CN103249255A - Method for directly preparing conducting circuit on resin baseplate - Google Patents
Method for directly preparing conducting circuit on resin baseplate Download PDFInfo
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- CN103249255A CN103249255A CN2013101318106A CN201310131810A CN103249255A CN 103249255 A CN103249255 A CN 103249255A CN 2013101318106 A CN2013101318106 A CN 2013101318106A CN 201310131810 A CN201310131810 A CN 201310131810A CN 103249255 A CN103249255 A CN 103249255A
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Abstract
The invention belongs to the field of flexible printed-circuit board preparation, particularly relates to a method for directly preparing conducting circuit on a resin baseplate. The method comprises the following specific steps: immersing a resin baseplate into strong alkaline solution to soak; cleaning and drying the soaked baseplate; printing a mask on the baseplate by adopting printing manners such as ink jet, silk screen, laser printing and gravure to show a conducting circuit shape; immersing the baseplate into water-solubility solution of metals such as copper, silver, cobalt and nickel; taking out and cleaning the baseplate after a specified period; reducing metal ions to elementary substances by adopting reducing agents such as methanal, DMAB (Dimethylamineborane), sodium borohydride, ascorbic acid to obtain a conductive metal clad layer; and thickening the metal clad layer by adopting the chemical plating and electroplating manners after dissolving away the printed mask to improve the conductive capability. Compared with the traditional printed-circuit line preparation method, the method provided by the invention has the advantages that the material is saved, the environment is friendly, the cost is reduced, and the like, and has greater application potential in the preparation of the flexible printed-circuit board.
Description
Technical field
The invention belongs to the flexible circuit board preparation field, be specially and a kind ofly directly prepare the method for conducting wire at resin substrate.
Background technology
The manufacturing of conducting wire is to adopt the method method of photoetching corrosion to etch line pattern in copper-clad plate, many shortcomings such as waste of material is big, production process is many, environmental protection pressure is heavy, cost height that it exists in the traditional printing circuit board.Emerging printed electronics technology is to adopt printing technology, functional printing ink or oar material, be printed on rapidly on the organic or inorganic base material, form various electronic devices and components and electronic circuit, have that operation is simple, advantages such as environmental friendliness, waste rate are low, cost reduction, have broad application prospects.
Use printed electronics technology to make the conducting wire, now what use is that ink-jet, silk screen printing silver are metallic conduction printing ink or the slurry of conducting medium more.Advantages such as use silver has the conductivity height as dielectric, and chemical property is stable, but the cost of silver is too high, has limited its large-scale utilization.Replace silver with copper cost is descended significantly, but the metallic copper of subparticle is oxidized easily in air, especially at heat treatment stages, causing is the requirement that nanometer copper printing ink or the electrical property of conductive copper paste all are difficult to reach high conductivity.
For the traditional preparation process technology that solves the printed circuit conducting wire and printed electronics preparation technology's problems, we have invented and have a kind ofly directly prepared the method for conducting wire at resin substrate.Printing technology is combined with the ion-exchange theory, set up the theoretical model of a kind of hydrolysis-ion-exchange-reduction, this theoretical model can be applied in silver, copper, nickel etc. and can form on the deposition of metal of ionic bond or coordinate bond with carboxyl, the fine and close adhesion of resulting metal level is strong, and electrical property is good.Lower if desired line resistance can impose chemical plating or plating at the metallic circuit that deposits before, thereby circuit is thickened, and obtains needed electrical property.
