CN103249255B - A kind of method directly preparing conducting wire on resin substrate - Google Patents
A kind of method directly preparing conducting wire on resin substrate Download PDFInfo
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- CN103249255B CN103249255B CN201310131810.6A CN201310131810A CN103249255B CN 103249255 B CN103249255 B CN 103249255B CN 201310131810 A CN201310131810 A CN 201310131810A CN 103249255 B CN103249255 B CN 103249255B
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Abstract
The invention belongs to flexible circuit board preparation field, be specially a kind of method directly preparing conducting wire on resin substrate.Its concrete steps are: immersed in strong alkali solution by resin substrate and soak, the base-plate cleaning post-drying after immersion; Use the mode of printings such as ink-jet, silk screen, laser printing, intaglio plate on substrate, print out mask, expose conductive circuit pattern; Immerse in the water-soluble solution of the metals such as copper, silver, cobalt, nickel and take out cleaning after special time; Use the reducing agent such as formaldehyde, dimethylamino borine (DMAB), sodium borohydride, ascorbic acid to make reducing metal ions become simple substance, thus obtain the coat of metal that can conduct electricity; After dissolving typographic mask, the mode of use chemical plating, plating makes the coat of metal thicken, thus improves conductive capability.The present invention has compared to conventional printed circuit-line preparation method advantages such as saving material, environmental friendliness, cost reduction, in the preparation of flexible circuit board, have larger application potential.
Description
Technical field
The invention belongs to flexible circuit board preparation field, be specially a kind of method directly preparing conducting wire on resin substrate.
Background technology
In conventional print-circuit board, the manufacture of conducting wire adopts the method for photoetching corrosion to etch line pattern in copper-clad plate, and it exists, and waste of material is large, production process is many, environmental protection pressure is heavy, high in cost of production shortcomings.Emerging printed electronics technique adopts printing technology, functional ink or oar material, be printed on organic or inorganic base material rapidly, form various electronic devices and components and electronic circuit, there is the advantages such as operation is simple, environmental friendliness, waste rate are low, cost reduction, have broad application prospects.
Use printed electronics manufacture technics conducting wire, use ink-jet now more, metallic conductive inks or slurry that silk screen printing silver is conducting medium.Use silver to have conductivity as dielectric high, the advantages such as stable chemical nature, but the high cost of silver, limit it and use on a large scale.Replacing silver with copper can make cost significantly decline, but the metallic copper of subparticle is easily oxidized in atmosphere, and especially at heat treatment stages, causing is the requirement that nano-copper ink or the electrical property of conductive copper paste are all difficult to reach high conductivity.
In order to the problems of the conventional preparation techniques and printed electronics preparation technology that solve printed circuit conducting wire, we have invented a kind of method directly preparing conducting wire on resin substrate.Printing technology is combined with ion-exchange theory, establish a kind of theoretical model of hydrolysis-ion-exchange-reduction, this theoretical model can be applied in silver, copper, nickel etc. and can be formed in the deposition of the metal of ionic bond or coordinate bond with carboxyl, the fine and close adhesion of the metal level obtained is strong, and electrical property is excellent.If need lower line resistance, chemical plating or plating can be imposed on the metallic circuit deposited before, thus circuit is thickened, the electrical property required for acquisition.
Summary of the invention
The object of the invention is to directly on resin substrate, prepare conducting wire, thus part replaces traditional photoetching corrosion preparation technology, enriches the content of printed electronics technique, a kind of method directly preparing conducting wire on resin substrate is provided.Specific resin substrate uses base extraction hydrolysis to fall surface molecules by the present invention, and printing mask reserved line figure, is bonded in substrate surface by ion-exchange by metal ion, and reduction obtains conducting wire, and chemical plating, plating make circuit thicken.Principle of the present invention is a kind of process of hydrolysis-ion-exchange-reduction.For PI, PI is the base polymer containing imide ring (-CO-N-CO-) on main chain, imide bond is easily hydrolyzed in the basic conditions, so insert in alkaline NaOH, potassium hydroxide solution by PI film, acid imide can be hydrolyzed and obtain carboxylic acid sodium or carboxylic acid potassium.This hydrolytic process can occur in the surface molecules of PI film within a certain period of time, obtains the hydrolysis layer of tens nanometers to several microns.Be placed in the 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 to reduce to insoluble petal carboxylate, just obtain the coating of metal simple-substance on the surface of PI film.This layer of thickness of coating may from tens nanometers to several microns not etc.If use mode of printing to print mask before PI film water solution or after hydrolysis, outside line pattern is exposed to needed for only retaining, the conductive path of specific circuit figure so just can be obtained.If the conducting wire electrical property obtained does not reach requirement, chemical plating can be continued through or plating makes coating thicken, thus obtain required electrical property.
