CN101525745B - Metal surface treatment agent and printed wiring board with protecting film formed thereby - Google Patents
Metal surface treatment agent and printed wiring board with protecting film formed thereby Download PDFInfo
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- CN101525745B CN101525745B CN2009100588332A CN200910058833A CN101525745B CN 101525745 B CN101525745 B CN 101525745B CN 2009100588332 A CN2009100588332 A CN 2009100588332A CN 200910058833 A CN200910058833 A CN 200910058833A CN 101525745 B CN101525745 B CN 101525745B
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Abstract
The invention relates to a metal surface treatment agent which is used for protecting the surface of metal from being oxidized, improving the solderability of the metal and providing a protective coating for the copper surface of a printed circuit board (PCB), and a printed wiring board with a protecting film formed by applying the treatment agent. The surface treatment agent contains azole compound, organic acid, cupric compound, zinc compound, iron compound and aqueous solution of the compounds having antioxidant effect; wherein, the compounds having antioxidant effect are calixarenes compound and thiacalixarenes compound which have the structure in formula (1), and can be sedimentated on the surface of the metal together with imidazole and metallic ions to form the protecting film. In the formula (1), R1 is SO3<->, COO<->or tert-butyl group, and R2 is S, SO or SO2. n=4, 6.
Description
Technical field
The present invention relates to a kind of treatment agent of metallic surface, particularly a kind ofly be used for metal conditioner weldability, that protective coating is provided for the copper surface of printed circuit board (PCB) (PCB) that the protective money metal surface is avoided oxidation and strengthened it.The invention still further relates to and use the printed-wiring board (PWB) that this treatment agent forms protective membrane.
Background technology
Extensively adopt highdensity surface mounting technique in recent years, this technology needs carry out multiple welding to PCB, makes PCB stand multiple high temp, and this has quickened the formation of the oxide film of the copper of part among the PCB or copper alloy surface, thereby can not keep the good weldability in surface.For the not oxidation by air of copper wire part of protection PCB, use surface treatment agent to form the chemical layer of protectiveness on the line usually.Typical protectiveness binder is imidazoles or benzimidizole derivatives, the common called after Organic Solderability protection of coating (OSP) coating.
Because plumbous harm to the mankind prevents that Lead contamination from having become world trends.Along with banning use of of tin-lead solder, lead-free solder (the SAC series that main flow is used, fusing point 217-230 ℃) melting temperature higher approximately 20-50 ℃ than wiping solder (187 ℃ of fusing points), thereby wish on the PCB copper surface to form and have the more OSP coating of excellent heat resistance.The organometallic polymer that the OSP film is mainly formed by imidazoles or benzimidizole derivatives and metal and carry organic molecule secretly and form in deposition process is as lipid acid and azole compounds.Organometallic polymer provides the surface hardness of necessary erosion resistance, copper surface adhesive and OSP.The fusing point that the degradation temperature of organometallic polymer must be higher than lead-free solder just can stand leadless process (the processing procedure top temperature can reach 250-260 ℃) processing.Otherwise the OSP film can handled the back degraded through leadless process.
The degradation temperature of OSP film depends on the thermotolerance of organometallic polymer to a great extent.Improve the thermotolerance of OSP, that is to say the antioxidant property that improves OSP.The common practice that improves the antioxidant property of material is to add a certain proportion of antioxidant addn.General antioxidant commonly used has butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), Tenox PG (PG), Tert. Butyl Hydroquinone (TBHQ), 1,3,5-three (3,5 tertiary butyl-4-hydroxy benzyls) Three methyl Benzene (TBM), four (β-(3,5-di-t-butyl 4-hydroxy phenyl) pentaerythritol ester (antioxidant 1010) propionic acid), β (3,5 di-tert-butyl-hydroxy phenyl) propionic acid stearyl alcohol ester (antioxidant 1076), 4,4 '-two uncle's octyl diphenylamines (DOD), 2,2 '-methylene bis (4-methyl-6-tert butyl phenol) (antioxidant 2246 B), Tyox B, the two octadecyl ester pentaerythritol esters (DPD) of diphosphorous acid, three (nonyl is for phenyl) phosphorous acid ester (TNP), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (TBP) etc.But since these traditional oxygenants can not with metal ion (as cupric ion), imidazolium compounds complexing, can't deposit to together in the organometallic polymer film (OSP), thereby can't in PCB welding processing procedure subsequently, strengthen the antioxidant property on exposed copper surface.So generally do not add antioxidant in existing this type of metal conditioner.
