CN103379747A - Method of preparing circuit with high adhesive force and high conductivity in additive mode - Google Patents
Method of preparing circuit with high adhesive force and high conductivity in additive mode Download PDFInfo
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- CN103379747A CN103379747A CN2013102534009A CN201310253400A CN103379747A CN 103379747 A CN103379747 A CN 103379747A CN 2013102534009 A CN2013102534009 A CN 2013102534009A CN 201310253400 A CN201310253400 A CN 201310253400A CN 103379747 A CN103379747 A CN 103379747A
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Abstract
The invention provides a method of preparing a circuit with high adhesive force and high conductivity by using the additive process. The method comprises the following steps that a mask of a circuit diagram is prepared on base material in a printing or photoetching mode, and the area where the conducting circuit is located is exposed; ink or slurry having the ionic adsorption function coats the mask through the processes of spin coating, dip coating, spray coating and the like and forms an adsorption layer after being dried; the base material coated with the ink or the slurry is immersed in specific solvent, the diagram of the mask is dissolved away, and the adsorption layer with the circuit diagram is obtained; the base material is immersed in catalytic ion solution, adsorbs catalytic ions, and is cleaned after being taken out; finally, metallization of the circuit is conducted by placing the base material in chemical plating solution, and the conducting circuit with the required diagram is obtained. As for the method, corrosion of metal is not needed, materials are saved, meanwhile, pollution to the environment is lowered, the number of the production steps is reduced, and therefore production cost is lowered. By means of adjustment of the formula of the functional ink or the functional slurry, the obtained conducting circuit and the base material can be tightly combined, and electrical properties can also meet the requirements of a printed-circuit board.
Description
Technical field
The invention belongs to the printed electronics field, be specially a kind of method that adopts additive process to prepare high adhesion high conductivity circuit.
Background technology
What the manufacturing of conducting wire was adopted in the traditional printing circuit board is lithography corrosion process, is specially to use the mode of photoetching to prepare mask in copper-clad plate, and at mask protection the copper layer is being carried out selective corrosion, exposes required line pattern, obtains the conducting wire.But the photoetching corrosion method exists that waste of material is large, environmental protection pressure is heavy, and production process is many, the high shortcomings that waits of production cost.Emerging printed electronics technique 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, the advantages such as environmental friendliness, waste rate are low, cost, have broad application prospects.Specifically comprise mode of printing printing conductive slurry or electrically conductive inks such as using ink-jet, silk screen, intaglio plate, gentle version, and improve electrical property by heat treatment.Existing electrocondution slurry or printing ink use silver as conducting medium more, and main cause is the stable chemical nature of silver, thus can be in heat treatment process the not oxidized conductive capability that loses, this is that copper, nickel, iron etc. do not have.But the high cost of silver has limited the large-scale utilization of electrocondution slurry and printing ink.
For traditional preparation technology of solving the printed circuit conducting wire and printed electronics preparation technology's problems, people combine printing technology with electroless plating technology, the slurry or the printing ink that contain catalysed particulate by printing form line pattern, and then the mode by chemical plating makes the circuit metallization.But this method faces the choice relation of an electrical property and adhesion.The wire of high electrical performance needs long-time chemical plating, and long-time chemical plating can make the adhesion of circuit greatly descend; Guarantee adhesion if reduce the chemical plating time, electrical property just can't reach requirement.In the face of this problem, we have invented a kind of method that directly prepares high adhesion high conductivity circuit at resin base material, make wire in long-time chemical plating, keep higher adhesion, thereby obtain all good circuits of adhesion and electrical property, satisfy the requirement of PCB circuit.
Summary of the invention
The object of the invention is to the high adhesion circuit of high conductivity at preparation PCB, thereby part replaces traditional lithography corrosion process.The present invention has utilized the suction-operated of adsorption function macromolecule to the catalysis ion, makes the catalysis ion distribution among line pattern, thus can catalytic chemistry the selectivity of plating reaction carry out.Selected catalysis ion is mainly cation and anionic polyelectrolyte, the main complexing absorption of suction-operated and electric charge absorption.The groups such as the carboxyl on the functional polymer, amido can form coordinate bond with the catalysis ion, thereby closely chemisorbed is to its surface with the catalysis ion, and this is complexing absorption; Simultaneously, because functional polymer is polyelectrolyte, in the catalysis solion partial ionization can occurs, thereby be with electric charge, if catalysis ion and polyelectrolyte opposite charge, just can by charge effect with the catalysis ion physical be adsorbed to its surface.
