CN101351090A - Ultra-roughening treating agent for cuprum surface - Google Patents
Ultra-roughening treating agent for cuprum surface Download PDFInfo
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- CN101351090A CN101351090A CNA2007100292777A CN200710029277A CN101351090A CN 101351090 A CN101351090 A CN 101351090A CN A2007100292777 A CNA2007100292777 A CN A2007100292777A CN 200710029277 A CN200710029277 A CN 200710029277A CN 101351090 A CN101351090 A CN 101351090A
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- copper
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- guanidine
- treating agent
- cuprum
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Abstract
The invention provides a cu surface super roughening treating agent composed of the following components and weight percents: 10 to 50 percent of organic copper, 10 to 30 percent of organic acids, 0.1 to 5 percent of guanidine compounds, 0.1 to 5 percent of azole compounds, 0.1 to 5 percent of alcohol amine compounds and the rest are de-ionized water. The cu surface super roughening treating agent of the organic copper system of the invention comprising guanidines and azoles can not only form uniform and compact columnar super-rough micro-surface on the cu surface, but also form a layer of organic metal film, thus greatly improving the adhesive power of copper foils and high tg resins.
Description
Technical field
The present invention relates to printed circuit board and make the field, specifically, relate to a kind of ultra-roughening treating agent for cuprum surface.
Background technology
In the manufacture craft of multilayer printed circuit board, need carry out surface treatment to the internal layer copper face, to strengthen the bonding of copper face and prepreg (resin), in order to avoid splitting.Traditional treatment process is that copper face is carried out oxidation processes, forms cupric oxide and cuprous oxide acicular crystal on copper surface, increases the surface area of Copper Foil, transforms the polarity on copper surface, thereby strengthens bonding between Copper Foil and the prepreg.United States Patent (USP) 440903,4844981,4642161,4902551 etc. has detailed description to this technology, but the oxide layer that this technology forms is received acid solution easily in follow-up PROCESS FOR TREATMENT attack, cause the local delamination of via periphery, so-called " pink circle " phenomenon occurs.In order to solve the problem of " pink circle ", industry is developed modification H again
2SO
4-H
2O
2The roughening treatment agent of system replaces traditional oxidation processes agent.Such roughening treatment agent is to add additives such as nitrogen heterocyclic ring compounds, halide ion and ethylene oxide polymer to form on the basis of sulfuric acid and hydrogen peroxide.Medicament forms one deck organic metal film in the alligatoring copper face, this film can not only form chemical bond makes a concerted effort with some radical reaction of prepreg, and can effectively resist the attack of acid solution, thereby prevents the generation of " pink circle ".United States Patent (USP) 5800859,5869130,6120639,6146701,6162503 etc. has detailed description to this technology.Along with the day by day application of high Tg (glass transition temperature) resin on printed circuit board, mechanical anchor that this roughening treatment medicament produces and power and chemical bond make a concerted effort to be difficult to guarantee the bonding of Copper Foil and high Tg resin, cause glass between board layer easily.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, propose a kind ofly can form the column super alligatoring microcosmic face and the organic metal film of even compact, thereby greatly improve the ultra-roughening treating agent for cuprum surface of Copper Foil and high Tg resin bonding force at copper face.
To achieve these goals, the present invention adopts following technical scheme:
A kind of ultra-roughening treating agent for cuprum surface, form by following component and percetage by weight: organic copper 10～50%, organic acid 10～30%, guanidine compound 0.1～5%, azole compounds 0.1～5%, alcohol amine compound 0.1～5%, surplus is a deionized water.
In above-mentioned ultra-roughening treating agent for cuprum surface, preferred ingredients and percetage by weight are: organic copper 15～30%, organic acid 15～20%, guanidine compound 0.5～1.0%, azole compounds 0.5～1.0%, alcohol amine compound 0.5～1.0%, surplus is a deionized water.
In above-mentioned ultra-roughening treating agent for cuprum surface, the mixture of one or more in described organic copper preferable formic acid copper, copper acetate, propionic acid copper, acrylic acid copper, glycolic copper, copper lactate, malic acid copper, copper citrate, the copper methanesulfonate.
In above-mentioned ultra-roughening treating agent for cuprum surface, the mixture of one or more in described organic acid preferable formic acid, acetate, propionic acid, acrylic acid, glycolic, lactic acid, malic acid, citric acid, the pyrovinic acid.
In above-mentioned ultra-roughening treating agent for cuprum surface, the mixture of one or more in the preferred guanidine hydrochloride of described guanidine compound, guanidine nitrate, guanidine carbonate, guanidine sulfate, guanidine thiocyanate, aminoguanidine, hydroxyl guanidine, the hydrochloric acid dioctyl phthalate guanidine.