Summary of the invention
The objective of the invention is to directly prepare the conducting wire at resin substrate, thereby part replaces traditional photoetching corrosion preparation technology, enriches the content of printed electronics technology, provides a kind of and directly prepares the method for conducting wire at resin substrate.The present invention uses alkali lye processing hydrolysis to fall the top layer molecule specific resin substrate, and printing mask reserved line figure is bonded in substrate surface by ion-exchange with metal ion, and reduction obtains the conducting wire, and chemical plating, plating thicken circuit.Principle of the present invention is the process of a kind of hydrolysis-ion-exchange-reduction.Be example with PI, PI contains imide ring (base polymer CO-N-CO-) on the main chain, hydrolysis takes place in imide bond easily under alkali condition, so the PI film is inserted in alkaline NaOH, the potassium hydroxide solution, acid imide can hydrolysis obtain carboxylic acid sodium or carboxylic acid potassium.This hydrolytic process can occur in the top layer molecule of PI film within a certain period of time, obtains extremely several microns hydrolysis layer of tens nanometers.Placing metal ion solution processes such as silver, copper, nickel, water miscible carboxylic acid sodium, potassium can react with metal ion, generate water-fast silver carboxylate, copper, nickel etc.This is a kind of reaction of ion-exchange, sodium, potassium ion and silver, copper, nickel plasma generation ion-exchange.Re-use reducing substances the insoluble petal carboxylate is reduced, just obtain the coating of metal simple-substance on the surface of PI film.This layer thickness of coating may not wait to several microns from tens nanometers.If before PI film water solution or use mode of printing to print mask after the hydrolysis, only keep outside required line pattern is exposed to, so just can obtain the conductive path of specific circuit figure.If the conducting wire electrical property that obtains does not reach requirement, can continue by chemical plating or plating coating to be thickened, thereby obtain required electrical property.
The a kind of of the present invention's proposition directly prepares the method for conducting wire at resin substrate, and concrete steps are as follows:
(1) use the substrate that has groups such as ester group, amide groups, cyano group, imide or anhydride group on main chain or the side chain, clean the rear surface oil removing, oil removing uses sodium stearate solution to soak, and takes out the back cleaning, drying;
(2) substrate that step (1) is obtained immerses in the NaOH or potassium hydroxide solution of 1 ~ 8mol/L, and 20 ℃ ~ 50 ℃ are soaked 3 ~ 15min down, take out the back cleaning, drying; Use method of printing to print out mask pattern on the resin substrate that obtains, make outside conductive circuit pattern is exposed to.Perhaps: the substrate that uses method of printing to obtain in step (1) prints out mask pattern earlier, make outside conductive circuit pattern is exposed to, immerse then in the NaOH or potassium hydroxide solution of 1 ~ 8mol/L, 20 ℃ ~ 50 ℃ are soaked 3 ~ 15min down, take out the back cleaning, drying;
(3) with 20 ℃ ~ 50 ℃ following 3 ~ 15min in the metal ion solution of the immersion of the substrate behind step (2) printing mask 10 ~ 100mmol/L, take out the back cleaning, drying;
(4) substrate behind step (3) the immersion metal ion solution is immersed in the solution of reducing agent, the control reductant concentration is 0.5 ~ 2%wt, and reduction temperature is 20 ℃ ~ 50 ℃, and the recovery time is 3 ~ 15min, metal ion is reduced into simple substance, makes circuit obtain conductivity;
(5) substrate after step (4) reduction is inserted in the appropriate solvent mask is dissolved cleaning, drying;
(6) substrate of step (5) being removed mask is inserted and is carried out the coating thickening in chemical plating or the electroplate liquid, chemical plating or electroplate after obtain both conducting wires of provisioning request.
Among the present invention, step (1) is selected is that to have ester group, amide groups, cyano group, imide or anhydride group on main chain or the side chain be the substrate that hydrolysis obtains the group of carboxyl, includes but not limited in polyimides, PETG, PEN, polyamide or the polyacrylonitrile etc. any.
Among the present invention, the employed printing process of step (2) is a kind of in ink jet printing, laser printing, silk screen printing, intaglio printing, flexographic printing or the offset printing etc., and the main component of the employed printing ink of typographic mask is carbon black, binding resin and solvent.
Among the present invention, the employed metal ion solution of step (3) be in solubility hydrochloric acid, sulfuric acid or the nitrate etc. of copper, silver, cobalt, nickel, aluminium, zinc, gold, platinum, palladium any, or be in chlorine palladium acid sodium or the sodium chloraurate any.
Among the present invention, the employed reducing agent of step (4) is a kind of in formaldehyde, sodium borohydride, dimethylamino borine, ascorbic acid or the acetaldehyde etc.
Among the present invention, employed solvent is one or more the mixing in ethyl acetate, acetonitrile, butanone, butyl acetate, toluene, ether, butyl ether, EGME, butyl glycol ether or the benzinum etc. in the step (5).
Among the present invention, in the step (6) employed chemical plating or electroplate liquid be copper facing, silver-plated, gold-plated, plating palladium, nickel plating, cobalt plating or zinc-plated etc. in a kind of.
Beneficial effect of the present invention:
1. the present invention has advantages such as operation is simple, material economy, pollution minimizing, cost reduction compared to the lithography corrosion process of traditional printed circuit board conducting wire.
2. the conducting wire that obtains of the present invention has good adhesion to flexible base, boards such as PI, PET, PAN.
3. the equipment of wanting required for the present invention is simple, does not need large-scale lithographic equipment, has reduced equipment cost.
4. production efficiency height of the present invention is with short production cycle, is beneficial to " volume to volume " that realize flexible printed circuit and produces.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) uses commercially available polyimide film (Dupont, Kapton
), thickness 0.05mm uses odium stearate that film surface is carried out oil removal treatment 5min, then with clear water flushing, oven dry.
(2) PI after the oil removing is soaked 5min under 50 ℃ in the 1mol/L potassium hydroxide solution, PI film surface is hydrolyzed.Clean oven dry after the hydrolysis with clear water.
(3) mode of use laser printing, the PI after hydrolysis prints out the circuit mask.
(4) the PI film after will printing immerses in the 50mmol/L copper-bath, soaks 5min down at 25 ℃, and ion is fully exchanged.Take out then with clear water and clean, oven dry.
(5) place the DMAB solution of 0.5mol/L to carry out reduction of metal ion the PI film after the ion-exchange, take out behind the immersion 5min, use the clear water cleaning, drying.
(6) configuration chemical bronze plating liquid, it is as follows to fill a prescription:
Substrate immersed under 40 ℃, carry out electroless copper 15min in the chemical bronze plating liquid, with the circuit board washed with de-ionized water, dry after copper facing finishes, obtain the metallic copper conducting wire.
(7) hindering with four point probe mensuration side after the copper facing is 0.03 Ω, and adhesion is 5B(ASTM D3359).
Embodiment 2:
(1) use commercially available pet film, thickness 0.05mm uses odium stearate that film surface is carried out oil removal treatment 5min, then with clear water flushing, oven dry.
(2) PET after the oil removing is soaked 3min under 50 ℃ in the 1mol/L potassium hydroxide solution, PET film surface is hydrolyzed.Clean oven dry after the hydrolysis with clear water.
(3) mode of use ink jet printing, the PET after hydrolysis prints out the circuit mask.
(4) the PET film after will printing immerses in the 50mmol/L copper-bath, soaks 10min down at 25 ℃, and ion is fully exchanged.Take out then with clear water and clean, oven dry.
(5) place the sodium borohydride solution of 0.2mol/L to carry out reduction of metal ion the PET film after the ion-exchange, take out behind the immersion 5min, use the clear water cleaning, drying.
(6) configuration electronickelling solution, it is as follows to fill a prescription:
Temperature is 55 ℃, and current density is 3A/dm
2, pH is 4; To electroplate 15min in the substrate immersion plating nickel, with the circuit board washed with de-ionized water, oven dry obtained the metallic nickel conducting wire after nickel plating finished.
(7) hindering with four point probe mensuration side after the nickel plating is 0.5 Ω, and adhesion is 5B(ASTM D3359).
Claims (7)
1. one kind directly prepares the method for conducting wire at resin substrate, it is characterized in that concrete steps are as follows:
(1) uses the resin substrate that has ester group, amide groups, cyano group, imide or anhydride group group on main chain or the side chain, use sodium stearate solution to soak surface degreasing, take out the back cleaning, drying;
(2) substrate that step (1) is obtained immerses in the NaOH or potassium hydroxide solution of 1 ~ 8mol/L, and 20 ℃ ~ 50 ℃ are soaked 3 ~ 15min down, take out the back cleaning, drying; Use method of printing to print out mask pattern at the resin substrate that obtains, make outside conductive circuit pattern is exposed to; Perhaps: the substrate that uses method of printing to obtain in step (1) prints out mask pattern earlier, make outside conductive circuit pattern is exposed to, immerse then in the NaOH or potassium hydroxide solution of 1 ~ 8mol/L, 20 ℃ ~ 50 ℃ are soaked 3 ~ 15min down, take out the back cleaning, drying;
(3) with 20 ℃ ~ 50 ℃ following 3 ~ 15min in the metal ion solution of the immersion of the substrate behind step (2) printing mask 10 ~ 100mmol/L, take out the back cleaning, drying;
(4) substrate behind step (3) the immersion metal ion solution is immersed in the solution of reducing agent, the control reductant concentration is 0.5 ~ 2%wt, and reduction temperature is 20 ℃ ~ 50 ℃, and the recovery time is 3 ~ 15min, metal ion is reduced into simple substance, makes circuit obtain conductivity;
(5) substrate after step (4) reduction is inserted in the appropriate solvent mask is dissolved cleaning, drying;
(6) substrate of step (5) being removed mask is inserted and is carried out the coating thickening in chemical plating or the electroplate liquid, chemical plating or electroplate after obtain both conducting wires of provisioning request.
2. method according to claim 1, it is characterized in that: step (1) is selected is that to have ester group, amide groups, cyano group, imide or anhydride group on main chain or the side chain be the substrate that hydrolysis obtains the group of carboxyl, includes but not limited in polyimides, PETG, PEN, polyamide or the polyacrylonitrile any.
3. method according to claim 1, it is characterized in that: the employed printing process of step (2) is a kind of in ink jet printing, laser printing, silk screen printing, intaglio printing, flexographic printing or the offset printing, the main component of the employed printing ink of typographic mask be in carbon black, binding resin or the solvent any.
4. method according to claim 1, it is characterized in that: the employed metal ion solution of step (3) be in solubility hydrochloric acid, sulfuric acid or the nitrate of copper, silver, cobalt, nickel, aluminium, zinc, gold, platinum, palladium any, or be in chlorine palladium acid sodium or the sodium chloraurate any.
5. method according to claim 1 is characterized in that: the employed reducing agent of step (4) is a kind of in formaldehyde, sodium borohydride, dimethylamino borine, ascorbic acid or the acetaldehyde.
6. method according to claim 1 is characterized in that: employed solvent is one or more the mixing in ethyl acetate, acetonitrile, butanone, butyl acetate, toluene, ether, butyl ether, EGME, butyl glycol ether or the benzinum in the step (5).
7. method according to claim 1 is characterized in that: in the step (6) employed chemical plating or electroplate liquid be copper facing, silver-plated, gold-plated, plating palladium, nickel plating, cobalt plating or zinc-plated in a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310131810.6A CN103249255B (en) | 2013-04-17 | 2013-04-17 | A kind of method directly preparing conducting wire on resin substrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310131810.6A CN103249255B (en) | 2013-04-17 | 2013-04-17 | A kind of method directly preparing conducting wire on resin substrate |
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| CN103249255A true CN103249255A (en) | 2013-08-14 |
| CN103249255B CN103249255B (en) | 2016-01-20 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906366A (en) * | 2014-04-03 | 2014-07-02 | 复旦大学 | Method for adding and manufacturing two-sided flexible printed circuit board on PI substrate |
| CN103906380A (en) * | 2014-04-03 | 2014-07-02 | 复旦大学 | Method for adding and manufacturing multilayer printed circuit board on PI substrate |
| CN105585676A (en) * | 2014-10-21 | 2016-05-18 | 中国科学院兰州化学物理研究所 | Laser printing method of flexible electronic device |
| CN107072039A (en) * | 2016-12-23 | 2017-08-18 | 中国科学院深圳先进技术研究院 | The method for preparing conducting wire |
| CN107484330A (en) * | 2016-06-07 | 2017-12-15 | 鹏鼎控股(深圳)股份有限公司 | High-frequency copper silver hybrid conductive line construction and preparation method thereof |
| CN107734868A (en) * | 2017-11-08 | 2018-02-23 | 广东光华科技股份有限公司 | Fine wire circuit and preparation method thereof |
| CN108156764A (en) * | 2017-12-21 | 2018-06-12 | 维沃移动通信有限公司 | Metallic circuit production method, transparent shell and mobile terminal on transparent shell |
| CN109808327A (en) * | 2019-02-13 | 2019-05-28 | 何彦青 | Ink-jet printed modification method is consolidated for transparent material plastic cement cushion |
| CN110028835A (en) * | 2019-05-07 | 2019-07-19 | 深圳市崯涛油墨科技有限公司 | A kind of silver lustre ink coating and preparation method thereof with stereoscopic effect on polycarbonate transparent material |
| CN110082407A (en) * | 2019-03-29 | 2019-08-02 | 华东师范大学 | A kind of flexibility gold electrode and preparation method |
| EP3681256A1 (en) * | 2019-01-09 | 2020-07-15 | BGT Materials Limited | A method for forming trace of circuit board |
| CN113293373A (en) * | 2020-02-24 | 2021-08-24 | 北京化工大学 | Polyimide film with surface covered with metal pattern layer and preparation method thereof |
| CN113593776A (en) * | 2021-07-30 | 2021-11-02 | 长春捷翼汽车零部件有限公司 | Wire harness production method and wire harness |
| CN115106537A (en) * | 2022-06-19 | 2022-09-27 | 华中科技大学 | Metal micro-nano 3D printing method based on laser direct writing |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906366A (en) * | 2014-04-03 | 2014-07-02 | 复旦大学 | Method for adding and manufacturing two-sided flexible printed circuit board on PI substrate |
| CN103906380A (en) * | 2014-04-03 | 2014-07-02 | 复旦大学 | Method for adding and manufacturing multilayer printed circuit board on PI substrate |
| CN105585676A (en) * | 2014-10-21 | 2016-05-18 | 中国科学院兰州化学物理研究所 | Laser printing method of flexible electronic device |
| CN105585676B (en) * | 2014-10-21 | 2018-06-22 | 中国科学院兰州化学物理研究所 | A kind of method of laser printing flexible electronic |
| CN107484330A (en) * | 2016-06-07 | 2017-12-15 | 鹏鼎控股(深圳)股份有限公司 | High-frequency copper silver hybrid conductive line construction and preparation method thereof |
| US10874016B2 (en) | 2016-06-07 | 2020-12-22 | Avary Holding (Shenzhen) Co., Limited. | Method of manufacturing physical structure for high frequency signal transmission |
| CN107072039A (en) * | 2016-12-23 | 2017-08-18 | 中国科学院深圳先进技术研究院 | The method for preparing conducting wire |
| CN107734868A (en) * | 2017-11-08 | 2018-02-23 | 广东光华科技股份有限公司 | Fine wire circuit and preparation method thereof |
| CN108156764A (en) * | 2017-12-21 | 2018-06-12 | 维沃移动通信有限公司 | Metallic circuit production method, transparent shell and mobile terminal on transparent shell |
| CN108156764B (en) * | 2017-12-21 | 2019-10-29 | 维沃移动通信有限公司 | Metallic circuit production method, transparent shell and mobile terminal on transparent shell |
| EP3681256A1 (en) * | 2019-01-09 | 2020-07-15 | BGT Materials Limited | A method for forming trace of circuit board |
| CN109808327B (en) * | 2019-02-13 | 2021-04-27 | 广东海亚新材料科技有限公司 | Stable ink-jet printing improvement method for transparent plastic cushion |
| CN109808327A (en) * | 2019-02-13 | 2019-05-28 | 何彦青 | Ink-jet printed modification method is consolidated for transparent material plastic cement cushion |
| CN110082407A (en) * | 2019-03-29 | 2019-08-02 | 华东师范大学 | A kind of flexibility gold electrode and preparation method |
| CN110028835A (en) * | 2019-05-07 | 2019-07-19 | 深圳市崯涛油墨科技有限公司 | A kind of silver lustre ink coating and preparation method thereof with stereoscopic effect on polycarbonate transparent material |
| CN113293373A (en) * | 2020-02-24 | 2021-08-24 | 北京化工大学 | Polyimide film with surface covered with metal pattern layer and preparation method thereof |
| CN113593776A (en) * | 2021-07-30 | 2021-11-02 | 长春捷翼汽车零部件有限公司 | Wire harness production method and wire harness |
| CN113593776B (en) * | 2021-07-30 | 2023-03-10 | 长春捷翼汽车零部件有限公司 | Wire harness production method and wire harness |
| CN115106537A (en) * | 2022-06-19 | 2022-09-27 | 华中科技大学 | Metal micro-nano 3D printing method based on laser direct writing |
| CN115106537B (en) * | 2022-06-19 | 2024-02-09 | 华中科技大学 | Metal micro-nano 3D printing method based on laser direct writing |
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