A kind of addition that the present invention proposes prepares the method for high adhesion high conductivity circuit, and concrete steps are as follows:
(1) preparation function printing ink or slurry, take gross mass as 1, resin with 0 ~ 0.7 gross mass, 0.2 the solvent of ~ 0.9 gross mass, the filler of 0 ~ 0.5 gross mass, the ionic adsorption functional polymer of 0.01 ~ 0.2 gross mass, the additive of 0.01 ~ 0.05 gross mass mixes, with 300-600 turn/min stirred 12-24 hour, obtained function printing ink or slurry;
(2) base material is carried out preliminary treatment, need cleaning before base material uses, concrete grammar is base material to be immersed the 30-50 degree soaked 0.5-1 hour in 1% sodium stearate solution, with the clear water flushing, dries and obtains pretreated base material after taking out;
(3) pretreated base material prepares mask in step (2).The preparation of mask can adopt the mode of laser printing, intaglio printing, silk screen printing, offset printing or photoetching to carry out, and exposes needed line pattern;
(4) obtaining base material that mask covers in step (3) is coated with and is covered with function printing ink or the slurry that step (1) obtains.The mode that applies comprises spin coating, dip-coating, spraying, blade coating and directly printing, makes function printing ink or slurry overlay on uniformly on the base material; Oven dry obtains adsorption layer;
(5) base material that the function printing ink that obtains in the step (4) or slurry is applied places specific solvent to make the mask dissolving, so just obtains the adsorption layer of line pattern; Clean post-drying;
(6) base material after processing in the step (5) is placed the solution of the ion with catalysis, adsorption layer can be with the catalysis ionic adsorption in the solution to substrate surface; Cleaning, drying after taking out;
(7) base material with the adsoption catalysis ion that obtains in the step (6) places chemical plating fluid to carry out the metallization of circuit, takes out cleaning, drying after 5-60 minute;
(8) with metallized circuit reprocessing, thereby obtain the conducting wire.
Among the present invention, in the step (1) the resin that uses be one or more mixing in epoxy resin, polyurethane, polyvinyl butyral resin, polyvinyl formal, polyacrylate, alkyd resins or the unsaturated polyester (UP).
Among the present invention, employed solvent is one or more the mixing in water, alcohols solvent, ketones solvent, lipid solvent or the ether solvent in the step (1).
Among the present invention, employed filler is one or more the mixing in powdered whiting, carbon black, aerosil, aluminium oxide or the titanium dioxide in the step (1).
Among the present invention, employed ionic adsorption functional polymer is one or more the mixing in polyacrylic acid, polypropylene amine, Sodium Polyacrylate, polyacrylamide, polyacrylonitrile, polymethylacrylic acid, shitosan, poly-amino silicone, kayexalate or polydiene base the third alkyl dimethyl ammonium chloride in the step (1).
Among the present invention, in the step (1) the additive that uses be levelling agent, thickener and flexibilizer.
Among the present invention, employed base material is a kind of in glass fabric reinforced epoxy, PETG, polypropylene, polyethylene, polyimides, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide or the polyether-ketone in the step (2).
Among the present invention, particular solution is ethyl acetate described in the step (5).
Among the present invention, the aqueous solution that employed catalysis solion is the soluble-salt of copper, nickel, palladium, silver, gold, cobalt, platinum or iron in the step (6).
Among the present invention, employed chemical plating fluid is a kind of in electroless copper, chemical nickel plating, electroless cobalt plating, chemical silvering, chemical palladium-plating, chemical gilding or the chemical plating stannum in the step (7).
Beneficial effect of the present invention is:
1. the present invention prepares used lithography corrosion process and compares and have economical with materials, protection of the environment, simplify working process, reduce the advantage of cost compared to the traditional PCB conducting wire.
2. the conducting wire that obtains of the present invention is close with bulk metal on conductivity, can obtain the very low wire of sheet resistance, thereby satisfy the requirement of PCB.
3. the conducting wire adhesion that obtains of the present invention is good, and obtains under the prerequisite of endlessly sacrificing electrical property.
4. the present invention does not need high-temperature heat treatment, and it is thermo-labile but on the base material that cost is low to can be applicable to PET etc.
Description of drawings
Fig. 1 is the conducting wire laboratory sample that is used for electronic label antenna of this technique preparation.
Fig. 2 is the surperficial SEM image in conducting wire (copper) of this technique preparation.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) preparation function printing ink: the bisphenol A epoxide resin with 0.1,0.1 conductive black, 0.05 shitosan, 0.45 butanone, 0.3 ethyl acetate mixes, turn 300/stir 24h under the min, the control whipping temp be no more than 10 ℃ in case the stop ring epoxy resins solidify.