The research that improves at present the antioxidant property of OSP mainly concentrates on the structure of modification to imidazoles or benzimidizole derivatives.Chinese patent CN1964949 (A) discloses the phenyl napthyl glyoxaline compound, as 2-phenyl-4-(1-naphthyl) imidazoles; Chinese patent CN1761773 (A) discloses 2-phenyl-4-phenylimidazole compounds, as 2-(2, the 3-dichloro) phenyl 4-phenyl-5-Methylimidazole; Chinese patent CN1391618 (B) discloses the benzimidazoles compound that replaces, preferred 2 substituted benzimidazoles compounds.But variable color or crack can take place in this type of OSP film (OSP film on the terminal pad that refers to not weld) after process multiple high temp welding process, influence weldability and reliability.Therefore still needing is that OSP is formed the improvement that continues, and continues to improve the antioxidant property of OSP, with the application of further expansion OSP film in PCB.
Summary of the invention
The purpose of this invention is to provide a kind of new type of metal surface treatment agent (OSP), its overcome the conventional oxidation agent can not with metal ion (as cupric ion), the imidazolium compounds complexing, can't deposit to together in the organometallic polymer film (OSP), thereby can't in PCB welding processing procedure subsequently, strengthen the shortcoming of the antioxidant property on exposed copper surface, make in the organometallic polymer film of formation and be inlaid with a certain proportion of oxidation resistant material (non-carrying secretly), thereby need not the structure of existing imidazoles or benzimidizole derivatives is transformed, just can improve the heat resisting temperature and the resistance toheat of corresponding OSP film, reach required standard in PCB welding processing procedure subsequently.
Another object of the present invention is to provide a kind of printed-wiring board (PWB) that this treatment agent has formed protective membrane of using, the heat resisting temperature and the resistance toheat of the OSP film on this wiring board are higher, can reach required standard in the welding processing procedure.
Technical scheme of the present invention is: a kind of metal conditioner, its essentially consist are the aqueous solution that contains glyoxaline compound, organic acid, copper compound, zn cpds, iron cpd and have the compound of antioxidant effect.Described compound with antioxidant effect be can with metal ion (as cupric ion) and (or) compound of imidazolium compounds complexing.
The calixarene compound that described compound with antioxidant effect is structure such as figure below also can use the mixture of two or more compounds or/and the sulfo-calixarene compound can use wherein a kind of compound, and its consumption is 0.001%-10%.
R
1=SO
3 -Or COO
-Or the tertiary butyl
R
2=S or SO or SO
2
The calixarene compound that described compound with antioxidant effect is structure such as figure below also can use the mixture of two or more compounds or/and the sulfo-calixarene compound can use wherein a kind of compound, and it is 0.001%-6% for consumption.
R
1=SO
3 -Or COO
-Or the tertiary butyl
R
2=S or SO or SO
2
Described metal conditioner also includes organic solvent.
The consumption of described organic solvent is 0.1-40%.
The consumption of described organic solvent is 0.5-10%.
Glyoxaline compound in the composition of the present invention is not done special qualification, can use various known glyoxaline compound and the benzimidazoles compounds that are applied to this area, preferred two or more imidazoles is used in combination.
Glyoxaline compound comprises the compound with imidazole ring, the exemplary that is fit to enforcement imidazolium compounds of the present invention comprises: 2, and 4-phenylbenzene-1H-imidazoles, 5-butyl-2,4-phenylbenzene-1H-imidazoles, 5-hexyl-2,4-phenylbenzene-1H-imidazoles, 5-ethylhexyl-2,4-phenylbenzene-1H-imidazoles, 2-phenyl-4-(2,4 dichloro benzene base) 5-Methylimidazole, 2-phenyl-4-(3, the 4-dichlorophenyl)-the 5-Methylimidazole, 2-(2, the 3-dichloro) phenyl-4-phenylimidazole, 2-(2, the 3-dichloro) phenyl-4-phenyl-5-Methylimidazole, 2-phenyl-4-(1-naphthyl) imidazoles, 2-phenyl-4-(2-naphthyl) imidazoles, 2-phenyl-4-(1-naphthyl)-5-Methylimidazole, 2-(1-naphthyl)-4-phenylimidazole, 2-(2-naphthyl)-4-phenylimidazole, 2-(1-naphthyl)-4-phenyl-5-Methylimidazole, 2-(1-naphthyl)-4-phenyl-5-hexyl imidazoles etc.
Benzimidazoles compound comprises all compounds that contain the benzoglyoxaline ring element, the exemplary that is fit to enforcement benzimidazole compound of the present invention comprises: 1-(p-chlorobenzyl) 2-(rubigan) benzoglyoxaline, 1-(to methoxy-benzyl)-2-(p-methoxyphenyl) benzoglyoxaline, 2-(8-phenyl octyl group) benzoglyoxaline, 4,5-two chloro-6-normal-butyl-2-(9-phenyl nonyl) benzoglyoxaline, 2-octyl group benzoglyoxaline, 2-(8-phenyl octyl group) benzoglyoxaline, 2-benzyl benzimidazole etc.
Described glyoxaline compound and benzimidazoles compound total amount are 0.01-10%.
Described glyoxaline compound and benzimidazoles compound total amount are 0.05-2%.
Described organic acid can be selected formic acid, acetate, Succinic Acid, hexanodioic acid etc. for use.
Described organic acid consumption is 0.1-40%.
Described organic acid consumption is 0.5-10%.
Described copper compound can be selected any water miscible copper compound that has for use, as cupric chloride, copper sulfate, cupric bromide, cupric phosphate, neutralized verdigris etc.
Described zn cpds can be selected any water miscible zn cpds that has for use, as zinc acetate, zinc oxalate, zinc bromide etc.
Described iron cpd can be selected any water miscible iron cpd that has for use, as iron acetate, ironic oxalate, iron bromide etc.
This three metal compound can use separately, also can two or more be used in combination, and its consumption is 0.01-10%.
This three metal compound can use separately, also can two or more be used in combination, and its consumption is 0.05-5%.
PCB through oil removing, washing, microetch, washing, pickling, washing, drying, is immersed in certain hour in 40-50 ℃ this surface treatment agent then,, can forms the OSP film of 0.1-0.5 micron thickness on the copper surface with after washing and drying.
The metal conditioner that adopts this technical scheme to form, because having added therein can be with metal ion (as cupric ion) or/and the compound with antioxygenation of imidazolium compounds complexing, the antioxygen thing is deposited with metal ion (as cupric ion), imidazolium compounds, just be inlaid with a certain proportion of oxidation resistant material (non-carrying secretly) in the organometallic polymer film that forms, improved the heat resisting temperature and the resistance toheat of corresponding OSP film.The structure that need not like this to seek again imidazoles or benzimidizole derivatives is transformed, and has just reached required standard in the PCB welding processing procedure subsequently.
Calixarene compound of described structure such as figure below and sulfo-calixarene compound can use wherein a kind of compound, also can use the mixture of two or more compounds, and its consumption is 0.001%-10%, and preferable amount is 0.001%-6%.
R
1=SO
3 -Or COO
-Or the tertiary butyl
R
2=S or SO or SO
2
When the R1 group was sulfonic group or carboxyl, used calixarene compound or sulfo-calixarene compound all had good water-solubility, and when being the tertiary butyl, poorly water-soluble can suitably be chosen organic solvent to promote its solvability in water.The present composition can contain organic solvent, also can not contain organic solvent.When with an organic solvent, can not add the organic solvent that selecting for use of restriction can be miscible with water, such as ethanol, acetone, ethylene glycol, glycol ether etc., preferred ethylene glycol or gylcol ether organic solvent, its typical amounts is 0.1-40%, and preferable amount is 0.5-10%.Organic solvent can use a kind of, also can use the combination of the organic solvent more than two kinds.Above-mentioned solvent can fully dissolve polyphenoils in the use of above-mentioned scope, simultaneously, can not increase the danger of the present composition at aspects such as incendivities.
