CN113260172A - Polydopamine-based copper surface modification method - Google Patents
Polydopamine-based copper surface modification method Download PDFInfo
- Publication number
- CN113260172A CN113260172A CN202110434728.5A CN202110434728A CN113260172A CN 113260172 A CN113260172 A CN 113260172A CN 202110434728 A CN202110434728 A CN 202110434728A CN 113260172 A CN113260172 A CN 113260172A
- Authority
- CN
- China
- Prior art keywords
- solution
- polydopamine
- copper surface
- functional monomer
- dopamine
- 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.)
- Granted
Links
Images
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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
Abstract
The invention relates to the technical field of printed circuit boards, in particular to a polydopamine-based copper surface modification method, which comprises the following steps: s1, dissolving dopamine hydrochloride in an acidic buffer solution to obtain a dopamine solution; s2, dissolving a functional monomer in a solvent to obtain a functional monomer solution, wherein the functional monomer is one or a combination of more of maleic anhydride and derivatives thereof; s3, adding the functional monomer solution into the dopamine solution, and stirring in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution; s4, adding a quaternary ammonium salt containing double bonds and an oxidant into the mixed solution, and stirring to obtain a modified solution; and S5, soaking the copper sheet with the smooth surface in the modification solution, heating and stirring to obtain the surface-modified copper sheet. The copper surface modification method provided by the invention has a simple process, can avoid pretreatment of the smooth copper sheet, can effectively improve the bonding strength of the smooth copper sheet and the base material, and has good environmental stability.
Description
Technical Field
The invention relates to the technical field of printed circuit boards, in particular to a polydopamine-based copper surface modification method.
Background
The 21 st century is an era of information explosion transmission, and people acquire various information at any time and any place through various portable electronic devices to carry out office, social and various entertainment activities and the like. Consumer demand for emerging electronic devices has driven them toward higher integration and faster data transfer. With the increasing popularity of 5G electronic devices, higher requirements are put on device integration and signal transmission, which is more challenging for traditional Printed Circuit Board (PCB) manufacturers.
PCBs have played an important role in electronic devices as carriers for electronic components and dielectrics for signal transmission. In the conventional preparation method, in order to make the surface of the component tightly combined with other components, the surface of the component is usually subjected to micro-etching to increase the surface roughness of the component, so as to improve the bonding force with other functional resins, and the method is widely adopted at present. However, with the advent of the 5G era, the requirement of high-frequency and high-speed data transmission makes the frequency of signal transmission reach GHz, and if the traditional method is continuously adopted, the "skin effect" of signal transmission caused by the rough copper surface will greatly reduce the efficiency of signal transmission, and affect the performance of equipment. The roughness of the copper surface for signal transmission needs to be as low as possible to reduce signal loss, but this tends to weaken the bonding force between the copper surface and the resin, thereby adversely affecting the reliability of the product. Therefore, there is a need to develop a new solution to reduce the roughness of the copper surface to eliminate the signal transmission loss to the maximum extent and ensure a strong bonding force between the copper surface and the resin.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: provides a copper surface modification method for directly modifying a smooth copper surface based on polydopamine to enhance the binding force of the smooth copper surface.
In order to solve the technical problems, the invention adopts the technical scheme that: a polydopamine-based copper surface modification method comprises the following steps:
s1, dissolving dopamine hydrochloride in an acidic buffer solution to obtain a dopamine solution;
s2, dissolving a functional monomer in a solvent to obtain a functional monomer solution, wherein the functional monomer is one or a combination of more of maleic anhydride and derivatives thereof;
s3, adding the functional monomer solution into the dopamine solution, and stirring in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution;
s4, adding a quaternary ammonium salt containing double bonds and an oxidant into the mixed solution, and stirring to obtain a modified solution;
and S5, soaking the copper sheet with the smooth surface in the modification solution, heating and stirring to obtain the surface-modified copper sheet.
The invention has the beneficial effects that: according to the polydopamine-based copper surface modification method provided by the invention, extra pretreatment on a smooth copper surface is not required in the copper surface modification process, operation steps are effectively saved, and the binding force between the copper surface and other base materials can be effectively improved under the condition of ensuring the flatness of the copper surface; the environment stability of the combination of the modified copper surface and the base material is good, and the peeling strength is high; the copper surface modification process is simple, the pollution is low, and the cost is low.