In above-mentioned ultra-roughening treating agent for cuprum surface, the mixture of one or more in the preferred triazole of described azole compounds, methyl-triazole, aminotriazole(ATA), tetrazolium, methyl tetrazolium, Aminotetrazole, phenyltetrazole, BTA, 1-hydroxy benzo triazole, imidazoles, methylimidazole, the benzimidazole.
In above-mentioned ultra-roughening treating agent for cuprum surface, the mixture of one or more in the preferred monoethanolamine of described alcohol amine compound, N-methyl-ethanolamine, diethanol amine, N methyldiethanol amine, the triethanolamine.
The present invention uses organic copper as oxidant, is used for the oxide etch of copper.The concentration of organic copper is less than 10%, and it is too slow then to lose copper speed, and efficient is low; If organic copper concentration, then is difficult to dissolving greater than 50%, easily produce stain, lose copper uniformity variation simultaneously.
The present invention uses organic acid to be used for the dissolving of copper, and organic acid concentration is less than 10%, and it is too slow then to lose copper speed, and efficient is low; If organic acid concentration is greater than 30%, the then steady dissolution decline of copper, the copper surface is oxidation again easily.
The guanidine compound that the present invention uses can impel organic copper to attack metallic copper towards vertical direction, is the functional additive that obtains the little surface of super alligatoring.This class material can with the univalent copper ion complexing on copper surface, thereby the energy strong adsorption is at the sidewall of copper microcosmic concave surface, make cupric constantly sting the erosion metallic copper towards the depth direction, thereby form the super alligatoring microcosmic of the column face of even compact, this coarse surface is very beneficial for " anchor with " of high Tg resin and copper face.The concentration of guanidine compound then is difficult to obtain little surface of super alligatoring less than 0.1%; If concentration greater than 5%, then can play reverse effect, form smooth surface configuration, cause erosion copper difficulty simultaneously.
The azole compounds that the present invention uses can form organic metal film at copper surface, and some radical reaction of these nitrogenous organic metal films energy prepreg resins forms chemical bonding, thereby strengthens the bonding force of copper face and prepreg resin.Azole compounds concentration does not then reach the effect that strengthens bonding force less than 0.1%; If concentration greater than 5%, then can cause separating out of organic copper, can cause erosion copper difficulty simultaneously.
The alcohol amine compound that the present invention uses can improve the steady dissolution of copper, promotes the uniformity of medicament erosion copper.The concentration of alcohol amine compound does not then reach stable and effect of uniform less than 0.1%; If concentration greater than 5%, then can reduce the steady dissolution of copper.
Super roughening treatment agent of the present invention uses deionized water as diluent, and adds to 100%.
Super roughening treatment agent of the present invention is preferably under 25～40 ℃ the temperature and uses, and the processing time is 45～120 seconds, and processing mode is spray, and the microetch amount is generally 1～4um.
Compared with prior art, the present invention has following beneficial effect: the ultra-roughening treating agent for cuprum surface that contains organic copper system of guanidine class and azole provided by the invention, can not only form the super alligatoring microcosmic of the column face of even compact at copper face, can also form one deck organic metal film, greatly improve the bonding force of Copper Foil and high Tg resin.
Embodiment
Embodiment 1～4 and comparative example 1～3 see Table 1.Take by weighing respective substance according to the prescription of table 1 and be mixed, can obtain super roughening treatment agent.Copper foil surface to 2OZ under the condition of 30 ℃ of temperature sprays processing 60 seconds, washing, hot blast drying.The Copper Foil that to handle is superimposed on the N4000-29 prepreg (Tg 〉=185 ℃, Park Electrochemical company produce) then, heating and pressurizing.According to the method for IPC-TM-650 2.4.8 Copper Foil is peeled off from prepreg after the moulding, tested its peel strength, the results are shown in the table 1.
As shown in table 1, super roughening treatment agent of the present invention can greatly strengthen the bonding force of copper face and high Tg resin, can be widely used in the preceding copper face of internal layer bonding and handle, and the hole copper that copper face is handled and the resin filling perforation is preceding before the coating of welding resistance printing ink is handled.
