CN105050324B - Copper surface roughening treatment liquid and its processing method - Google Patents
Copper surface roughening treatment liquid and its processing method Download PDFInfo
- Publication number
- CN105050324B CN105050324B CN201510382835.2A CN201510382835A CN105050324B CN 105050324 B CN105050324 B CN 105050324B CN 201510382835 A CN201510382835 A CN 201510382835A CN 105050324 B CN105050324 B CN 105050324B
- Authority
- CN
- China
- Prior art keywords
- copper surface
- roughening treatment
- treatment liquid
- tetrafluoroborate
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- 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 kind of copper surface roughening treatment liquid, including following component：98wt%H2SO4The H of 50 150g/L, volumetric concentration 30%2O240 60ml/L, 0.5 5g/L of organo silane coupling agent, 8 12g/L of soluble zinc salt, 50 150g/L of stabilizer, 0.5 7.5g/L of composite corrosion inhibitor, deionized water surplus.The cellular structure of one layer of dense uniform can be formed on copper surface by being handled through roughening treatment liquid in copper surface of the present invention, this structure can increase the specific surface area with semi-solid preparation resin-bonded, simultaneously in lamination process, participate in cross-linking reaction during resin solidification, so as to form chemical bond, the binding force with semi-solid preparation resin is further increased.
Description
Technical field
The present invention relates to technical field of surface, more particularly to a kind of copper surface roughening treatment liquid and its processing side
Method.
Background technology
China has become the producing country and country of consumption of the first big printed circuit board in the world, PCB industry by
Gradually develop from small and weak, entire industrial chain tends to be complete, and product is also from the low side of beginning, to middle-end and high-end development.And it gives birth to
Middle-end, high-end printed wiring board are produced, not only needs a large amount of research and development of printed wiring board producer input and engineering staff, it is also desirable to upstream
Equipment and the cooperation of raw material producer.Printed wiring industry is in the early stage of development by Hong Kong and Taiwan manufacturer gradually by Europe, the United States, Deng states
Advanced technology introduce domestic, the material technology of equipment design, equipment production and PCB all rests in external some high-tech enterprise
In industry hand, domestic production quotient is using the equipment of these imports and raw material, technology, and production cost is higher, and profitability is insufficient.With
PCB occupies more and more important position towards the fast development of " short, small, light, thin " direction, multiple-plate yield, improves and improves
Inter-layer bonding force is always an important research content for improving interlayer hot property.Under the pressure of the office of the black oxidation law technology of conventional alkaline
Sex-limited and production cost pressure etc. finds new technique to substitute basic black oxidation technology be imperative.
Brown oxidation technology (brown oxide) gradually grows up under increasingly surging demand.Its core procedure brown
Processing is to immerse copper-clad plate in the brown liquid prepared by hydrogen peroxide, sulfuric acid and additive, makes roughened copper surface, and in copper
The organic metal film of one layer of brown of Surface Creation.Treated copper surface has relatively regular roughness, increases with polymerizeing
The contact area of object, improves mechanical bonding force；In addition, the organic metal film that surface is formed can be merged with polymer phase, with
Additional chemical bond mode further improves the binding force of internal layer copper face and polymeric material, is provided enough for subsequent bonding operation
Adhesion strength, prevent pressing after occur plate bursting layering and pink circle phenomenon.
Hydrogen peroxide plays the role of etching copper in brown liquid, and copper surface is made to form rugged dentalation, and sulphur
Acid can enhance the oxidability of hydrogen peroxide, and keep the acidic environment of solution.Organic additive in brown liquid then contains
On the one hand the several functions organic compound such as corrosion inhibiter, auxiliary film former, these compound effects can be helped on copper surface
Hydrogen peroxide carries out uneven etching to exposed copper face, increases the surface area of copper face, deepens the rough degree of copper face；Other one
Aspect forms stable metallo-organic compound film on copper surface.
Corrosion inhibiter is a kind of organic component important in brown liquid, is mostly containing N, O, S heterocycle triazole class compounds, mainly
There are benzotriazole (BTA), 2-mercaptobenzothiazole (MBT), methyl benzotriazole (TTA), 2- (5- amylamines)-benzimidazole
(PAB), 5- carboxyl benzotriazoles (5-CBTA) and 4- carboxyl benzotriazoles (4-CBTA) etc., these compounds are all to pass through triazole
N, O, S atom and the copper face Cu of ring2O generates covalent bond and coordinate bond forms polymer and is covered on copper face, this to pass through chemistry
The organic metal film of bond altogether is sufficiently stable.Corrosion inhibiter has the important work of two aspects in the function in brown treatment fluid
With：First, inhibition, avoids the erosion of acid solution and forms pink circle；Another effect is to generate one layer of organic metal film with copper face, this
Tunic is brown film, due to its special construction, in lamination process it both with metal bonding, also with prepreg bonding, this
Just it is improved the binding force of copper face and resin by brown.Due to the critical function of corrosion inhibiter, it, which also becomes, matches
The core research object of brown treatment fluid processed.
Invention content
Based on this, the object of the present invention is to provide a kind of copper surface roughening treatment liquid.
Specific technical solution is as follows：
A kind of copper surface roughening treatment liquid, including following component：
The composite corrosion inhibitor includes the component of following mass percentage：
Aromatic heterocyclic compounds 1-50% containing S, N, O
The tetrafluoroborate 1-50% of organic ion liquid
Aliphatic mercaptan 1-50%.
The composite corrosion inhibitor includes the component of following mass percentage in one of the embodiments,：
Aromatic heterocyclic compounds 20-40% containing S, N, O
The tetrafluoroborate 20-40% of organic ion liquid
Aliphatic mercaptan 20-40%；
The aromatic heterocyclic compounds containing S, N, O be selected from benzotriazole and its derivative, mercaptobenzothiazoler and
One or more of its derivative；
The tetrafluoroborate of the organic ion liquid is selected from and the tetrafluoro boric acid of substituted imidazole quaternary ammonium salt and its derivative
The tetrafluoroborate of the alkyl-substituted pyridinium ion of salt, N- and its derivative, alkyl quaternary are seen the tetrafluoro boron of ion and its derivative
One or more of hydrochlorate.
The aromatic heterocyclic compounds containing S, N, O are selected from benzotriazole, methylbenzene in one of the embodiments,
Triazole；The tetrafluoroborate of the organic ion liquid is selected from 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- ethyl -3- first
Base tetrafluoroborate.
The aliphatic mercaptan is selected from lauryl mercaptan, Stearyl mercaptan in one of the embodiments,.
The organo silane coupling agent is selected from such as lower structure compound represented, X and is selected from one of the embodiments,
OH, Cl, OMe, OEt, OC2H4OCH3Or Oac, n=0,1 or 2, Y are C1-C12 alkyl, C1-C12 alkenyls, end with Cl,
NH2, SH, epoxy, N3, (methyl) acryloxy or isocyanate group C1-C12 alkyl, as DOW CORNING Z-6011, Z-6030,
The commercializations such as Z-6040, Z-6124, Z-6185 silane coupling agent or the silane coupling agent voluntarily synthesized with above structure.
In one of the embodiments, the stabilizer be selected from benzene sulfonic acid, toluenesulfonic acid, ethyl phenenyl azochlorosulfonate acid, silicic acid, partially
Magnesium silicate or fatty acid magnesium.
It is a further object of the present invention to provide a kind of surface coarsing processing methods of printed wiring board.
Specific technical solution is as follows：
A kind of surface coarsing processing method of printed wiring board, includes the following steps：By the printed wiring Jing Guo pre-treatment
Plate is immersed in above-mentioned copper surface roughening treatment liquid 30-150 second, treatment temperature be 32-38 DEG C to get.
It is a further object of the present invention to provide a kind of printed wiring boards.
Specific technical solution is as follows：
The printed wiring board that above-mentioned surface coarsing processing method obtains.
The principle of the present invention is as follows：
The mechanism of action of brown liquid of the present invention is to aoxidize to form Cu by Cu using oxidant2O, then corrosion inhibiter etc. have
Machine additive and Cu2O forms organic copper oxide layer by chemical bonding.Reaction mechanism is as follows：
Lose copper reaction：Cu+H2SO4+H2O2→CuSO4+2H2O (1)
Film formation reaction：Cu2++ CuA+B → organic metal film (2)
In roughening treatment liquid in copper surface of the present invention, a certain amount of zinc ion is added, can be played in brown liquid
Thicken the effect of sedimentary.Between the first layer benzotriazole of copper face absorption and the benzotriazole of subsequent adsorbtion, zinc metal
Ion participates in forming co-ordination complex, can form sufficiently thick sedimentary in this way, which shows as burgundy.If no
Using these additional metal ions, then deposit thickness is very thin, color is very light, and sedimentary can be caused very uneven.
In roughening treatment liquid in copper surface of the present invention, Cu oxide and the organic heterocyclic molecule inhibition containing N, S, O
Agent generates organic metal copper film, is deposited on above Cu oxide.Because this kind of organic heterocyclic molecule has orphan to electricity containing center
N, S, O atom and the aromatic rings of son, and copper atom has the space d tracks of underfill in cuprous oxide, is easily accepted by electronically forming π
Key and coordinate bond, the infusible precipitate film that organo-metallic compound polymerization generation is made of both keys are highly stable.
If a kind of corrosion inhibiter is used alone, one-component film is can be only formed on copper surface, the thickness and binding force of film are poor.
Research shows that the inhibition efficiency of single corrosion inhibiter is far below compound corrosion inhibitor.Such as document report is by benzotriazole and citric acid
Sodium is used in compounding, and is measured as a concentration of 2mg/L of benzotriazole, inhibition efficiency improves when sodium citrate concentration is 20mg/L
40%.In addition, by compounding different types of corrosion inhibiter, the compound of the compound with different function can be formed on copper surface
Film, other than improving copper surface roughness and protection copper excessive corrosion, additionally it is possible to pass through the organic functional similar with resin structure
The binding force of copper face and resin improves in group.
The present invention innovative point and advantageous effect be：
1st, after roughening treatment liquid in copper surface of the present invention processing the cellular knot of one layer of dense uniform is formed on copper surface
Structure, this structure can increase the specific surface area with semi-solid preparation resin-bonded, while in lamination process, participate in resin solidification when
Cross-linking reaction so as to form chemical bond, further increases the binding force with semi-solid preparation resin.
2nd, organic ion liquid tetrafluoroborate etc. is added in roughening treatment liquid in copper surface of the present invention as compounding
Corrosion inhibiter component can play synergistic effect with other corrosion inhibiter components such as benzotriazole, mercaptan etc., increase film forming thickness,
Enhance film toughness and the binding force of film and resin layer.The lone electron pair of nitrogen, oxygen, sulphur atom is with providing unoccupied orbital in corrosion inhibiter
Cuprous oxide ion enhances the binding force of copper face and resin by chemical bonds.
3rd, also containing hydrogen peroxide stabilizer (such as benzene sulfonic acid) in roughening treatment liquid in copper surface of the present invention, stabilizer can
To play the role of delaying the decomposition of hydrogen peroxide, the oxidation efficiency of hydrogen peroxide is improved.
4th, hydrogen peroxide (30%) a concentration of 50 ± 10mL/L in roughening treatment liquid in copper surface of the present invention, it is more commercially available than other
Respective substance content concn low 30% or so in copper surface roughening treatment liquid, this to keep brown slot in each active principle it is steady
It is fixed, reduce hydrogen peroxide add so as to reduce operation and maintenance cost most important.
5th, roughening treatment liquid in copper surface of the present invention, operation processing temperature is 34 ± 1 DEG C, than other commercially available brown liquid
Operation processing temperature it is 5 DEG C low.
Description of the drawings
Fig. 1 is copper foil, and through brown liquid obtained by the present invention, by treated the scanning electron microscope (SEM) photograph of embodiment 7, (a is without brown
Processing, b are handled 60 seconds for brown, and c is handled 90 seconds for brown, and d is handled 120 seconds for brown)；
Fig. 2 is copper foil through treated the X-ray diffractogram of brown liquid obtained by the present invention；
Fig. 3 is to each group sample measured after copper foil progress brown processing using embodiment copper surface roughening treatment liquid
The peel strength of (every group of mean value for taking 15 samples).