A kind of method directly preparing conducting wire on resin substrate that the present invention proposes, concrete steps are as follows:
(1) use the substrate with groups such as ester group, amide groups, cyano group, imide or anhydride group on main chain or side chain, cleaning rear surface oil removing, oil removing uses sodium stearate solution to soak, cleaning, drying after taking out;
(2), in the NaOH that the substrate that step (1) obtained immerses 1 ~ 8mol/L or potassium hydroxide solution, 3 ~ 15min is soaked at 20 DEG C ~ 50 DEG C, cleaning, drying after taking out; Use the method for printing to print out mask pattern by the resin substrate obtained, make outside conductive circuit pattern is exposed to.Or: the substrate first using the method for printing to obtain in step (1) prints out mask pattern, make outside conductive circuit pattern is exposed to, then in the NaOH immersing 1 ~ 8mol/L or potassium hydroxide solution, at 20 DEG C ~ 50 DEG C, 3 ~ 15min is soaked, cleaning, drying after taking out;
(3) by 3 ~ 15min in the metal ion solution of the substrate immersion 10 ~ 100mmol/L after step (2) printing mask 20 DEG C ~ 50 DEG C, cleaning, drying after taking out;
(4) step (3) being immersed the substrate after metal ion solution immerses in the solution of reducing agent, control reductant concentration is 0.5 ~ 2%wt, and reduction temperature is 20 DEG C ~ 50 DEG C, and the recovery time is 3 ~ 15min, metal ion is reduced into simple substance, makes circuit obtain conductivity;
(5) substrate after step (4) being reduced is inserted in appropriate solvent and is dissolved by mask, cleaning, drying;
(6) substrate of step (5) removing mask is inserted in chemical plating or electroplate liquid and carried out coating thickening, after chemical plating or plating, obtain the conducting wire of given requirements.
In the present invention, selected by step (1) is that main chain or side chain be the substrate that hydrolysis obtains the group of carboxyl with ester group, amide groups, cyano group, imide or anhydride group, includes but not limited to any one in polyimides, PETG, PEN, polyamide or polyacrylonitrile etc.
In the present invention, the printing process that step (2) uses is the one in ink jet printing, laser printing, silk screen printing, intaglio printing, flexographic printing or offset printing etc., and the main component of the ink that typographic mask uses is carbon black, binding resin and solvent.
In the present invention, the metal ion solution that step (3) uses is copper, in the solubility hydrochloric acid of silver, cobalt, nickel, aluminium, zinc, gold, platinum, palladium, sulfuric acid or nitrate etc. any one, or be any one in chlorine palladium acid sodium or sodium chloraurate.
In the present invention, the reducing agent that step (4) uses is formaldehyde, one in sodium borohydride, dimethylamino borine, ascorbic acid or acetaldehyde etc.
In the present invention, the solvent used in step (5) is ethyl acetate, the mixing of one or more in acetonitrile, butanone, butyl acetate, toluene, ether, butyl ether, EGME, butyl glycol ether or benzinum etc.
In the present invention, the chemical plating used in step (6) or electroplate liquid be copper facing, silver-plated, gold-plated, plating palladium, nickel plating, cobalt plating or zinc-plated etc. in one.
beneficial effect of the present invention:
1. the present invention has the 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 the present invention obtains has excellent adhesion to flexible base, boards such as PI, PET, PAN.
3. the equipment wanted required for the present invention is simple, does not need large-scale lithographic equipment, reduces equipment cost.
4. production efficiency of the present invention is high, with short production cycle, is beneficial to " volume to volume " that realize flexible printed circuit and produces.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1:
(1) commercially available polyimide film (Dupont, Kapton is used
), thickness 0.05mm, uses odium stearate to carry out oil removal treatment 5min to film surface, then rinses with clear water, dries.
(2) PI after oil removing is soaked 5min at 50 DEG C in 1mol/L potassium hydroxide solution, PI film surface is hydrolyzed.Be hydrolyzed rear clean water, dry.
(3) use the mode of laser printing, PI after hydrolyzing prints out circuit mask.
(4) the PI film after printing is immersed in 50mmol/L copper-bath, at 25 DEG C, soak 5min, ion is fully exchanged.Then taking-up clean water, dries.
(5) the DMAB solution PI film after ion-exchange being placed in 0.5mol/L carries out the reduction of metal ion, takes out, dry by clean water after soaking 5min.
(6) configure chemical bronze plating liquid, fill a prescription as follows:
Substrate is immersed in chemical bronze plating liquid and carry out electroless copper 15min at 40 DEG C, by circuit board washed with de-ionized water after copper facing terminates, dry, obtain metallic copper conducting wire.
(7) measuring sheet resistance with four point probe after copper facing is 0.03 Ω, and adhesion is 5B(ASTMD3359).
Embodiment 2:
(1) use commercially available pet film, thickness 0.05mm, use odium stearate to carry out oil removal treatment 5min to film surface, then rinse with clear water, dry.
(2) PET after oil removing is soaked 3min at 50 DEG C in 1mol/L potassium hydroxide solution, PET film surface is hydrolyzed.Be hydrolyzed rear clean water, dry.
(3) use the mode of ink jet printing, PET after hydrolyzing prints out circuit mask.
(4) PET film after printing is immersed in 50mmol/L copper-bath, at 25 DEG C, soak 10min, ion is fully exchanged.Then taking-up clean water, dries.
(5) sodium borohydride solution PET film after ion-exchange being placed in 0.2mol/L carries out the reduction of metal ion, takes out, dry by clean water after soaking 5min.
(6) configure nickel plating solution, fill a prescription as follows:
Temperature is 55 DEG C, and current density is 3A/dm
2, pH is 4; By in substrate immersion plating nickel plating 15min, by circuit board washed with de-ionized water after nickel plating terminates, dry, obtain metallic nickel conducting wire.
(7) measuring sheet resistance with four point probe after nickel plating is 0.5 Ω, and adhesion is 5B(ASTMD3359).
Claims (7)
1. on resin substrate, directly prepare a method for conducting wire, it is characterized in that concrete steps are as follows:
(1) use the resin substrate with ester group, amide groups, cyano group, imide or anhydride group group on main chain or side chain, use sodium stearate solution to soak surface degreasing, cleaning, drying after taking out;
(2), in the NaOH that the substrate that step (1) obtained immerses 1 ~ 8mol/L or potassium hydroxide solution, 3 ~ 15min is soaked at 20 DEG C ~ 50 DEG C, cleaning, drying after taking out; Use the method for printing to print out mask pattern on the resin substrate obtained, make outside conductive circuit pattern is exposed to; Or: the substrate first using the method for printing to obtain in step (1) prints out mask pattern, make outside conductive circuit pattern is exposed to, then in the NaOH immersing 1 ~ 8mol/L or potassium hydroxide solution, at 20 DEG C ~ 50 DEG C, 3 ~ 15min is soaked, cleaning, drying after taking out;
(3) by 3 ~ 15min in the metal ion solution of the substrate immersion 10 ~ 100mmol/L after step (2) printing mask 20 DEG C ~ 50 DEG C, cleaning, drying after taking out;
(4) step (3) being immersed the substrate after metal ion solution immerses in the solution of reducing agent, control reductant concentration is 0.5 ~ 2%wt, and reduction temperature is 20 DEG C ~ 50 DEG C, and the recovery time is 3 ~ 15min, metal ion is reduced into simple substance, makes circuit obtain conductivity;
(5) substrate after step (4) being reduced is inserted in appropriate solvent and is dissolved by mask, cleaning, drying;
(6) substrate of step (5) removing mask is inserted in chemical plating or electroplate liquid and carried out coating thickening, after chemical plating or plating, obtain the conducting wire of given requirements.
2. method according to claim 1, it is characterized in that: selected by step (1) is resin substrate with ester group, amide groups, cyano group, imide or anhydride group group on main chain or side chain, described group is the group that hydrolysis obtains carboxyl, and described resin substrate is any one in polyimides, PETG, PEN, polyamide or polyacrylonitrile.
3. method according to claim 1, it is characterized in that: the printing process that step (2) uses is the one in ink jet printing, laser printing, silk screen printing, intaglio printing, flexographic printing or offset printing, the main component of the ink that typographic mask uses be carbon black, in binding resin or solvent any one.
4. method according to claim 1, it is characterized in that: the metal ion solution that step (3) uses is copper, in the solubility hydrochloric acid of silver, cobalt, nickel, aluminium, zinc, gold, platinum, palladium, sulfuric acid or nitrate any one, or be any one in chlorine palladium acid sodium or sodium chloraurate.
5. method according to claim 1, is characterized in that: the reducing agent that step (4) uses is formaldehyde, one in sodium borohydride, dimethylamino borine, ascorbic acid or acetaldehyde.
6. method according to claim 1, is characterized in that: the solvent used in step (5) is ethyl acetate, the mixing of one or more in acetonitrile, butanone, butyl acetate, toluene, ether, butyl ether, EGME, butyl glycol ether or benzinum.
7. method according to claim 1, is characterized in that: the chemical plating used in step (6) or electroplate liquid be copper facing, silver-plated, gold-plated, plating palladium, nickel plating, cobalt plating or zinc-plated in one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| 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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| 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 CN103249255A (en) | 2013-08-14 |
| CN103249255B true CN103249255B (en) | 2016-01-20 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906380A (en) * | 2014-04-03 | 2014-07-02 | 复旦大学 | Method for adding and manufacturing multilayer printed circuit board on PI substrate |
| 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 |
| 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 |
| 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 |
| CN107734868B (en) * | 2017-11-08 | 2020-01-03 | 广东光华科技股份有限公司 | Fine wire circuit and preparation method thereof |
| 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 |
| CN110082407A (en) * | 2019-03-29 | 2019-08-02 | 华东师范大学 | A kind of flexibility gold electrode and preparation method |
| CN110028835B (en) * | 2019-05-07 | 2021-09-28 | 深圳市崯涛油墨科技有限公司 | Bright silver ink coating with three-dimensional effect for polycarbonate transparent material and preparation method thereof |
| 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 |
| 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 |
| 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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| JP2001073159A (en) * | 1999-09-01 | 2001-03-21 | Nippon Riironaaru Kk | Formation of electric conductive film on surface of polyimide resin |
| CN1406288A (en) * | 2000-04-25 | 2003-03-26 | 株式会社日矿材料 | Pretreating agent for plating and method for metal plating using the same |
| CN101479404A (en) * | 2006-06-28 | 2009-07-08 | 欧姆龙株式会社 | Method for producing metal film, foundation composition, metal film and use thereof |
| CN102883543A (en) * | 2012-10-08 | 2013-01-16 | 复旦大学 | Method for manufacturing conducting circuit by additive process |
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- 2013-04-17 CN CN201310131810.6A patent/CN103249255B/en not_active Expired - Fee Related
Patent Citations (4)
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|---|---|---|---|---|
| JP2001073159A (en) * | 1999-09-01 | 2001-03-21 | Nippon Riironaaru Kk | Formation of electric conductive film on surface of polyimide resin |
| CN1406288A (en) * | 2000-04-25 | 2003-03-26 | 株式会社日矿材料 | Pretreating agent for plating and method for metal plating using the same |
| CN101479404A (en) * | 2006-06-28 | 2009-07-08 | 欧姆龙株式会社 | Method for producing metal film, foundation composition, metal film and use thereof |
| CN102883543A (en) * | 2012-10-08 | 2013-01-16 | 复旦大学 | Method for manufacturing conducting circuit by additive process |
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