(2) base material is selected the thick PET of commercially available 0.05 μ m, need to soak 30min in 0.5% sodium stearate solution before using, dried for standby after cleaning.
(3) laser printing circuit mask on the PET base material.
(4) base material behind the printing mask is immersed 1min in the function printing ink, make printing ink infiltrate equably its surface.Taking-up is placed on 2h in 70 ℃ the baking oven.
(5) base material after will drying places in the middle of the ethyl acetate, and cooperates ultrasonicly, dissolves the circuit mask, and the function printing ink on the mask also comes off together.Cleaning, drying after taking out.
(6) place the chlorine palladium acid sodium solution 30min of 0.02mol/L, with absorption chlorine palladium acid group.Clean after taking out.
(7) configuration chemical nickel-plating solution, it is as follows to fill a prescription:
| Reagent | Concentration |
| Single nickel salts | 20g/L |
| Ammonium chloride | 30g/L |
| Sodium hypophosphite | 30g/L |
| Ammoniacal liquor (28%wt) | 30ml/L |
| Natrium citricum | 10g/L |
The chemical plating temperature is 40 ℃, and pH is 9 to 10.
(8) take out behind the 30min, measuring sheet resistance is 0.5 Ω, and adhesion is that 5B(is according to ASTM D3359 standard).
Embodiment 2:
(1) preparation function printing ink: the polyvinyl butyral resin with 0.05,0.05 bisphenol A epoxide resin, 0.1 aerosil, 0.1 polyacrylic acid, 0.7 ethanol mix, turn 500/stir 24h under the min, the control whipping temp be no more than 10 ℃ in case the stop ring epoxy resins solidify.
(2) base material is selected the thick PI of commercially available 0.05 μ m, need to soak 30min in 0.5% sodium stearate solution before using, dried for standby after cleaning.
(3) screen printing brushes out mask pattern on the PI base material.
(4) base material behind the printing mask is immersed 1min in the function printing ink, make printing ink infiltrate equably its surface.Taking-up is placed on 2h in 70 ℃ the baking oven.
(5) base material after will drying places in the middle of the ethyl acetate, and cooperates ultrasonicly, dissolves the circuit mask, and the function printing ink on the mask also comes off together.Cleaning, drying after taking out.
(6) place the liquor argenti nitratis ophthalmicus 30min of 0.05mol/L, clean after taking out.
(7) configuration chemical copper plating solution, it is as follows to fill a prescription:
| Reagent | Concentration |
| Salzburg vitriol | 15g/L |
| Sodium potassium tartrate tetrahydrate | 14.5g/L |
| EDETATE SODIUM | 17.5g/L |
| NaOH | 16g/L |
| Formaldehyde | 15ml/L |
The chemical plating temperature is 40 ℃, and pH is 12 to 13.
(8) take out behind the certain hour, measure the sheet resistance adhesion, as shown in table 1.
Table 1 chemical plating time and link performance relation
| The chemical plating time | Sheet resistance | Adhesion | Apparent pattern |
| 5 | 15.8 | 5B | Coating covers inhomogeneous |
| 10 | 0.35 | 5B | The coating uniform fold |
| 15 | 0.082 | 5B | The coating uniform fold |
| 20 | 0.041 | 5B | The coating uniform fold |
| 30 | 0.025 | 5B | The coating uniform fold |
| 60 | 0.021 | 4B | Coating has a little bubble |
Claims (10)
1. an addition prepares the method for high adhesion high conductivity circuit, it is characterized in that concrete steps are as follows:
(1) preparation function printing ink or slurry, take gross mass as 1, resin with 0 ~ 0.7 gross mass, 0.2 the solvent of ~ 0.9 gross mass, the filler of 0 ~ 0.5 gross mass, the ionic adsorption functional polymer of 0.01 ~ 0.2 gross mass, the additive of 0.01 ~ 0.05 gross mass mixes, with 300-600 turn/min stirred 12-24 hour, obtained function printing ink or slurry;
(2) base material is carried out preliminary treatment, need cleaning before base material uses, concrete grammar is base material to be immersed the 30-50 degree soaked 0.5-1 hour in 1% sodium stearate solution, with the clear water flushing, dries and obtains pretreated base material after taking out;
(3) pretreated base material prepares mask in step (2); The preparation of mask adopts the mode of laser printing, intaglio printing, silk screen printing, offset printing or photoetching to carry out, and exposes needed line pattern;
(4) obtaining base material that mask covers in step (3) is coated with and is covered with function printing ink or the slurry that step (1) obtains;
The mode that applies comprises spin coating, dip-coating, spraying, blade coating and directly printing, makes function printing ink or slurry overlay on uniformly on the base material; Oven dry obtains adsorption layer;
(5) base material that the function printing ink that obtains in the step (4) or slurry is applied places specific solvent to make the mask dissolving, so just obtains the adsorption layer of line pattern; Clean post-drying;
(6) base material after processing in the step (5) is placed the solution of the ion with catalysis, adsorption layer can be with the catalysis ionic adsorption in the solution to substrate surface; Cleaning, drying after taking out;
(7) base material with the adsoption catalysis ion that obtains in the step (6) places chemical plating fluid to carry out the metallization of circuit, takes out cleaning, drying after 5-60 minute;
(8) with metallized circuit reprocessing, thereby obtain the conducting wire.
2. method according to claim 1, it is characterized in that in the step (1) the resin that uses be one or more mixing in epoxy resin, polyurethane, polyvinyl butyral resin, polyvinyl formal, polyacrylate, alkyd resins or the unsaturated polyester (UP).
3. method according to claim 1 is characterized in that employed solvent in the step (1) is one or more the mixing in water, alcohols solvent, ketones solvent, lipid solvent or the ether solvent.
4. method according to claim 1 is characterized in that employed filler in the step (1) is one or more the mixing in powdered whiting, carbon black, aerosil, aluminium oxide or the titanium dioxide.
5. method according to claim 1 is characterized in that employed ionic adsorption functional polymer in the step (1) is one or more the mixing in polyacrylic acid, polypropylene amine, Sodium Polyacrylate, polyacrylamide, polyacrylonitrile, polymethylacrylic acid, shitosan, poly-amino silicone, kayexalate or polydiene base the third alkyl dimethyl ammonium chloride.
6. method according to claim 1, it is characterized in that in the step (1) the additive that uses be levelling agent, thickener and flexibilizer.
7. method according to claim 1 is characterized in that employed base material in the step (2) is a kind of in glass fabric reinforced epoxy, PETG, polypropylene, polyethylene, polyimides, polyacrylonitrile, polyphenylene sulfide, polyphenylene oxide or the polyether-ketone.
8. method according to claim 1 is characterized in that particular solution is ethyl acetate described in the step (5).
9. method according to claim 1 is characterized in that the aqueous solution that employed catalysis solion is the soluble-salt of copper, nickel, palladium, silver, gold, cobalt, platinum or iron in the step (6).
10. method according to claim 1 is characterized in that employed chemical plating fluid in the step (7) is a kind of in electroless copper, chemical nickel plating, electroless cobalt plating, chemical silvering, chemical palladium-plating, chemical gilding or the chemical plating stannum.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103648243A (en) * | 2013-12-13 | 2014-03-19 | 复旦大学 | Method for preparing multilayer board in additive mode |
| CN108456875A (en) * | 2018-03-16 | 2018-08-28 | 华南理工大学 | A kind of low roughness silverskin and the preparation method and application thereof |
| CN109251591A (en) * | 2018-11-19 | 2019-01-22 | 宁波石墨烯创新中心有限公司 | Electrically conductive ink, electronic tag, preparation method and radio-frequency recognition system |
| CN109686502A (en) * | 2019-01-28 | 2019-04-26 | 青岛九维华盾科技研究院有限公司 | A method of printing prepares transparent conductive film with chemical reduction method |
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| US20130106942A1 (en) * | 2011-10-31 | 2013-05-02 | Samsung Electronics Co., Ltd. | Methods of forming patterns on a substrate |
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Patent Citations (5)
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| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103648243A (en) * | 2013-12-13 | 2014-03-19 | 复旦大学 | Method for preparing multilayer board in additive mode |
| CN103648243B (en) * | 2013-12-13 | 2016-05-25 | 复旦大学 | A kind of multiple-plate addition preparation method |
| CN108456875A (en) * | 2018-03-16 | 2018-08-28 | 华南理工大学 | A kind of low roughness silverskin and the preparation method and application thereof |
| 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 |
| CN109251591A (en) * | 2018-11-19 | 2019-01-22 | 宁波石墨烯创新中心有限公司 | Electrically conductive ink, electronic tag, preparation method and radio-frequency recognition system |
| 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 |
| CN109686502A (en) * | 2019-01-28 | 2019-04-26 | 青岛九维华盾科技研究院有限公司 | A method of printing prepares transparent conductive film with chemical reduction method |
| 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 |
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