper and copper alloy surface form anti-oxidation protection epithelium method on printed wiring board |
Publications (2)
| Publication Number | Publication Date |
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| CN105744753A true CN105744753A (en) | 2016-07-06 |
| CN105744753B CN105744753B (en) | 2018-06-15 |
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| CN201610295555.2A Active CN105744753B (en) | 2016-05-06 | 2016-05-06 | Copper and copper alloy surface form anti-oxidation protection epithelium method on printed wiring board |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107046776A (en) * | 2017-04-06 | 2017-08-15 | 江门崇达电路技术有限公司 | A kind of anti-oxidant surface treatment method of PCB |
| CN107635357A (en) * | 2017-09-13 | 2018-01-26 | 东莞联桥电子有限公司 | A kind of pcb board golden finger guard method of easy to clean |
| CN108566737A (en) * | 2018-06-08 | 2018-09-21 | 深圳市五株科技股份有限公司 | A kind of processing method and PCB of PCB |
| CN110418514A (en) * | 2019-06-12 | 2019-11-05 | 惠州市特创电子科技有限公司 | A kind of preparation method of the anti-oxidant wiring board of 24G high frequency |
| CN112226721A (en) * | 2020-07-28 | 2021-01-15 | 安徽富乐德科技发展股份有限公司 | Preparation process of copper meltallizing layer applied to electronic industry equipment cavity |
| CN112853341A (en) * | 2020-12-31 | 2021-05-28 | 南通赛可特电子有限公司 | Cleaning and oxidation resisting process for surface treatment of copper foil of printed circuit board |
| CN113737167A (en) * | 2021-09-22 | 2021-12-03 | 东莞市四辉表面处理科技有限公司 | Copper material antioxidant and preparation method thereof |
| CN114025507A (en) * | 2021-11-23 | 2022-02-08 | 广德宝达精密电路有限公司 | Oxidation-resistant production process of circuit board |
| CN115125541A (en) * | 2022-05-19 | 2022-09-30 | 宁波博曼特工业有限公司 | Surface oxidation resistance treatment process of tin bronze |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619333A2 (en) * | 1993-04-03 | 1994-10-12 | ATOTECH Deutschland GmbH | Process for coating metals |
| CN101867009A (en) * | 2010-05-07 | 2010-10-20 | 厦门永红科技有限公司 | LED lead frame and electroplating method and electroplating equipment thereof |
| CN103928302A (en) * | 2014-04-28 | 2014-07-16 | 四川金湾电子有限责任公司 | Semiconductor lead frame manufacturing technology |
| CN104900536A (en) * | 2015-04-10 | 2015-09-09 | 四川金湾电子有限责任公司 | Semiconductor lead frame surface treatment method |
-
2016
- 2016-05-06 CN CN201610295555.2A patent/CN105744753B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0619333A2 (en) * | 1993-04-03 | 1994-10-12 | ATOTECH Deutschland GmbH | Process for coating metals |
| CN101867009A (en) * | 2010-05-07 | 2010-10-20 | 厦门永红科技有限公司 | LED lead frame and electroplating method and electroplating equipment thereof |
| CN103928302A (en) * | 2014-04-28 | 2014-07-16 | 四川金湾电子有限责任公司 | Semiconductor lead frame manufacturing technology |
| CN104900536A (en) * | 2015-04-10 | 2015-09-09 | 四川金湾电子有限责任公司 | Semiconductor lead frame surface treatment method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107046776A (en) * | 2017-04-06 | 2017-08-15 | 江门崇达电路技术有限公司 | A kind of anti-oxidant surface treatment method of PCB |
| CN107046776B (en) * | 2017-04-06 | 2019-04-02 | 江门崇达电路技术有限公司 | A kind of anti-oxidant surface treatment method of PCB |
| CN107635357A (en) * | 2017-09-13 | 2018-01-26 | 东莞联桥电子有限公司 | A kind of pcb board golden finger guard method of easy to clean |
| CN108566737A (en) * | 2018-06-08 | 2018-09-21 | 深圳市五株科技股份有限公司 | A kind of processing method and PCB of PCB |
| CN110418514A (en) * | 2019-06-12 | 2019-11-05 | 惠州市特创电子科技有限公司 | A kind of preparation method of the anti-oxidant wiring board of 24G high frequency |
| CN112226721A (en) * | 2020-07-28 | 2021-01-15 | 安徽富乐德科技发展股份有限公司 | Preparation process of copper meltallizing layer applied to electronic industry equipment cavity |
| CN112853341A (en) * | 2020-12-31 | 2021-05-28 | 南通赛可特电子有限公司 | Cleaning and oxidation resisting process for surface treatment of copper foil of printed circuit board |
| CN113737167A (en) * | 2021-09-22 | 2021-12-03 | 东莞市四辉表面处理科技有限公司 | Copper material antioxidant and preparation method thereof |
| CN114025507A (en) * | 2021-11-23 | 2022-02-08 | 广德宝达精密电路有限公司 | Oxidation-resistant production process of circuit board |
| CN114025507B (en) * | 2021-11-23 | 2023-12-12 | 广德宝达精密电路有限公司 | Production process for antioxidation of circuit board |
| CN115125541A (en) * | 2022-05-19 | 2022-09-30 | 宁波博曼特工业有限公司 | Surface oxidation resistance treatment process of tin bronze |
| CN115125541B (en) * | 2022-05-19 | 2024-04-12 | 宁波博曼特工业有限公司 | Surface antioxidation treatment process for tin bronze |
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