Table 1
| Embodiment | One-tenth is grouped into | Weight ratio (%) | Peel strength (kgf/cm) |
| 1 | Copper acetate acetic acid hydrochloride guanidine aminotriazole(ATA) triethanolamine deionized water | 10 12 1 0.5 2 surpluses | 1.0 |
| 2 | Copper acetate acetate aminoguanidine Aminotetrazole N methyldiethanol amine deionized water | 25 15 211 surpluses | 1.3 |
| 3 | Copper formate formic acid guanidine thiocyanate 1-hydroxy benzo triazole triethanolamine deionized water | 15 20 1.5 0.8 1.5 surpluses | 1.2 |
| 4 | Copper formate glycolic hydrochloric acid guanidine methylimidazole monoethanolamine deionized water | 20 15 3 2.5 2 surpluses | 1.1 |
| Comparative example 1 | Sulfuric acid hydrogen peroxide BTA cetomacrogol 1000 sodium chloride deionized water | 10 4 0.8 0.3 0.0015 surpluses | 0.5 |
| Comparative example 2 | Sulfuric acid hydrogen peroxide 1-hydroxy benzo triazole BTA 5-Aminotetrazole deionized water | 53 0.15 0.2 0.05 surpluses | 0.6 |
| Comparative example 3 | Sulfuric acid hydrogen peroxide 3-aminotriazole(ATA) 5-phenyltetrazole sodium chloride deionized water | 94 0.1 0.3 0.002 surpluses | 0.6 |
Claims (7)
1. a ultra-roughening treating agent for cuprum surface is characterized in that being made up of following component and percetage by weight: organic copper 10～50%, organic acid 10～30%, guanidine compound 0.1～5%, azole compounds 0.1～5%, alcohol amine compound 0.1～5%, surplus is a deionized water.
2. ultra-roughening treating agent for cuprum surface as claimed in claim 1, it is characterized in that forming: organic copper 15～30% by following component and percetage by weight, organic acid 15～20%, guanidine compound 0.5～1.0%, azole compounds 0.5～1.0%, alcohol amine compound 0.5～1.0%, surplus are deionized water.
3. ultra-roughening treating agent for cuprum surface as claimed in claim 1 is characterized in that described organic copper is one or more the mixture in copper formate, copper acetate, propionic acid copper, acrylic acid copper, glycolic copper, copper lactate, malic acid copper, copper citrate, the copper methanesulfonate.
4. ultra-roughening treating agent for cuprum surface as claimed in claim 1 is characterized in that described organic acid is one or more the mixture in formic acid, acetate, propionic acid, acrylic acid, glycolic, lactic acid, malic acid, citric acid, the pyrovinic acid.
5. ultra-roughening treating agent for cuprum surface as claimed in claim 1 is characterized in that described guanidine compound is one or more the mixture in guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine sulfate, guanidine thiocyanate, aminoguanidine, hydroxyl guanidine, the hydrochloric acid dioctyl phthalate guanidine.
6. ultra-roughening treating agent for cuprum surface as claimed in claim 1 is characterized in that described azole compounds is one or more the mixture in triazole, methyl-triazole, aminotriazole(ATA), tetrazolium, methyl tetrazolium, Aminotetrazole, phenyltetrazole, BTA, 1-hydroxy benzo triazole, imidazoles, methylimidazole, the benzimidazole.
7. ultra-roughening treating agent for cuprum surface as claimed in claim 1 is characterized in that described alcohol amine compound is one or more the mixture in monoethanolamine, N-methyl-ethanolamine, diethanol amine, N methyldiethanol amine, the triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100292777A CN100574568C (en) | 2007-07-20 | 2007-07-20 | A kind of ultra-roughening treating agent for cuprum surface |
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| CNB2007100292777A CN100574568C (en) | 2007-07-20 | 2007-07-20 | A kind of ultra-roughening treating agent for cuprum surface |
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| CN101351090A true CN101351090A (en) | 2009-01-21 |
| CN100574568C CN100574568C (en) | 2009-12-23 |
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| CNB2007100292777A Expired - Fee Related CN100574568C (en) | 2007-07-20 | 2007-07-20 | A kind of ultra-roughening treating agent for cuprum surface |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286739A (en) * | 2011-08-31 | 2011-12-21 | 上海应用技术学院 | Blackening agent for inner layer of multilayer board of printed circuit board and preparation method and application thereof |
| CN102477359A (en) * | 2010-11-26 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing cleaning solution |