Specific embodiment
The application is further elaborated by the following examples.
Make to test the advantage of brown liquid of the present invention and embody the compounding of herein described composite corrosion inhibitor
With having separately designed different types of brown formula of liquid and be compared.Entire brown flow carries out as described below, embodiment
Between difference be only brown formula of liquid difference：
Brown flow implementation step：
1. according to brown liquid is prepared described in formula, the sink temperature that setting is cleaned by ultrasonic instrument is 50 ± 5 DEG C, and alkali will be housed
Property degreasing fluid beaker be put into sink, be inserted into thermometer in beaker registration reach preset temperature after, with tweezers grip sample
Product copper foil is immersed in beaker and starts timing, takes out and is immersed in warm water after five minutes and is cleaned by ultrasonic 2 minutes；
2. adjust sink temperature in the same way carries out copper foil pickling for 35 ± 5 DEG C, 2 minutes processing times, pickling
Purpose is the remaining Cu oxide of cleaning；
3. above-mentioned processed copper foil is put into prepreg solution, bath temperature is set as 38 ± 2 DEG C, handling duration is 1 point
Clock, the purpose of microetch is the serious oxide in copper removal surface, forms a coarse appearance on copper surface, to a certain extent
The surface area that copper is contacted with resin can be increased, uniform reaction surface is provided for subsequent brown oxidation reaction.In addition preimpregnation is gone back
It rises and neutralizes acid copper face caused by after microetch is handled, plate face is made to tend to alkalinity, prevents the work of neutralization of the acid to brown tank liquor
With being conducive to the uniformity to form a film after oxidation processes, it is ensured that reach ideal effect, protect brown slot, while copper face is also functioned to
Certain pre- heat effect, in favor of the progress of next committed step palm fibre oxidation reaction.
4. being at once put into sample in copper surface roughening treatment liquid (brown liquid) 30-150 seconds after preimpregnation, treatment temperature is
32-38 DEG C, since processing time interval is shorter so needing stringent timing in operation in order to avoid there is error.
5. brown treated copper foil after being stacked with prepreg, is placed in progress thermosphere press operation in laminating machine
6. the tearing strength between copper foil and resin after hot pressing is tested according to standard method.
Embodiment 1
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98wt%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30v/v%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 0.5g/L |
| - 3 methyl imidazolium tetrafluoroborate of 1- butyl | 0.5g/L |
| Deionized water | It is diluted to 1L |
Embodiment 2
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 1g/L |
| Lauryl mercaptan | 1.5g/L |
| Deionized water | It is diluted to 1L |
Embodiment 3
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
Embodiment 4
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 1g/L |
| Lauryl mercaptan | 1.5g/L |
| - 3 methyl imidazolium tetrafluoroborate of 1- butyl | 2.5g/L |
| Deionized water | It is diluted to 1L |
Embodiment 5
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
Embodiment 6
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 5g/L |
| Lauryl mercaptan | 5g/L |
| - 3 methylimidazole private of 1- butyl takes borate | 2.5g/L |
| Deionized water | It is diluted to 1L |
Embodiment 7
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 2.5g/L |
| Lauryl mercaptan | 2.5g/L |
| - 3 methyl imidazolium tetrafluoroborate of 1- butyl | 5g/L |
| Deionized water | It is diluted to 1L |
Embodiment 8
A kind of copper surface roughening treatment liquid of the present embodiment, including following component：
| H2SO4(98%) | 95g/L |
| Organo silane coupling agent | 3.5g/L |
| H2O2(30%) | 60mL/L |
| Zinc sulfate | 10g/L |
| Benzene sulfonic acid | 100mg/L |
| Benzotriazole | 7.5g/L |
| Lauryl mercaptan | 7.5g/L |
| - 3 methyl imidazolium tetrafluoroborate of 1- butyl | 5g/L |
| Deionized water | It is diluted to 1L |
Brown processing is implemented to copper foil according to said program, wherein through obtained by the embodiment of the present invention 7 at the roughening of copper surface
Manage liquid (brown liquid) treated sem test result such as Fig. 2, X-ray diffraction analysis result such as Fig. 3, according to IPC-TM-
650 standards, after pressing shown in reliability test result table 1.By Fig. 2 (a) as can be seen, the copper foil surface without brown processing does not have
Have and significantly sting erosion phenomenon, inner plating is after brown processing 30s (Fig. 2 (b)), and one layer of formation is uniform cellular on copper surface
Structure, illustrate that brown is functional.But brown effect is further promoted not as brown processing time lengthens.30s is left
The right brown time has been enough copper surface carrying out super roughening to sting erosion, and form organic hybrid films, prevention on copper surface
The further corroding of copper.With being used in compounding for corrosion inhibiter, it is more obvious and sting erosion depth and increase to sting erosion range, this structure
The specific surface area with semi-solid preparation resin-bonded can be increased, while in lamination process, participate in cross-linking reaction during resin solidification, from
And chemical bond is formed, further increase the binding force with semi-solid preparation resin.X-ray diffraction analysis is the result shows that copper foil passes through palm fibre
After changing processing 30s, start Cu occur2O (111) peak, and with the increase of oxidization time, peak gradually enhances, this result with
The test result of SEM matches in Fig. 2.Remaining sample analysis test method is identical with 7 sample of embodiment, test result is similar.
Fig. 4 is strong according to the stripping of each group sample (every group of mean value for taking 15 samples) measured after the progress brown processing of each embodiment
Degree, the results showed that as the increase of density of corrosion inhibitor, peel strength increase therewith in the range of a certain concentration；But further increase
Density of corrosion inhibitor is more than after certain value, and peel strength has to be reduced to a certain extent, and analysis may be due to the azepine of compounding
The increase of cycle compound concentration, molecule aggregate gradually form, and lead to the nitrogen heterocyclic of compounding in copper adsorption degree
Decrease, corrosion inhibition is declined, but no matter 2 kinds of corrosion inhibiter compounding or 3 kinds of corrosion inhibiter compoundings, reach on the whole
To the requirement of testing standard (IPQC), than only with a kind of formula of corrosion inhibiter, brown effect all significantly improves.Copper foil surface exists
After using benzotriazole as the brown solution treatment of main corrosion inhibiter, copper foil surface has formed microcosmic cellular knot
Structure, browning reaction is that the intercrystalline of copper foil is corroded, and forms organic metal film in copper foil surface.Copper foil surface and tree
Fat reacts under high-temperature and high-pressure conditions, and the crystal grain gap of copper foil surface can be by resin fully penetrated.The coarse knot of copper foil surface
Structure and corrosion inhibition film have codetermined the size of peel strength value.New corrosion inhibiter is added in brown solution, increases copper foil table
The roughness in face.It can see from the experimental result of peel strength, by 3 kinds of corrosion inhibiter collective effects, effect is better than only with 2
The compounding effect of kind corrosion inhibiter.
1 embodiment reliability test result of table
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. a kind of copper surface roughening treatment liquid, which is characterized in that including following component：
The composite corrosion inhibitor includes the component of following mass percentage：
Aromatic heterocyclic compounds 1-50% containing S, N, O
The tetrafluoroborate 1-50% of organic ion liquid
Aliphatic mercaptan 1-50%.
2. roughening treatment liquid in copper surface according to claim 1, which is characterized in that the composite corrosion inhibitor includes as follows
The component of mass percentage：
Aromatic heterocyclic compounds 20-40% containing S, N, O
The tetrafluoroborate 20-40% of organic ion liquid
Aliphatic mercaptan 20-40%；
The aromatic heterocyclic compounds containing S, N, O are selected from benzotriazole and its derivative, mercaptobenzothiazoler and its spread out
One or more of biology；
The tetrafluoroborate of the organic ion liquid is selected from tetrafluoroborate, the N- of disubstituted imidazole quaternary ammonium salt and its derivative
The tetrafluoroborate of alkyl-substituted pyridinium ion and its derivative, alkyl quaternary see ion and its derivative tetrafluoroborate in
One or more.
3. roughening treatment liquid in copper surface according to claim 2, which is characterized in that the heteroaromatic containing S, N, O
Compound is selected from benzotriazole, methyl benzotriazole；The tetrafluoroborate of the organic ion liquid is selected from 1- butyl -3- methyl
Tetrafluoroborate, 1- ethyl-3-methylimidazole tetrafluoroborates.
4. according to claim 1-3 any one of them copper surface roughening treatment liquid, which is characterized in that the aliphatic mercaptan choosing
From lauryl mercaptan, Stearyl mercaptan.
5. according to claim 1-3 any one of them copper surface roughening treatment liquid, which is characterized in that the organosilan coupling
Agent is selected from such as lower structure compound represented,
Wherein, X is selected from OH, Cl, OMe, OEt, OC2H4OCH3Or OAc, n=0,1 or 2, Y for C1-C12 alkyl, C1-C12 alkenyls,
End carries Cl, NH2, SH, epoxy, N3, (methyl) acryloxy or isocyanate group C1-C12 alkyl.
6. according to claim 1-3 any one of them copper surface roughening treatment liquid, which is characterized in that the stabilizer is selected from benzene
Sulfonic acid, toluenesulfonic acid, ethyl phenenyl azochlorosulfonate acid, silicic acid, metasilicic acid magnesium or fatty acid magnesium.
7. the surface coarsing processing method of a kind of printed wiring board, which is characterized in that include the following steps：It will be by pre-treatment
Printed wiring board is immersed in claim 1-6 any one of them copper surface roughening treatment liquid 30-150 seconds, treatment temperature 32-
38 DEG C to get.
8. the printed wiring board that the surface coarsing processing method described in claim 7 obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510382835.2A CN105050324B (en) | 2015-07-01 | 2015-07-01 | Copper surface roughening treatment liquid and its processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510382835.2A CN105050324B (en) | 2015-07-01 | 2015-07-01 | Copper surface roughening treatment liquid and its processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105050324A CN105050324A (en) | 2015-11-11 |
| CN105050324B true CN105050324B (en) | 2018-06-12 |
Family
ID=54456383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510382835.2A Active CN105050324B (en) | 2015-07-01 | 2015-07-01 | Copper surface roughening treatment liquid and its processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105050324B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107278052A (en) * | 2016-04-08 | 2017-10-20 | 东莞市斯坦得电子材料有限公司 | Chemical roughening process for the photic pattern transfer pre-treatment of printed wiring board |
| CN107190254B (en) * | 2017-05-22 | 2019-04-23 | 博敏电子股份有限公司 | A kind of novel brownification treatment fluid of printed circuit board |
| CN109267110B (en) * | 2018-10-09 | 2020-05-15 | 九江德福科技股份有限公司 | Production process of double-layer composite electrolytic copper foil |
| CN109275269A (en) * | 2018-11-16 | 2019-01-25 | 深圳市和美精艺科技有限公司 | A kind of the micropore production method and its structure of PCB substrate |
| CN109385635B (en) * | 2018-12-07 | 2020-12-01 | 华侨大学 | Compound ionic liquid corrosion inhibitor and preparation method thereof |
| CN110241422B (en) * | 2019-05-28 | 2021-03-30 | 电子科技大学 | Multilayer high-frequency printed circuit board copper foil surface roughening liquid and use method thereof |
| CN110273148B (en) * | 2019-07-25 | 2021-03-23 | 华侨大学 | Compound browning liquid containing ionic liquid and preparation method thereof |
| CN110446355A (en) * | 2019-08-23 | 2019-11-12 | 惠州中京电子科技有限公司 | A kind of LED lamp bead package board filling holes with resin technique |
| CN112624786B (en) * | 2019-09-24 | 2022-08-30 | 佳总兴业股份有限公司 | Method for manufacturing composite substrate |
| CN111826645A (en) * | 2020-07-31 | 2020-10-27 | 国网河南省电力公司西峡县供电公司 | Browning liquid for inner layer copper foil of circuit board |
| CN112469209B (en) * | 2020-11-17 | 2021-10-26 | 胜宏科技（惠州）股份有限公司 | Method for synchronously metalizing metal layer and nonmetal layer in hole of PCB (printed circuit board) |
| CN113462217A (en) * | 2021-06-08 | 2021-10-01 | 上海应用技术大学 | Treatment method for improving antibacterial and antioxidant properties of copper surface |
| CN114885532A (en) * | 2022-05-30 | 2022-08-09 | 莆田市涵江区依吨多层电路有限公司 | Method for cooperatively enhancing glue filling of high-thickness copper and high-density circuit of printed circuit |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492595A (en) * | 1994-04-11 | 1996-02-20 | Electrochemicals, Inc. | Method for treating an oxidized copper film |
| CN1564650A (en) * | 2004-04-13 | 2005-01-12 | 广东光华化学厂有限公司 | Brownized treatment liquid for increasing adhesion of internal copper surface of circuit board and polymer material |
-
2015
- 2015-07-01 CN CN201510382835.2A patent/CN105050324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492595A (en) * | 1994-04-11 | 1996-02-20 | Electrochemicals, Inc. | Method for treating an oxidized copper film |
| CN1564650A (en) * | 2004-04-13 | 2005-01-12 | 广东光华化学厂有限公司 | Brownized treatment liquid for increasing adhesion of internal copper surface of circuit board and polymer material |
Non-Patent Citations (4)
| Title |
|---|
| NaCl溶液中烷基咪唑对铜的缓蚀作用;张大全;《中国腐蚀与防护学报》;20020830;全文 * |
| Study on brown oxidation process with imidazole group, mercapto group and heterocyclic compounds in printed circuit board industry;Chong Wang;《Journal of Adhesion Science and Technology》;20150618;第29卷(第12期);第1179-1180页，表1-2 * |
| 新型内层铜箔棕化处理液的研制;符飞燕;《电镀与涂饰》;20131215;全文 * |
| 新型离子液体的缓蚀性能研究;冷菁;《中国优秀硕士学位论文全文数据库工程科技I辑》;20120715;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105050324A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105050324B (en) | Copper surface roughening treatment liquid and its processing method | |
| EP2341167B1 (en) | Method for surface treatment of copper and copper material | |
| CN104620394B (en) | Method for the metallization of solar cell substrate | |
| KR102060983B1 (en) | Electroless copper plating compositions | |
| JP4033237B2 (en) | Copper surface treatment method and copper | |
| CN102893709A (en) | A method for manufacturing a base material having gold-coated metallic fine pattern, a base material having gold-coated metallic fine pattern, a printed wiring board, an interposer and a semiconductor device | |
| KR101632450B1 (en) | Adhesion promotion of metal to laminate with a multi-functional compound | |
| TWI630176B (en) | Pretreatment agent for electroless plating, pretreatment method using electroplating substrate using the above pretreatment method for electroless plating, and manufacturing method thereof | |
| KR101614169B1 (en) | Non-etching non-resist adhesion composition and method of preparing a work piece | |
| TWI645073B (en) | Copper foil and semiconductor package substrate | |
| CN101962776A (en) | Solder stripping agent and preparation method thereof | |
| TWI707984B (en) | Surface treatment agent for copper and copper alloy surfaces and method for treating copper or copper alloy surfaces | |
| TW201212755A (en) | Method and agent for surface processing of printed circuit board substrate | |
| TWI732045B (en) | Manufacturing method of printed wiring board | |
| CN108601245A (en) | A kind of electro-plating method of HDI plates high thickness to diameter ratio blind hole | |
| CN110029336B (en) | Copper surface treatment liquid for manufacturing multilayer printed circuit board and treatment method | |
| CN109563623A (en) | The preparation method of the chemical plating pretreatment liquid and printed circuit board that are used simultaneously with reduction treatment | |
| TW200523108A (en) | Chromium-free antitarnish adhesion promoting treatment composition | |
| CN101736328A (en) | Pretreatment solution and process of electroless copper plating of flexible printed circuit board | |
| CN108823555B (en) | Reduced chemical gold plating solution and preparation method, use method and application thereof | |
| JP2007262579A (en) | Copper surface treatment method and copper | |
| CN103173752B (en) | Plating solution formula, plating solution preparation method and application | |
| CN102120828B (en) | Swelling solution for removing through-hole residues of epoxy resin circuit board | |
| KR101494618B1 (en) | Conversion coating composition for flexible print circuit board and surface treating method using the same | |
| CN110117791B (en) | Binding force promoter for brown oxide liquid of high-density interconnection printed circuit board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |