CN103379747B - The method of high adhesion high conductivity circuit is prepared in a kind of addition - Google Patents
The method of high adhesion high conductivity circuit is prepared in a kind of addition Download PDFInfo
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- CN103379747B CN103379747B CN201310253400.9A CN201310253400A CN103379747B CN 103379747 B CN103379747 B CN 103379747B CN 201310253400 A CN201310253400 A CN 201310253400A CN 103379747 B CN103379747 B CN 103379747B
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Abstract
The present invention is a kind of method using additive process to prepare high adhesion high conductivity circuit.Concretely comprise the following steps: use the mode of printing or photoetching to prepare the mask of line pattern on base material, expose the region at place, conducting wire；Use the techniques such as spin coating, dip-coating, spraying the ink or slurry with ionic adsorption function to be coated on mask, after drying, form adsorption layer；Immerse in specific solvent, dissolve mask pattern, obtain the adsorption layer with line pattern；Base material is immersed in catalytic ionic solution, adsoption catalysis ion, cleans after taking-up；Finally it is placed in the metallization carrying out circuit in chemical plating fluid, obtains the conducting wire of required figure.The present invention need not corrosion of metal, has saved material, also reduces the pollution to environment simultaneously, decreases production stage, so that production cost declines.By adjusting function ink or the formula of slurry to conducting wire combine closely with base material, and electrical property also can reach printed circuit board (pcb) requirement.
Description
Technical field
The invention belongs to printed electronics field, be specially one and use additive process to prepare high adhesion high conductivity circuit
Method.
Background technology
In conventional print-circuit board, the manufacture of conducting wire uses lithography corrosion process, is specially the side using photoetching
Formula prepares mask in copper-clad plate, and at mask protection, layers of copper is carrying out selective corrosion, exposes required line pattern, obtains
Conducting wire.But photoetching corrosion method exists that waste of material is big, environmental protection pressure weight, and production process is many, and it is many that production cost is high etc.
Shortcoming.Emerging printed electronics technique be use printing technology, functional ink or oar material, be printed on rapidly organic or
On inorganic substrate, form various electronic devices and components and electronic circuit, have that operation is simple, environmental friendliness, waste rate are low, cost fall
The advantage such as low, has broad application prospects.Specifically include the mode of printing printing conductions such as use ink-jet, silk screen, intaglio plate, soft version
Slurry or electrically conductive ink, and improve electrical property by heat treatment.Existing electrocondution slurry or ink many uses silver are as conduction
Medium, main cause is the stable chemical nature of silver, can be not oxidized thus lose conductive capability in heat treatment process, this
It is that copper, nickel, ferrum etc. do not have.The but high cost of silver, limits the large-scale utilization of electrocondution slurry and ink.
The problems of conventional preparation techniques Yu printed electronics preparation technology in order to solve printed circuit conducting wire, people
Printing technology is combined with electroless plating technology, form line pattern by printing containing the slurry of catalysed particulate or ink,
Then by the way of chemical plating, make wired foil.The most this method faces the choice pass of an electrical property and adhesion
System.The wire of high electrical performance needs long-time chemical plating, and long-time chemical plating can make the adhesion of circuit be greatly reduced；If
If reducing electroless plating time guarantee adhesion, electrical property is just unable to reach requirement.In the face of this problem, we have invented a kind of straight
It is connected on resin base material the method preparing high adhesion high conductivity circuit, makes wire keep relatively while long-time chemical plating
High adhesion, thus obtain the circuit that adhesion is the most excellent with electrical property, meet the requirement of PCB circuit.
Summary of the invention
It is an object of the invention at preparation PCB high conductivity height adhesion circuit, thus part replaces traditional light
Carve etching process.Present invention utilizes the adsorption function macromolecule adsorption to catalytic ionic, make catalytic ionic distribution online
Among the figure of road, such that it is able to the selectivity of catalytic chemistry plating reaction is carried out.Selected catalytic ionic be mainly cation with
Anionic polyelectrolyte, the main Absorptive complex wave of adsorption and charge adsorption.The bases such as carboxyl on functional polymer, amido
Group, can form coordinate bond with catalytic ionic, thus by catalytic ionic closely chemisorbed to its surface, this is Absorptive complex wave；
Simultaneously as functional polymer is polyelectrolyte, catalytic ionic solution can occur partial ionization, thus carry upper electric charge,
If catalytic ionic and polyelectrolyte opposite charge, it is possible to catalytic ionic is physically adsorbed to its table by charge effect
Face.
The method that high adhesion high conductivity circuit is prepared in a kind of addition that the present invention proposes, specifically comprises the following steps that
(1) prepare function ink or slurry, be in terms of 1 by gross mass, by the resin of 0 ~ 0.7 gross mass, 0.2 ~ 0.9 gross mass
Solvent, the filler of 0 ~ 0.5 gross mass, the ionic adsorption functional polymer of 0.01 ~ 0.2 gross mass, 0.01 ~ 0.05 gross mass
Additive mix, with 300-600 turn/min stir 12-24 hour, obtain function ink or slurry；
(2) base material carrying out pretreatment, base material needs cleaning before using, concrete grammar is that base material immerses 1% sodium stearate
In solution, 30-50 degree soaks 0.5-1 hour, rinses with clear water, dry and obtain pretreated base material after taking-up；
(3) in step (2), mask is prepared on pretreated base material.The preparation of mask can use laser printing, recessed
The mode of version printing, silk screen printing, offset printing or photoetching is carried out, and exposes required line pattern；
(4) obtain in step (3) being coated with on the base material that mask covers being covered with function ink or the slurry that step (1) obtains.
The mode of coating includes spin coating, dip-coating, sprays, scratches and directly print, and makes function ink or slurry overlay on uniformly on base material；
Dry, obtain adsorption layer；
(5) base material that the function ink obtained in step (4) or slurry coat be placed in specific solvent make mask dissolve,
Thus obtain the adsorption layer of line pattern；Clean post-drying；
(6) base material after processing in step (5) is placed in the solution of the ion with catalysis, and adsorption layer can be by molten
Catalytic ionic in liquid is adsorbed to substrate surface；Cleaning, drying after taking-up；
(7) base material of the adsoption catalysis ion obtained in step (6) be placed in chemical plating fluid carry out the metallization of circuit,
Cleaning, drying is taken out after 5-60 minute；
(8) by metallized circuit post processing, thus conducting wire is obtained.
In the present invention, used in step (1), resin is epoxy resin, polyurethane, polyvinyl butyral resin, polyvinyl alcohol
The mixing of one or more in formal, polyacrylate, alkyd resin or unsaturated polyester (UP).
In the present invention, the solvent used in step (1) is that water, alcohols solvent, ketones solvent, lipid solvent or ethers are molten
The mixing of one or more in agent.
In the present invention, the filler used in step (1) be ground calcium carbonate, white carbon black, aerosil, aluminium oxide or
The mixing of one or more in titanium dioxide.
In the present invention, the ionic adsorption functional polymer used in step (1) be polyacrylic acid, polypropylene amine, poly-third
Olefin(e) acid sodium, polyacrylamide, polyacrylonitrile, polymethylacrylic acid, chitosan, poly-amino silicone, kayexalate or
The mixing of one or more in polydiene base the third alkyl dimethyl ammonium chloride.
In the present invention, used in step (1), additive is levelling agent, thickening agent and toughener.
In the present invention, the base material used in step (2) is glass fabric reinforced epoxy, poly terephthalic acid second
One in diol ester, polypropylene, polyethylene, polyimides, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide or polyether-ketone.
In the present invention, described in step (5), particular solution is ethyl acetate.
In the present invention, the catalytic ionic solution used in step (6) be copper, nickel, palladium, silver, gold, cobalt, platinum or ferrum can
The aqueous solution of soluble.
In the present invention, the chemical plating fluid used in step (7) is electroless copper, chemical nickel plating, electroless cobalt plating, chemical plating
One in silver, chemical palladium-plating, chemical gilding or chemical plating stannum.
The beneficial effects of the present invention is:
1. the present invention compared to traditional PCB conducting wire preparation used by lithography corrosion process compare have saving material,
Protection environment, simplification operation, the advantage of reduction cost.
2. the conducting wire that the present invention obtains is close with bulk metal in electrical conductivity, can obtain the lowest the leading of sheet resistance
Line, thus meet the requirement of PCB.
3. the conducting wire good adhesion that the present invention obtains, and obtain on the premise of endlessly sacrificing electrical property.
4. the present invention need not high-temperature heat treatment, can be applicable to PET etc. thermo-labile but on the base material of low cost.
Accompanying drawing explanation
Fig. 1 is the conducting wire laboratory sample for electronic label antenna prepared by this technique.
Fig. 2 is conducting wire (copper) surface SEM image prepared by this technique.
Detailed description of the invention
The following examples are to further illustrate the present invention rather than limit the scope of the present invention.
Embodiment 1:
(1) function ink is prepared: by the bisphenol A epoxide resin of 0.1, the conductive black of 0.1, the chitosan of 0.05,0.45
Butanone, the ethyl acetate mixing of 0.3, under 300 turns/min, stir 24h, control whipping temp less than 10 DEG C in case stop ring
Epoxy resins solidifies.
(2) PET of commercially available 0.05 μ m-thick selected by base material, needs to soak 30min before using in 0.5% sodium stearate solution,
Dried for standby after cleaning.
(3) laser printing circuit mask in PET base material.
(4) base material after printing mask is immersed 1min in function ink, make ink infiltrate its surface equably.After taking-up
It is placed in 2h in the baking oven of 70 DEG C.
(5) base material after drying is placed in the middle of ethyl acetate, and coordinates ultrasonic, dissolves circuit mask, on mask
Function ink comes off the most together.Cleaning, drying after taking-up.
(6) 30min in the chlorine palladium acid sodium solution of 0.02mol/L it is placed in, to adsorb chlorine palladium acid group.Clean after taking-up.
(7) configuration chemical nickel-plating solution, formula is as follows:
| Reagent | Concentration |
| Single nickel salts | 20g/L |
| Ammonium chloride | 30g/L |
| Sodium hypophosphite | 30g/L |
| Ammonia (28%wt) | 30ml/L |
| Sodium citrate | 10g/L |
Chemical plating temperature is 40 DEG C, and pH is 9 to 10.
(8) taking out after 30min, measuring sheet resistance is 0.5 Ω, and adhesion is that 5B(is according to ASTM D3359 standard).
Embodiment 2:
(1) function ink is prepared: by the polyvinyl butyral resin of 0.05, the bisphenol A epoxide resin of 0.05, the gas phase of 0.1
Silicon dioxide, the polyacrylic acid of 0.1, the ethanol mixing of 0.7, under 500 turns/min, stir 24h, control whipping temp and be less than
10 DEG C to prevent epoxy resin cure.
(2) PI of commercially available 0.05 μ m-thick selected by base material, needs to soak 30min before using in 0.5% sodium stearate solution,
Dried for standby after cleaning.
(3) on PI base material, screen printing brushes out mask pattern.
(4) base material after printing mask is immersed 1min in function ink, make ink infiltrate its surface equably.After taking-up
It is placed in 2h in the baking oven of 70 DEG C.
(5) base material after drying is placed in the middle of ethyl acetate, and coordinates ultrasonic, dissolves circuit mask, on mask
Function ink comes off the most together.Cleaning, drying after taking-up.
(6) it is placed in 30min in the silver nitrate solution of 0.05mol/L, cleans after taking-up.
(7) configuration chemical copper plating solution, formula is as follows:
| Reagent | Concentration |
| Copper sulfate pentahydrate | 15g/L |
| Sodium potassium tartrate tetrahydrate | 14.5g/L |
| EDETATE SODIUM | 17.5g/L |
| Sodium hydroxide | 16g/L |
| Formaldehyde | 15ml/L |
Chemical plating temperature is 40 DEG C, and pH is 12 to 13.
(8) take out after certain time, measure sheet resistance adhesion, as shown in table 1.
Table 1 electroless plating time and link performance relation
| Electroless plating time | Sheet resistance | Adhesion | Apparent form |
| 5 | 15.8 | 5B | Coating covers uneven |
| 10 | 0.35 | 5B | Coating uniform fold |
| 15 | 0.082 | 5B | Coating uniform fold |
| 20 | 0.041 | 5B | Coating uniform fold |
| 30 | 0.025 | 5B | Coating uniform fold |
| 60 | 0.021 | 4B | Coating has a little bubble |
Claims (8)
1. the method that high adhesion high conductivity circuit is prepared in an addition, it is characterised in that specifically comprise the following steps that
(1) prepare function ink or slurry, be in terms of 1 by gross mass, by the resin of 0 ~ 0.7 gross mass, 0.2 ~ 0.9 gross mass molten
Agent, the filler of 0 ~ 0.5 gross mass, the ionic adsorption functional polymer of 0.01 ~ 0.2 gross mass, the interpolation of 0.01 ~ 0.05 gross mass
Agent mix, with 300-600 turn/min stir 12-24 hour, obtain function ink or slurry；Ionic adsorption functional polymer is shell
Polysaccharide or poly-amino silicone；
(2) base material carrying out pretreatment, base material needs cleaning before using, concrete grammar is that base material immerses 1% sodium stearate solution
Middle 30-50 degree soaks 0.5-1 hour, rinses with clear water, dry and obtain pretreated base material after taking-up；
(3) in step (2), mask is prepared on pretreated base material；The preparation of mask uses laser printing, intaglio printing, silk
The mode of wire mark brush, offset printing or photoetching is carried out, and exposes required line pattern；
(4) obtain in step (3) being coated with on the base material that mask covers being covered with function ink or the slurry that step (1) obtains；
The mode of coating includes spin coating, dip-coating, sprays, scratches and directly print, and makes function ink or slurry overlay on base uniformly
On material；Dry, obtain adsorption layer；
(5) base material that the function ink obtained in step (4) or slurry coat is placed in specific solvent makes mask dissolve, so
Just obtain the adsorption layer of line pattern；Clean post-drying；Described particular solution is ethyl acetate；
(6) base material after processing in step (5) is placed in the solution of the ion with catalysis, and adsorption layer can be by solution
Catalytic ionic be adsorbed to substrate surface；Cleaning, drying after taking-up；
(7) base material of the adsoption catalysis ion obtained in step (6) is placed in chemical plating fluid carries out the metallization of circuit, 5-60
Cleaning, drying is taken out after minute；
(8) by metallized circuit post processing, thus conducting wire is obtained.
Method the most according to claim 1, it is characterised in that used in step (1) resin be epoxy resin, polyurethane,
In polyvinyl butyral resin, polyvinyl formal, polyacrylate, alkyd resin or unsaturated polyester (UP), one or more is mixed
Close.
Method the most according to claim 1, it is characterised in that the solvent used in step (1) is water, alcohols solvent, ketone
The mixing of one or more in kind solvent, lipid solvent or ether solvent.
Method the most according to claim 1, it is characterised in that the filler used in step (1) is ground calcium carbonate, charcoal
The mixing of one or more in black, aerosil, aluminium oxide or titanium dioxide.
Method the most according to claim 1, it is characterised in that used in step (1), additive is levelling agent, thickening agent
And toughener.
Method the most according to claim 1, it is characterised in that the base material used in step (2) is that glass fabric strengthens
Epoxy resin, polyethylene terephthalate, polypropylene, polyethylene, polyimides, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide
Or the one in polyether-ketone.
Method the most according to claim 1, it is characterised in that the catalytic ionic solution used in step (6) be copper, nickel,
The aqueous solution of the soluble-salt of palladium, silver, gold, cobalt, platinum or ferrum.
Method the most according to claim 1, it is characterised in that the chemical plating fluid used in step (7) be electroless copper,
One in chemical nickel plating, electroless cobalt plating, chemical silvering, chemical palladium-plating, chemical gilding or chemical plating stannum.
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| CN201310253400.9A CN103379747B (en) | 2013-06-25 | 2013-06-25 | The method of high adhesion high conductivity circuit is prepared in a kind of addition |
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| CN201310253400.9A CN103379747B (en) | 2013-06-25 | 2013-06-25 | The method of high adhesion high conductivity circuit is prepared in a kind of addition |
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| CN103379747B true CN103379747B (en) | 2016-08-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103648243B (en) * | 2013-12-13 | 2016-05-25 | 复旦大学 | A kind of multiple-plate addition preparation method |
| CN108456875B (en) * | 2018-03-16 | 2019-10-18 | 华南理工大学 | A kind of low roughness silverskin and the preparation method and application thereof |
| CN109251591B (en) * | 2018-11-19 | 2021-10-15 | 宁波石墨烯创新中心有限公司 | Conductive ink, electronic tag, preparation method of electronic tag and radio frequency identification system |
| CN109686502B (en) * | 2019-01-28 | 2020-07-24 | 青岛九维华盾科技研究院有限公司 | Method for preparing transparent conductive film by printing and chemical reduction method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139369A (en) * | 1995-06-26 | 1997-01-01 | 三星航空产业株式会社 | Circuit board and fabricating method thereof |
| CN101036423A (en) * | 2004-08-26 | 2007-09-12 | 富士胶片株式会社 | Method for producing conductive pattern material |
| CN101684190A (en) * | 2008-09-26 | 2010-03-31 | 富士胶片株式会社 | Composition for forming layer to be plated, method of producing metal pattern material, metal pattern material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5819619B2 (en) * | 2010-03-19 | 2015-11-24 | 富士フイルム株式会社 | Ink jet ink, surface metal film material and method for producing the same, metal pattern material and method for producing the same |
| KR101844412B1 (en) * | 2011-10-31 | 2018-05-15 | 삼성전자주식회사 | method of forming conductive pattern on a substrate using inkjet printing technique |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139369A (en) * | 1995-06-26 | 1997-01-01 | 三星航空产业株式会社 | Circuit board and fabricating method thereof |
| CN101036423A (en) * | 2004-08-26 | 2007-09-12 | 富士胶片株式会社 | Method for producing conductive pattern material |
| CN101684190A (en) * | 2008-09-26 | 2010-03-31 | 富士胶片株式会社 | Composition for forming layer to be plated, method of producing metal pattern material, metal pattern material |
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