| CN101962766B (en) * | 2009-07-22 | 2012-10-31 | 深圳市正天伟科技有限公司 | Copper plated organic coating preparation for preventing copper surface from oxidation |
| CN104694909A (en) * | 2014-07-03 | 2015-06-10 | 广东丹邦科技有限公司 | Copper surface coarsening agent |
| CN105050337A (en) * | 2015-07-02 | 2015-11-11 | 广州杰赛科技股份有限公司 | Manufacturing method for rigid-flex printed circuit board |
| CN105671538A (en) * | 2016-01-08 | 2016-06-15 | 滁州嘉泰科技有限公司 | Compound organic solderability preservatives (OSP) treating agent for lead-free printed circuit board (PCB) |
| CN106521503A (en) * | 2016-11-23 | 2017-03-22 | 昆山尚宇电子科技有限公司 | Organic acid type super coarsening agent for copper surface |
| CN107267986A (en) * | 2016-04-08 | 2017-10-20 | 东莞市斯坦得电子材料有限公司 | A kind of super roughening process of organic acid for printed wiring board welding resistance film layer pre-treatment |
| CN109379857A (en) * | 2018-09-18 | 2019-02-22 | 宏维科技（深圳）有限公司 | A kind of preparation method and application method being bonded inorganic agent, the inorganic agent |
| CN111601460A (en) * | 2020-05-30 | 2020-08-28 | 涟水县苏杭科技有限公司 | Multi-spelling two-color solder mask, character plug hole adding and tin melting surface treatment processing method |
| CN112624786A (en) * | 2019-09-24 | 2021-04-09 | 佳总兴业股份有限公司 | Method for manufacturing composite substrate |
| CN114134505A (en) * | 2021-12-02 | 2022-03-04 | 上海贝尼塔实业有限公司 | Alkaline microetching coarsening liquid and circuit board lead coarsening method |
| CN114231982A (en) * | 2021-12-20 | 2022-03-25 | 昆山市板明电子科技有限公司 | Self-etching copper surface bonding agent and preparation method thereof |
| CN116607136A (en) * | 2023-06-01 | 2023-08-18 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
-
2007
- 2007-07-20 CN CNB2007100292777A patent/CN100574568C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962766B (en) * | 2009-07-22 | 2012-10-31 | 深圳市正天伟科技有限公司 | Copper plated organic coating preparation for preventing copper surface from oxidation |
| CN102477359A (en) * | 2010-11-26 | 2012-05-30 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing cleaning solution |
| CN102477359B (en) * | 2010-11-26 | 2015-12-02 | 安集微电子（上海）有限公司 | A kind of chemically mechanical polishing cleaning liquid |
| CN102286739A (en) * | 2011-08-31 | 2011-12-21 | 上海应用技术学院 | Blackening agent for inner layer of multilayer board of printed circuit board and preparation method and application thereof |
| CN104694909A (en) * | 2014-07-03 | 2015-06-10 | 广东丹邦科技有限公司 | Copper surface coarsening agent |
| CN104694909B (en) * | 2014-07-03 | 2017-01-25 | 广东丹邦科技有限公司 | Copper surface coarsening agent |
| CN105050337B (en) * | 2015-07-02 | 2018-09-04 | 广州杰赛科技股份有限公司 | A kind of production method of rigid-flex combined board |
| CN105050337A (en) * | 2015-07-02 | 2015-11-11 | 广州杰赛科技股份有限公司 | Manufacturing method for rigid-flex printed circuit board |
| CN105671538A (en) * | 2016-01-08 | 2016-06-15 | 滁州嘉泰科技有限公司 | Compound organic solderability preservatives (OSP) treating agent for lead-free printed circuit board (PCB) |
| CN107267986A (en) * | 2016-04-08 | 2017-10-20 | 东莞市斯坦得电子材料有限公司 | A kind of super roughening process of organic acid for printed wiring board welding resistance film layer pre-treatment |
| CN106521503A (en) * | 2016-11-23 | 2017-03-22 | 昆山尚宇电子科技有限公司 | Organic acid type super coarsening agent for copper surface |
| CN109379857A (en) * | 2018-09-18 | 2019-02-22 | 宏维科技（深圳）有限公司 | A kind of preparation method and application method being bonded inorganic agent, the inorganic agent |
| CN112624786A (en) * | 2019-09-24 | 2021-04-09 | 佳总兴业股份有限公司 | Method for manufacturing composite substrate |
| CN112624786B (en) * | 2019-09-24 | 2022-08-30 | 佳总兴业股份有限公司 | Method for manufacturing composite substrate |
| CN111601460A (en) * | 2020-05-30 | 2020-08-28 | 涟水县苏杭科技有限公司 | Multi-spelling two-color solder mask, character plug hole adding and tin melting surface treatment processing method |
| CN114134505A (en) * | 2021-12-02 | 2022-03-04 | 上海贝尼塔实业有限公司 | Alkaline microetching coarsening liquid and circuit board lead coarsening method |
| CN114231982A (en) * | 2021-12-20 | 2022-03-25 | 昆山市板明电子科技有限公司 | Self-etching copper surface bonding agent and preparation method thereof |
| CN116607136A (en) * | 2023-06-01 | 2023-08-18 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
| CN116607136B (en) * | 2023-06-01 | 2024-01-05 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
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