Glyoxaline compound in the composition of the present invention is not done special qualification, can use various known glyoxaline compound and the benzimidazoles compounds that are applied to this area, preferred two or more imidazoles is used in combination.When glyoxaline compound and benzimidazoles compound total amount less than 0.01% the time, can not form effective protective membrane, and greater than 10% o'clock, insolubles can increase.
Another technical scheme of the present invention is: a kind of printed-wiring board (PWB), used the described metal conditioner of last technical scheme, and formed protective membrane.The heat resisting temperature and the resistance toheat of the OSP film on this wiring board are higher, can reach required standard in the welding processing procedure.
Embodiment
Embodiment 1
Component and each components contents of the OSP aqueous solution treatment agent of embodiment 1 see Table 1.
After the composition of record is dissolved in deionized water in the embodiment 1 usefulness table 1, regulate pH to 3.0, prepare metal conditioner thus with ammoniacal liquor.Then with the test film of printed circuit board (PCB) (as schematic circuit; Copper Foil by 10 40 * 0.7mm forms; each Copper Foil is at width interval 1mm) degrease in clean-out system; washing; in the micro-etching agent that sulfuric acid/hydrogen peroxide is done, soak 60-120 second; deionization washing 3 times; drying is soaked 15-30 second, deionization washing 3 times in the aqueous hydrochloric acid of 3-5%; dry; in 40 ℃ surface treatment agent, soaked drying, deionization washing 3 times 60 seconds; drying can form the protective membrane of 0.1-0.5 micron in PCB surface.
Embodiment 2-10
The metal conditioner that has the composition of table 1 record according to operation preparation similarly to Example 1.Adopt the art breading printed-wiring board (PWB) identical, then at the protective membrane for preparing under the condition that table 1 is put down in writing on the PCB with embodiment 1.
Comparative example 1-3
The metal conditioner that has the composition of table 1 record according to operation preparation similarly to Example 1.Adopt the art breading printed-wiring board (PWB) identical, then at the protective membrane for preparing under the condition that table 1 is put down in writing on the PCB with embodiment 1.
To the stable on heating evaluation of protective membrane
The printed-wiring board (PWB) that is formed with protective membrane is positioned in the used reflow ovens of welding heating, backflow 0-3 time, the peak temperature of printed circuit board (PCB) in reflow ovens is 245 ℃.Examine under a microscope the outward appearance of protective membrane, use then 0.2 micron metal form (die plate pattern: the hole of 10 3.0 * 0.7mm, between the hole at width 1mm at interval) carry out paste solder printing, put into reflow ovens then and heat, measure and sprawl length.It is big more to sprawl length, shows that the wettability of protective membrane is high more, shows that the thermostability after standing high temperature is good more.The evaluation result of each embodiment and comparative example is listed in table 2.As seen the effect of the embodiment of the invention obviously is better than traditional comparative example.
Table 2
Annotate: ◎ does not have variable color and be full of cracks
Light discolouration * obviously variable color and be full of cracks
Claims (9)
1. metal conditioner, its essentially consist is the aqueous solution that contains glyoxaline compound, organic acid, copper compound, zn cpds, iron cpd and have the compound of antioxidant effect, described compound with antioxidant effect be can with the compound of metal ion and/or imidazolium compounds complexing, it is characterized in that calixarene compound that described compound with antioxidant effect is structure such as figure below is or/and the sulfo-calixarene compound:
R
1=SO
3-Or COO
-Or the tertiary butyl
R
2=S or SO or SO
2
2. metal conditioner as claimed in claim 1 is characterized in that described compound amount with antioxidant effect is 0.001%-10%.
3. metal conditioner as claimed in claim 1 is characterized in that described compound amount with antioxidant effect is 0.001%-6%.
4. as claim 2 or 3 described metal conditioners, it is characterized in that it also includes organic solvent.
5. metal conditioner as claimed in claim 4, the consumption that it is characterized in that described organic solvent is 0.1-40%.
6. metal conditioner as claimed in claim 5, the consumption that it is characterized in that described organic solvent is 0.5-10%.
7. as arbitrary metal conditioner as described in the claim 1 to 3, it is characterized in that described glyoxaline compound is that two or more imidazoles is used in combination.
8. as metal conditioner as described in the claim 7, it is characterized in that described glyoxaline compound total amount is 0.05-2%.
9. a printed-wiring board (PWB) is characterized in that using the described surface treatment agent of claim 1, has formed protective membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100588332A CN101525745B (en) | 2009-04-03 | 2009-04-03 | Metal surface treatment agent and printed wiring board with protecting film formed thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100588332A CN101525745B (en) | 2009-04-03 | 2009-04-03 | Metal surface treatment agent and printed wiring board with protecting film formed thereby |
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| Publication Number | Publication Date |
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| CN101525745A CN101525745A (en) | 2009-09-09 |
| CN101525745B true CN101525745B (en) | 2011-03-30 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104918417A (en) * | 2015-05-15 | 2015-09-16 | 江门崇达电路技术有限公司 | Method for producing organic solderability preservative on surface of circuit board |
| CN105838193B (en) * | 2016-05-12 | 2018-11-20 | 江苏永阳新材料科技有限公司 | A kind of water-base epoxy priming paint |
| CN106852005B (en) * | 2017-02-24 | 2019-05-14 | 广东成德电子科技股份有限公司 | A method of printed circuit board is made using calixarenes |
| CN106793537B (en) * | 2017-02-24 | 2019-04-30 | 广东成德电子科技股份有限公司 | A method of printed circuit board is made using calixarenes |
| CN106686900B (en) * | 2017-02-24 | 2019-06-25 | 广东成德电子科技股份有限公司 | A method of printed circuit board is processed using calixarenes |
| CN107971655B (en) * | 2018-01-23 | 2019-12-27 | 永星化工(上海)有限公司 | High-heat-resistance organic solder flux and application thereof |
| CN109735838B (en) * | 2019-03-14 | 2021-06-29 | 广东省石油与精细化工研究院 | Selective organic weldable protective agent for copper surface |
| CN113556885B (en) * | 2021-06-29 | 2023-08-04 | 联宝(合肥)电子科技有限公司 | Welding process based on oxidation protection |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654709A (en) * | 2004-02-10 | 2005-08-17 | 田村化研株式会社 | Surface treatment agents for metal films of printed circuit boards |
| CN1737198A (en) * | 2005-09-07 | 2006-02-22 | 陈光凤 | Metal oxidation resistance liquid and method for producing the same |
| CN101379219A (en) * | 2005-10-25 | 2009-03-04 | 德国艾托科技公司 | Composition and method for improved adhesion of polymeric materials to copper or copper alloy surfaces |
-
2009
- 2009-04-03 CN CN2009100588332A patent/CN101525745B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654709A (en) * | 2004-02-10 | 2005-08-17 | 田村化研株式会社 | Surface treatment agents for metal films of printed circuit boards |
| CN1737198A (en) * | 2005-09-07 | 2006-02-22 | 陈光凤 | Metal oxidation resistance liquid and method for producing the same |
| CN101379219A (en) * | 2005-10-25 | 2009-03-04 | 德国艾托科技公司 | Composition and method for improved adhesion of polymeric materials to copper or copper alloy surfaces |
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| CN101525745A (en) | 2009-09-09 |
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Application publication date: 20090909 Assignee: Beijing Kds Co., Ltd. Assignor: Sichuan University Contract record no.: 2013990000811 Denomination of invention: Metal surface treatment agent and printed wiring board with protecting film formed thereby Granted publication date: 20110330 License type: Exclusive License Record date: 20131203 |
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