Drawings
FIG. 1 shows an optical photograph of a modified copper surface;
FIG. 2 is a scanning electron micrograph of a modified copper surface;
FIG. 3 shows infrared spectra before and after modification of a smooth copper surface;
FIG. 4 is a photograph showing the contact angle of a modified copper side and an unmodified copper side;
FIG. 5 shows the 90 ° peel curves for the modified and unmodified copper faces;
FIG. 6 is a bar graph showing the change in peel strength of a modified copper surface under a single influence of "number of rinses".
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The most key concept of the invention is as follows: the modification treatment based on polydopamine is directly carried out on the smooth copper surface, so that the copper surface is not pretreated in advance.
A polydopamine-based copper surface modification method comprises the following steps:
s1, dissolving dopamine hydrochloride in an acidic buffer solution to obtain a dopamine solution;
s2, dissolving a functional monomer in a solvent to obtain a functional monomer solution, wherein the functional monomer is one or a combination of more of maleic anhydride and derivatives thereof;
s3, adding the functional monomer solution into the dopamine solution, and stirring in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution;
s4, adding a quaternary ammonium salt containing double bonds and an oxidant into the mixed solution, and stirring to obtain a modified solution;
and S5, soaking the copper sheet with the smooth surface in the modification solution, heating and stirring to obtain the surface-modified copper sheet.
Preferably, in S3, the stirring time is 12-24 h;
preferably, in S5, the soaking time is 1-15 min;
preferably, in S5, the heating method is microwave heating.
From the above description, the beneficial effects of the present invention are: in the copper surface modification process, extra pretreatment on the smooth copper surface is not needed, so that the operation steps are effectively saved, and the binding force between the copper surface and other base materials can be effectively improved under the condition of ensuring the flatness of the copper surface; the environment stability of the combination of the modified copper surface and the base material is good, and the peeling strength is high; the copper surface modification process is simple, the pollution is low, and the cost is low; maleic anhydride or a derivative thereof is grafted on polydopamine, so that the modified copper surface is tangled and crosslinked when being pressed with other resins, and the binding force of the modified copper surface is further improved.
Further, the acid buffer solution comprises 0.1mol/L-0.5mol/L sodium bicarbonate and 0.1mol/L-0.3mol/L sodium tetraborate decahydrate.
Further, the functional monomer is one or a combination of more of maleic anhydride, citraconic anhydride, phenyl maleic anhydride, 2, 3-diphenyl maleic anhydride and dimethyl maleic anhydride.
Further, the molar concentration of the functional monomer solution is 1mol/L-1.5 mol/L.
Further, the solvent is one of tetrahydrofuran, dimethyl sulfoxide and ethyl acetate.
Further, in S3, the molar ratio of the functional monomer to dopamine is 1.5:1 to 1: 1.
Further, the quaternary ammonium salt containing double bonds is one or a combination of more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, allyl trimethyl ammonium chloride, trimethyl vinyl ammonium bromide and methacryloyloxyethyl dimethyl benzyl ammonium chloride.
Further, the oxidant is one of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzoyl peroxide.
Further, in S4, the molar ratio of the amount of the double-bond containing quaternary ammonium salt to dopamine is 2:1 to 1: 2.
Furthermore, the mol percentage of the addition amount of the oxidant and the sum of the addition amounts of the dopamine and the quaternary ammonium salt containing double bonds is 1mol percent to 5mol percent.
Example one
A polydopamine-based copper surface modification method comprises the following steps:
s1: adding 8g of sodium bicarbonate and 20g of sodium tetraborate decahydrate into 250mL of deionized water, heating the acidic buffer solution at 45 ℃ to promote solid particles to be completely dissolved in the water, degassing for 30min by using nitrogen, adding 10g of dopamine hydrochloride into the acidic buffer solution, and stirring and uniformly stirring to obtain a dopamine solution.
S2: weighing 6.2g of maleic anhydride, adding into 50mL of tetrahydrofuran solvent, and uniformly stirring to obtain a functional monomer solution;
s3: adding the functional monomer solution into the dopamine solution, and uniformly stirring for 12h at room temperature in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution;
s4: weighing 10g of acryloyloxyethyl trimethyl ammonium chloride and 0.3g of ammonium persulfate, adding into the mixed solution, and uniformly stirring to obtain a modified solution;
s5: and (3) vertically soaking a clean smooth copper sheet in the modified solution, carrying out microwave-assisted heating for 10min, taking out, and washing with deionized water to obtain the polydopamine-modified copper surface.
