CN105050324A - Copper surface roughening treatment solution and treatment method thereof - Google Patents
Copper surface roughening treatment solution and treatment method thereof Download PDFInfo
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- CN105050324A CN105050324A CN201510382835.2A CN201510382835A CN105050324A CN 105050324 A CN105050324 A CN 105050324A CN 201510382835 A CN201510382835 A CN 201510382835A CN 105050324 A CN105050324 A CN 105050324A
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- copper surface
- tetrafluoroborate
- treatment fluid
- surface coarsening
- copper
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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
- H05K3/0085—Apparatus for treatments of printed circuits with liquids not provided for in groups H05K3/02 - H05K3/46; conveyors and holding means therefor
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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
- 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
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a copper surface roughening treatment solution, which comprises the following components: 98wt% of H2SO4 50 to 150g/L, volume concentration 30% of H2O2 40 to 60ml/L, a silane coupling agent 0.5 to 5g/L, dissolvable zinc salt 8 to 12g/L, a stabilizer 50 to 150g/L, a corrosion inhibitor composition 0.5 to 7.5g/L, and deionized water residual. Through treatment of the copper surface roughening treatment solution, a layer of dense and uniform honeycomb structure is formed on the copper surface, the structure can increase the specific surface area combined with semi-curing resin, and during a laminating process, a crosslinking reaction for resin curing is involved, a chemical bond is formed, and the binding force with the semi-curing resin is further enhanced.
Description
Technical field
The present invention relates to technical field of surface, particularly relate to a kind of copper surface coarsening treatment fluid and processing method thereof.
Background technology
China has become producing country and the country of consumption of first printed circuit board in the world, and PCB industry is developed from small and weak gradually, and whole industrial chain is tending towards complete, product also from low side, to middle-end and high-end development.And production middle-end, high-end printed wiring board, not only need printed wiring board factory
family throwsenter a large amount of research and development and engineering staff, also need upstream equipment and raw material producer to coordinate.Printed wiring industry the early stage of development by Hong Kong and
taiwanthe advanced technology of Europe, the United States, Deng state is introduced domestic by manufacturer gradually, the material technology of equipment de-sign, device fabrication and PCB all rests in more external high-tech enterprise's hands, domestic production business uses equipment and raw material, the technology of these imports, and production cost is higher, and profitability is not enough.Along with PCB is fast-developing towards " short, little, light, thin " direction, multiple-plate output occupies more and more important position, and improve and improve inter-layer bonding force is the important research content improving interlayer hot property always.Under the pressure of the black limitation of oxidizing process technology of conventional alkaline and the pressure etc. of production cost, finding new technique, to carry out alternative basic black oxidation technology be imperative.
Palm fibre oxidation technology (brownoxide) grows up gradually under day by day surging demand.Its core procedure brown process is immersed in the brown liquid prepared by hydrogen peroxide, sulfuric acid and additive at copper-clad plate, makes roughened copper surface, and at the brown organic metal film of copper Surface Creation one deck.Treated copper surface has more regular roughness, adds the contact area with polymer, improves mechanical bonding force; In addition, the organic metal film that surface is formed can merge mutually with polymer, improve the adhesion of internal layer copper face and polymeric material in extra chemical bond mode further, for follow-up bonding operation provides enough adhesion strengths, after preventing pressing, occur plate bursting layering and pink circle phenomenon.
Hydrogen peroxide plays the effect of etching copper in brown liquid, make copper surface form rugged dentalation, and sulfuric acid can strengthen the oxidability of hydrogen peroxide, and keep the sour environment of solution.Organic additive in brown liquid then contains the several functions such as corrosion inhibiter, secondary film formers organic compound, these compound effects are on copper surface, hydrogen peroxide can be helped to carry out uneven etching to exposed copper face on the one hand, increase the surface area of copper face, deepen the rough degree of copper face; Stable metallo-organic compound film is formed on the one hand in addition on copper surface.
Corrosion inhibiter is a kind of organic component important in brown liquid, be mostly containing N, O, S heterocycle triazole class compounds, mainly contain BTA (BTA), 2-mercaptobenzothiazole (MBT), methyl benzotriazole (TTA), 2-(5-amylamine)-benzimidazole (PAB), 5-carboxyl benzotriazole (5-CBTA) and 4-carboxyl benzotriazole (4-CBTA) etc., these compounds are all N, O, S atom by triazole ring and copper face Cu
2o generates covalent bond and coordinate bond formation polymer covers on copper face, this very stable by chemical bonded refractory organic metal film altogether.Corrosion inhibiter functionally has effect important in two in brown treatment fluid: one is inhibition, avoids the erosion of acid solution and forms pink circle; Another effect generates one deck organic metal film, and this tunic is brown film, due to its special construction, in lamination process it both with metal bonding, also with prepreg Cheng Jian, this just makes to be improved through the copper face of brown and the adhesion of resin.Due to the critical function of corrosion inhibiter, therefore it also becomes the core research object of preparation brown treatment fluid.
Summary of the invention
Based on this, the object of this invention is to provide a kind of copper surface coarsening treatment fluid.
Concrete technical scheme is as follows:
A kind of copper surface coarsening treatment fluid, comprises following component:
Described composite corrosion inhibitor comprises the component of following mass percentage:
Containing the aromatic heterocyclic compounds 1-50% of S, N, O
The tetrafluoroborate 1-50% of organic ion liquid
Aliphat mercaptan 1-50%.
Wherein in an embodiment, described composite corrosion inhibitor comprises the component of following mass percentage:
Containing the aromatic heterocyclic compounds 20-40% of S, N, O
The tetrafluoroborate 20-40% of organic ion liquid
Aliphat mercaptan 20-40%;
The described aromatic heterocyclic compounds containing S, N, O is selected from one or more in benzotriazole and its derivative, mercaptobenzothiazoler and derivative thereof;
The tetrafluoroborate of described organic ion liquid is selected from and pyridinium ion that the tetrafluoroborate of substituted imidazole quaternary ammonium salt and derivative thereof, N-alkyl replace and the tetrafluoroborate of derivative thereof, alkyl quaternary are seen in the tetrafluoroborate of ion and derivative thereof one or more.
Wherein in an embodiment, the described aromatic heterocyclic compounds containing S, N, O is selected from BTA, methyl benzotriazole; The tetrafluoroborate of described organic ion liquid is selected from 1-butyl-3-methyl imidazolium tetrafluoroborate, _ 1-ethyl-3-methylimidazole tetrafluoroborate.
Wherein in an embodiment, described aliphat mercaptan is selected from lauryl mercaptan, Stearyl mercaptan.
Wherein in an embodiment, described organo silane coupling agent is selected from the compound shown in following structure, and X is selected from OH, Cl, OMe, OEt, OC
2h
4oCH
3, or Oac, n=0,1 or 2, Y be that C1-C12 alkyl, C1-C12 thiazolinyl, end are with Cl, NH
2, SH, epoxy, N
3, (methyl) acryloxy or NCO C1-C12 alkyl, as the commercialization silane couplers such as DOW CORNING Z-6011, Z-6030, Z-6040, Z-6124, Z-6185 or the silane coupler synthesized voluntarily with said structure.
Wherein in an embodiment, described stabilizer is selected from benzene sulfonic acid, toluene sulfonic acide, ethyl phenenyl azochlorosulfonate acid, silicic acid, metasilicic acid magnesium or fatty acid magnesium.
Another object of the present invention is to provide a kind of surface coarsening processing method of printed wiring board.
Concrete technical scheme is as follows:
A surface coarsening processing method for printed wiring board, comprise the steps: the printed wiring board through pre-treatment to immerse in above-mentioned copper surface coarsening treatment fluid 30-150 second, treatment temperature is 32-38 DEG C, to obtain final product.
Another object of the present invention is to provide a kind of printed wiring board.
Concrete technical scheme is as follows:
The printed wiring board that above-mentioned surface coarsening processing method obtains.
Principle of the present invention is as follows:
The mechanism of action of brown liquid of the present invention utilizes oxidant that Cu oxidation is formed Cu
2o, then organic additive and the Cu such as corrosion inhibiter
2o forms organic copper oxide layer by chemical bonding.Reaction mechanism is as follows:
Erosion copper reaction: Cu+H
2sO
4+ H
2o
2→ CuSO
4+ 2H
2o (1)
Film formation reaction: Cu
2++ CuA+B → organic metal film (2)
In copper surface coarsening treatment fluid of the present invention, add a certain amount of zinc ion, the effect thickening sedimentary deposit can be played in brown liquid.Between the ground floor BTA of copper face absorption and the BTA of subsequent adsorbtion, zinc metal ion participates in forming co-ordination complex, and can form enough thick sedimentary deposit like this, this sedimentary deposit shows as burgundy.If do not use these extra metal ions, then deposit thickness is very thin, color is very light, and sedimentary deposit can be caused very uneven.
In copper surface coarsening treatment fluid of the present invention, Cu oxide generates organic metal copper film with the organic heterocyclic molecule corrosion inhibiter containing N, S, O, is deposited on above Cu oxide.Because this kind of organic heterocyclic molecule has N, S, O atom and the aromatic rings of lone pair electrons containing center, and copper atom has the space d track of underfill in cuprous oxide, easily accept electronics and form π key and coordinate bond, the infusible precipitate film being made up of organo-metallic compound polymerization generation these two kinds of keys is highly stable.
If be used alone a kind of corrosion inhibiter, can only form one-component film on copper surface, thickness and the adhesion of film are poor.Research shows that the inhibition efficiency of single corrosion inhibiter is far below compound corrosion inhibitor.Such as bibliographical information is by BTA and the composite use of natrium citricum, and record when BTA concentration is 2mg/L, when sodium citrate concentration is 20mg/L, inhibition efficiency improves 40%.In addition, by composite dissimilar corrosion inhibiter, the composite membrane with the compound of difference in functionality can be formed on copper surface, except improving roughened copper surface degree and protection copper excessive corrosion, the adhesion of copper face and resin can also be improved by the organo-functional group similar with resin structure.
Innovative point of the present invention and beneficial effect are:
1, after copper surface coarsening treatment fluid of the present invention process, the cellular structure of one deck dense uniform is formed on copper surface, this structure can increase the specific area with semi-solid preparation resin-bonded, simultaneously in lamination process, participate in cross-linking reaction during resin solidification, thus formation chemical bond, further increase the adhesion with semi-solid preparation resin.
2, organic ion liquid tetrafluoroborate etc. is added in copper surface coarsening treatment fluid of the present invention as composite corrosion inhibiter component, synergy can be played with other corrosion inhibiter component such as BTA, mercaptan etc., increase film forming thickness, strengthen the adhesion of film toughness and film and resin bed.In corrosion inhibiter nitrogen, oxygen, sulphur atom lone electron pair with provide the cuprous oxide ion of unoccupied orbital by chemical bonds, strengthen the adhesion of copper face and resin.
3, also contain hydrogen peroxide stabilizer (as benzene sulfonic acid etc.) in copper surface coarsening treatment fluid of the present invention, stabilizer can play the effect of the decomposition delaying hydrogen peroxide, improves the oxidation efficiency of hydrogen peroxide.
4, in copper surface coarsening treatment fluid of the present invention, hydrogen peroxide (30%) concentration is 50 ± 10mL/L, lower by about 30% than respective substance content concn in other commercially available copper surface coarsening treatment fluids, this is to keeping the stable of each active principle in brown groove, reduce hydrogen peroxide add to reduce operation and maintenance cost most important.
5, copper surface coarsening treatment fluid of the present invention, operational processes temperature is 34 ± 1 DEG C, and the operational processes temperature of brown liquid more commercially available than other is low 5 DEG C.
Accompanying drawing explanation
fig. 1for the ESEM of Copper Foil after brown liquid obtained by the present invention processes by embodiment 7
figure (a is without brown process, and b is brown process 60 seconds, and c is brown process 90 seconds, and d is brown process 120 seconds);
fig. 2for the X-ray diffraction of Copper Foil after brown liquid process obtained by the present invention
figure;
fig. 3the peel strength of each group of sample (often group gets the average of 15 samples) measured after brown process being carried out to Copper Foil for adopting embodiment copper surface coarsening treatment fluid.
Embodiment
By the following examples the application is further elaborated.
In order to test the advantage of brown liquid of the present invention and embody the complex role of composite corrosion inhibitor described in the application, devise different types of brown formula of liquid respectively and compare.Whole brown flow process is carried out according to following description, and the difference between embodiment is only the difference of brown formula of liquid:
Brown flow implementation step:
1. described in formula, prepare brown liquid, the tank temperature arranging ultrasonic cleaning instrument is 50 ± 5 DEG C, the beaker that alkaline degreasing liquid is housed is put into tank, be inserted into after in beaker, the registration of thermometer reaches preset temperature, to be immersed in beaker with tweezers gripping sample Copper Foil and to start timing, take out after 5 minutes and to immerse in warm water ultrasonic cleaning 2 minutes;
2. regulate tank temperature to be 35 ± 5 DEG C by same method and carry out pickling to Copper Foil, 2 minutes processing times, the object of pickling is the Cu oxide that cleaning remains;
3. the Copper Foil of above-mentioned process is put into presoak, setting bath temperature is 38 ± 2 DEG C, handling duration is 1 minute, the object of microetch removes the serious oxide in copper surface, in the appearance that copper surface formation one is coarse, the surface area of copper and resin contact can be increased to a certain extent, for follow-up brown oxidation reaction provides uniform reaction surface.Preimpregnation also works the acid copper face neutralizing and cause after microetch process in addition; plate face is made to be tending towards alkalescence; prevent the effect of acid to the neutralization of brown tank liquor; be conducive to the uniformity of film forming after oxidation processes; guarantee to reach ideal effect; protection brown groove, also plays certain pre-heat effect to copper face simultaneously, is beneficial to the carrying out of next committed step palm fibre oxidation reaction.
4. at once sample is put into copper surface coarsening treatment fluid (brown liquid) 30-150 second after preimpregnation, treatment temperature is 32-38 DEG C, because processing time interval is shorter so need strict timing in order to avoid there is error in operation.
5. the Copper Foil after brown process, after stacking, is placed in laminating machine and carries out heat lamination operation with prepreg
6. according to the tearing strength between the Copper Foil after standard method test hot pressing and resin.
Embodiment 1
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98wt％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30v/v％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 0.5g/L |
| 1-butyl-3 methyl imidazolium tetrafluoroborate | 0.5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 2
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 1g/L |
| Lauryl mercaptan | 1.5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 3
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 2.5g/L |
| Lauryl mercaptan | 2.5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 4
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 1g/L |
| Lauryl mercaptan | 1.5g/L |
| 1-butyl-3 methyl imidazolium tetrafluoroborate | 2.5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 5
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 2.5g/L |
| Lauryl mercaptan | 2.5g/L |
| 1-butyl-3 methyl imidazolium tetrafluoroborate | 5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 6
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 5g/L |
| Lauryl mercaptan | 5g/L |
| The private of 1-butyl-3 methylimidazole takes borate | 2.5g/L |
| Deionized water | Be diluted to 1L |
Embodiment 7
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 2.5g/L |
| Lauryl mercaptan | 2.5g/L |
| 1-butyl-3 methyl imidazolium tetrafluoroborate | 5g/L |
| Deionized water | Be diluted to 1L |
> embodiment 8
A kind of copper surface coarsening of the present embodiment treatment fluid, comprises following component:
| H 2SO 4(98％) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H 2O 2(30％) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| BTA | 7.5g/L |
| Lauryl mercaptan | 7.5g/L |
| 1-butyl-3 methyl imidazolium tetrafluoroborate | 5g/L |
| Deionized water | Be diluted to 1L |
According to such scheme, brown process is implemented to Copper Foil, the sem test result wherein after copper surface coarsening treatment fluid (brown liquid) process obtained by the embodiment of the present invention 7
as Fig. 1, X-ray diffraction analysis result
as Fig. 2, according to IPC-TM-650 standard, reliability test result after pressing
table 1shown in.By
fig. 1a () can be found out, the copper foil surface without brown process does not significantly sting erosion phenomenon, inner plating through brown process 30s (
fig. 1(b)) after, form the uniform cellular structure of one deck on copper surface, illustrate that brown is functional.But brown effect does not lengthen along with the brown processing time and promotes further.The brown time of about 30s has been enough to that super roughening is carried out on copper surface and has stung erosion, and forms organic hybrid films on copper surface, prevents the further corrosion of copper.Along with the composite use of corrosion inhibiter, sting erosion scope more obviously and sting the erosion degree of depth and increase, this structure can increase the specific area with semi-solid preparation resin-bonded, simultaneously in lamination process, participate in cross-linking reaction during resin solidification, thus formation chemical bond, further increase the adhesion with semi-solid preparation resin.X-ray diffraction analysis result shows that Copper Foil is after brown process 30s, starts to occur Cu
2o (111) peak, and along with the increase of oxidization time, peak strengthens gradually, this result with
fig. 1the test result of middle SEM matches.All the other sample analysis method of testings are identical with embodiment 7 sample, test result is similar.
fig. 3be the peel strength of each group of sample (often group gets the average of 15 samples) measured after carrying out brown process according to each embodiment, result shows the increase along with density of corrosion inhibitor within the scope of finite concentration, and peel strength increases thereupon; But after increase density of corrosion inhibitor exceedes certain value further, peel strength has and reduces to a certain extent, analysis may be due to the increase along with composite nitrogen heterocyclic concentration, molecule aggregate is formed gradually, composite nitrogen heterocyclic is caused to decrease in copper adsorption degree, its corrosion inhibition declines to some extent, but no matter 2 kinds corrosion inhibiter is composite or 3 kinds of corrosion inhibiter are composite, all reach the requirement of testing standard (IPQC) on the whole, than the formula only adopting a kind of corrosion inhibiter, brown effect all significantly improves.Copper foil surface is after using BTA as the brown solution-treated of main corrosion inhibiter, and copper foil surface has formed the alveolate texture of microcosmic, and browning reaction corrodes the intercrystalline of Copper Foil, and form organic metal film at copper foil surface.Copper foil surface and resin react under high-temperature and high-pressure conditions, and the crystal grain gap of copper foil surface fully can be permeated by resin.The coarse structure of copper foil surface and corrosion inhibition film determine the size of peel strength value jointly.New corrosion inhibiter joins in brown solution, increases the roughness of copper foil surface.Can see from the experimental result of peel strength, by 3 kinds of corrosion inhibiter actings in conjunction, effect is more better than the composite effect only adopting 2 kinds of corrosion inhibiter.
table 1embodiment reliability test result
Each technical characteristic of the above embodiment can combine arbitrarily, for making description succinct, all possible combination of each technical characteristic in above-described embodiment is not all described, but, as long as the combination of these technical characteristics does not exist contradiction, be all considered to be this explanation
secretarythe scope of carrying.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (8)
1. a copper surface coarsening treatment fluid, is characterized in that, comprises following component:
Described composite corrosion inhibitor comprises the component of following mass percentage:
Containing the aromatic heterocyclic compounds 1-50% of S, N, O
The tetrafluoroborate 1-50% of organic ion liquid
Aliphat mercaptan 1-50%.
2. copper surface coarsening treatment fluid according to claim 1, it is characterized in that, described composite corrosion inhibitor comprises the component of following mass percentage:
Containing the aromatic heterocyclic compounds 20-40% of S, N, O
The tetrafluoroborate 20-40% of organic ion liquid
Aliphat mercaptan 20-40%;
The described aromatic heterocyclic compounds containing S, N, O is selected from one or more in benzotriazole and its derivative, mercaptobenzothiazoler and derivative thereof;
The tetrafluoroborate of described organic ion liquid is selected from the tetrafluoroborate of the tetrafluoroborate of disubstituted imidazole quaternary ammonium salt and derivative thereof, pyridinium ion that N-alkyl replaces and derivative thereof, alkyl quaternary is seen in the tetrafluoroborate of ion and derivative thereof one or more.
3. copper surface coarsening treatment fluid according to claim 2, is characterized in that, the described aromatic heterocyclic compounds containing S, N, O is selected from BTA, methyl benzotriazole; The tetrafluoroborate of described organic ion liquid is selected from 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate.
4. the copper surface coarsening treatment fluid according to any one of claim 1-3, is characterized in that, described aliphat mercaptan is selected from lauryl mercaptan, Stearyl mercaptan.
5. the copper surface coarsening treatment fluid according to any one of claim 1-3, it is characterized in that, described organo silane coupling agent is selected from the compound shown in following structure,
Wherein, X is selected from OH, Cl, OMe, OEt, OC
2h
4oCH
3, or Oac, n=0,1 or 2, Y be that C1-C12 alkyl, C1-C12 thiazolinyl, end are with Cl, NH
2, SH, epoxy, N
3, (methyl) acryloxy or NCO C1-C12 alkyl.
6. the copper surface coarsening treatment fluid according to any one of claim 1-3, is characterized in that, described stabilizer is selected from benzene sulfonic acid, toluene sulfonic acide, ethyl phenenyl azochlorosulfonate acid, silicic acid, metasilicic acid magnesium or fatty acid magnesium.
7. the surface coarsening processing method of a printed wiring board, it is characterized in that, comprise the steps: the printed wiring board through pre-treatment to immerse in the copper surface coarsening treatment fluid described in any one of claim 1-6 30-150 second, treatment temperature is 32-38 DEG C, to obtain final product.
8. the printed wiring board that obtains of surface coarsening processing method according to claim 7.
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