Example two
A polydopamine-based copper surface modification method comprises the following steps:
s1: adding 10g of sodium bicarbonate and 18g of sodium tetraborate decahydrate into 300mL of deionized water, heating the acidic buffer solution at 45 ℃ to promote solid particles to be completely dissolved in the water, degassing for 30min by using nitrogen, adding 8g of dopamine hydrochloride into the acidic buffer solution, and uniformly stirring to obtain a dopamine solution.
S2: weighing 6.5g of dimethyl maleic anhydride, adding into 50mL of tetrahydrofuran solvent, and uniformly stirring to obtain a functional monomer solution;
s3: adding the functional monomer solution into the dopamine solution, and uniformly stirring for 18h at room temperature in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution;
s4: weighing 12g of (3-acrylamide propyl) trimethyl ammonium chloride and 0.5g of ammonium persulfate, adding into the mixed solution, and uniformly stirring to obtain a modified solution;
s5: and (3) vertically soaking a clean smooth copper sheet in the modified solution, carrying out microwave-assisted heating for 15min, taking out, and washing with deionized water to obtain the polydopamine-modified copper surface.
Detection example 1
The polydopamine modified copper surfaces obtained in the first and second examples were photographed, as shown in fig. 1, wherein (a) is the first example and (b) is the second example. As can be seen from fig. 1, a black-red functional layer copolymerized by dopamine under alkaline conditions is attached to the surface of the modified smooth copper surface.
Example two
Scanning electron micrographs of the surfaces of the polydopamine-modified copper surfaces obtained in the first and second examples are shown in fig. 2, wherein the left side photograph is the first example, and the right side photograph is the second example. As can be seen from fig. 2, the fine particles of polydopamine are uniformly distributed on the surfaces of the polydopamine modified copper surfaces obtained in the first and second examples. Therefore, the method for modifying the copper surface provided by the invention has the advantages of uniform polydopamine sedimentation effect and uniform copper surface binding property.
Example III
Polydopamine modified copper surface and smoothness obtained in example oneThe ir spectra collection was performed on copper sheets (unmodified copper sheets) as shown in fig. 3. As can be seen from FIG. 3, the smooth copper sheet has no obvious absorption peak in the infrared spectrum, while the modified smooth copper sheet has obvious absorption peak typical to polydopamine in the infrared spectrum, such as 1494cm-1And 1596cm-1-N-H bending vibration peak of amino group appearing nearby, 1294cm-1The tensile vibration peak of phenol aldehyde C-O-H, and the peak length of the tensile vibration peak is 3250cm-1The peak shape of the peak appears to be strong and wide-OH absorption peak. Therefore, by carrying out modification treatment based on polydopamine on the smooth copper sheet, a large number of hydrophilic groups (hydroxyl, amino and the like) can be introduced on the surface of the smooth copper sheet, and the bonding property between the surface of the smooth copper surface and the base material is effectively improved.
Example four
Contact angle tests were performed on the polydopamine modified copper surfaces obtained in example one and example two, as well as on unmodified copper sheets, and the results are shown in fig. 4. Wherein, (a) is a contact angle test result chart of an unmodified copper sheet, (b) is a contact angle test result chart of a first embodiment, and (c) is a contact angle test result chart of a second embodiment. As can be seen from fig. 4, the contact angle of the surface of the smooth copper sheet treated by the modification based on poly-dopamine is significantly reduced (58 ° -65 °) compared with the unmodified copper sheet (99 °), i.e. the surface is hydrophilic. Therefore, the surface energy of the modified smooth copper sheet is increased due to the introduction of a large number of hydrophilic groups, so that the contact angle of the modified smooth copper sheet is obviously reduced compared with that of the unmodified smooth copper sheet, and the fact that various hydrophilic groups are introduced to the surface of the smooth copper surface is also proved from the side surface.
Example five of detection
The polydopamine modified copper surfaces obtained in the first and second examples and the unmodified copper surfaces were subjected to 90 ° peel strength tests according to ASTM C794-2018, and the test results are shown in fig. 5. As can be seen from FIG. 5, the peel strength of the modified copper surface is significantly improved compared to the unmodified copper surface, and the peel strength of the modified copper surface is between 900N/m and 1500N/m. Therefore, the glass strength of the smooth copper surface can be effectively improved by carrying out modification treatment based on polydopamine on the smooth copper surface, and the bonding property between the smooth copper surface and the base material can be effectively improved.
Example six
The polydopamine modified copper surfaces obtained in example one and example two were subjected to a rinse resistance test, and the results are shown in fig. 6. As can be seen from fig. 6, after the modified copper surface is washed with water for multiple times, the peel strength of the modified copper surface remains almost unchanged, which indicates that the modified copper surface has excellent adhesion performance and good environmental stability.
In conclusion, the invention provides a polydopamine-based copper surface modification method, no additional pretreatment is needed to be carried out on a smooth copper surface in the copper surface modification process, operation steps are effectively saved, and the bonding force between the copper surface and other base materials can be effectively improved under the condition of ensuring the flatness of the copper surface; the environment stability of the combination of the modified copper surface and the base material is good, and the peeling strength is high; the copper surface modification process is simple, the pollution is low, and the cost is low.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (10)
1. A polydopamine-based copper surface modification method is characterized by comprising the following steps:
s1, dissolving dopamine hydrochloride in an acidic buffer solution to obtain a dopamine solution;
s2, dissolving a functional monomer in a solvent to obtain a functional monomer solution, wherein the functional monomer is one or a combination of more of maleic anhydride and derivatives thereof;
s3, adding the functional monomer solution into the dopamine solution, and stirring in a nitrogen atmosphere to obtain a functional monomer modified dopamine mixed solution;
s4, adding a double-bond quaternary ammonium salt and an oxidant into the mixed solution and stirring to obtain a modified solution;
and S5, soaking the copper sheet with the smooth surface in the modification solution, heating and stirring to obtain the surface-modified copper sheet.
2. The method for modifying a copper surface based on polydopamine according to claim 1, wherein the acidic buffer solution comprises 0.1mol/L-0.5mol/L sodium bicarbonate and 0.1mol/L-0.3mol/L sodium tetraborate decahydrate.
3. The method for modifying copper surface based on polydopamine of claim 1, wherein the functional monomer is one or more of maleic anhydride, citraconic anhydride, phenyl maleic anhydride, 2, 3-diphenyl maleic anhydride, and dimethyl maleic anhydride.
4. The method for modifying a copper surface based on polydopamine according to claim 1, wherein the molar concentration of the functional monomer solution is 1mol/L-1.5 mol/L.
5. The method for modifying a copper surface based on polydopamine of claim 1, wherein the solvent is one of tetrahydrofuran, dimethyl sulfoxide and ethyl acetate.
6. The method for modifying a copper surface based on polydopamine of claim 1, wherein the molar ratio of the functional monomer to dopamine in S3 is 1.5:1-1: 1.
7. The method for modifying copper surface based on polydopamine of claim 1, wherein the double-bond containing quaternary ammonium salt is one or more of (3-acrylamidopropyl) trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, allyl trimethyl ammonium chloride, trimethyl vinyl ammonium bromide, and methacryloyloxyethyl dimethyl benzyl ammonium chloride.
8. The method for modifying the copper surface based on polydopamine in claim 1, wherein the oxidant is one of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzoyl peroxide.
9. The method for modifying a copper surface based on polydopamine of claim 1, wherein the molar ratio of the amount of the double-bond containing quaternary ammonium salt added to dopamine in S4 is 2:1 to 1: 2.
10. The method for modifying a copper surface based on polydopamine according to claim 1, characterised in that the molar percentage of the oxidant added to the sum of the amounts of dopamine and quaternary ammonium salt containing double bonds is between 1 mol% and 5 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434728.5A CN113260172B (en) | 2021-04-22 | 2021-04-22 | Polydopamine-based copper surface modification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434728.5A CN113260172B (en) | 2021-04-22 | 2021-04-22 | Polydopamine-based copper surface modification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113260172A true CN113260172A (en) | 2021-08-13 |
| CN113260172B CN113260172B (en) | 2022-03-18 |
Family
ID=77221522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110434728.5A Active CN113260172B (en) | 2021-04-22 | 2021-04-22 | Polydopamine-based copper surface modification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113260172B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804187A (en) * | 2015-04-24 | 2015-07-29 | 厦门双瑞船舶涂料有限公司 | Preparation method of multifunctional group bionic mussel adhesive protein polymer |
| CN107250359A (en) * | 2014-12-30 | 2017-10-13 | 生物梅里埃公司 | The purposes of layered composite, the method for the manufacture compound and the compound |
| CN107645852A (en) * | 2017-09-18 | 2018-01-30 | 乐凯特科技铜陵有限公司 | A kind of two-sided surface treatment process of copper foil of high frequency printed circuit boards |
| CN111939331A (en) * | 2020-08-25 | 2020-11-17 | 南京工程学院 | Degradable metal surface gradient polymer layer and preparation method thereof |
-
2021
- 2021-04-22 CN CN202110434728.5A patent/CN113260172B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107250359A (en) * | 2014-12-30 | 2017-10-13 | 生物梅里埃公司 | The purposes of layered composite, the method for the manufacture compound and the compound |
| US20170342400A1 (en) * | 2014-12-30 | 2017-11-30 | bioMérieux | Multilayer complex, method for manufacturing said complex and use of said complex |
| CN104804187A (en) * | 2015-04-24 | 2015-07-29 | 厦门双瑞船舶涂料有限公司 | Preparation method of multifunctional group bionic mussel adhesive protein polymer |
| CN107645852A (en) * | 2017-09-18 | 2018-01-30 | 乐凯特科技铜陵有限公司 | A kind of two-sided surface treatment process of copper foil of high frequency printed circuit boards |
| CN111939331A (en) * | 2020-08-25 | 2020-11-17 | 南京工程学院 | Degradable metal surface gradient polymer layer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113260172B (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100610649B1 (en) | Resin composition, prepreg, laminate sheet and printed wiring board using the same | |
| CN112442202B (en) | Interlayer bonding sheet for multilayer board and preparation method and application thereof | |
| CN206481556U (en) | Have the high shielding EMI screened films of black polyamide thin film | |
| CN113260172B (en) | Polydopamine-based copper surface modification method | |
| US4033840A (en) | Thermosetting acryloyloxy-terminate butadiene polymers | |
| TW202311398A (en) | Polyphenylene ether resin modified by bismaleimide, manufacturing method thereof, and substrate material of circuit board | |
| WO2010087402A1 (en) | Prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board | |
| CN109852182B (en) | Composition for improving solder resist ink adhesion and use method thereof | |
| CN1947476A (en) | Flexible printed wiring board and manufacturing method thereof | |
| TWI742945B (en) | Low-dissipation flexible copper-coated laminate, manufacturing method thereof, and electronic device | |
| CN109735276B (en) | Micron copper sheet-polyphenyl ether-epoxy resin conductive adhesive and preparation method thereof | |
| JP7243953B2 (en) | Compositions for forming circuit board structures and insulating substrates | |
| KR20230069183A (en) | Hybrid adhesive composition for electromagnetic wave shielding, manufacturing method of hybrid adhesive for electromagnetic wave shielding, and hybrid adhesive film for electromagnetic wave shielding | |
| JP2000129086A (en) | Epoxy resin composition, prepreg, resin-coated metallic foil and laminate | |
| JPH0148142B2 (en) | ||
| CN111424272A (en) | Browning liquid for printed circuit board | |
| WO2021026987A1 (en) | Resin composition, prepreg, and related substrate | |
| CN110831335A (en) | Drilling deslagging electroplating process for FPC board | |
| JP4742426B2 (en) | Heat resistant resin composition, prepreg and laminate using the same | |
| JP2000218734A (en) | Production of metal foil-clad laminated plate | |
| JP2572835B2 (en) | Resin composition for wiring board and prepreg | |
| JPH11181052A (en) | Epoxy resin composition, prepreg and lamtnated plate | |
| CN117690902B (en) | Packaging substrate containing modified adhesive film | |
| CN117586714A (en) | Conductive adhesive film with anisotropy and preparation method thereof | |
| JP2000239347A (en) | Epoxy resin composition and prepreg and laminate using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |