CN103619128B - Preparing method of flexible circuit board based on ink-jet printing technique - Google Patents
Preparing method of flexible circuit board based on ink-jet printing technique Download PDFInfo
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- CN103619128B CN103619128B CN201310606414.4A CN201310606414A CN103619128B CN 103619128 B CN103619128 B CN 103619128B CN 201310606414 A CN201310606414 A CN 201310606414A CN 103619128 B CN103619128 B CN 103619128B
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- ink
- silver salt
- electroless copper
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- flexible pcb
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Abstract
The invention relates to the field of flexible circuit board manufacture, and provides a preparing method of a flexible circuit board based on an ink-jet printing technique. The preparing method is characterized by including the following steps of providing activated ink containing silver salt, carrying out ink-jet printing on a substrate with the activated ink containing the silver salt, sintering the substrate undergoing ink-jet printing to obtain a sintered product, providing electroless copper plating liquid and carrying out electroless copper plating on the sintered product. According to the preparing method of the flexible circuit board based on the ink-jet printing technique, solid objects do not exist in the ink, the ink cannot settle and can be stored for a long time, viscosity of the ink is low, ink-jet holes cannot be blocked, printing can be carried out through a common ink-jet printer, the amount of silver used in the method is little, cost is low, an obtained copper conductive line is continuous, compact and high in conductivity, and wiring accuracy and density cannot be influenced by an electroless copper plating process.
Description
Technical field
The invention belongs to flexible PCB manufactures field and in particular to a kind of flexible PCB based on inkjet technology
Preparation method.
Background technology
Printed electronic（Printed Electronics）Printing technology and the organically blending of electronic technology, it using plus
Legal system is become to make electronic device and circuit, ratio traditional photoengraving subtractive process environmental protection, efficiently.Wherein, based on nano metal conductive ink
The inkjet technology of water is in flexible printed circuit board（Flexible Printed Circuit, FPC）Preparation aspect advantage is bright
Aobvious, it make the production of circuit board as office's mimeograph documents easily, can achieve " What You See Is What You Get ", and wiring be close, can make life
Produce flexibility, miniaturization of electronic products.The basic procedure of inkjet printing circuit is：The CAD designing wiring diagram is passed through to calculate
The ink-jet system that machine controls, is printed upon flexible base board（Typically polyimides, PI）On, send in low-temperature sintering stove after being dried and burn
Knot, you can obtain flexible print circuit board finely.This flow process can achieve rolling to rolling（roll to roll）High-efficiency and continuous metaplasia
Produce, process is simple, only 1 μm of minimum wiring spacing.Obviously, the key of this technology is nano metal conductive ink, and it requires ink
Viscosity is low, do not settle, and can preserve for a long time, ink of not spreading and sinking in during printing, not block jet orifice, metallic particles antioxidation in ink, no
Reunion, sintering temperature are low.It is suitable for the mainly golden ink of nano metal conductive ink and silver inks that this requires.With gold or silvery for nanometer
Metallic conduction ink is although price, but gold and silver chemical stable in properties, not oxidizable, and particle diameter very little can be dispersed into
Nano-particle（Typically smaller than 20nm）, it is easy to be constructed to the metallic conduction ink of stable suspersion and nonchoking nozzle.Typically, nanometer
The particle diameter of metallic particles is more tiny, and sintering temperature is lower, such as typically smaller than 230 DEG C of the sintering temperature of nanometer silver, and this makes printing
Thing, in addition to the PI of heatproof, can also select other more common organic polymer.
As wire, though the electrical conductivity of copper be slightly below silver, inexpensive, in addition copper also have good welding performance and resistance to from
Sub- animal migration.By contrast, not only electrical conductivity is not so good as copper to golden wire, and welding performance is also poor, excessively thin pad（pad）Growing
Weld interval under, gold can diffuse into solder, so that fusing point is increased rapidly, sometimes due to the difference of diffusion coefficient, there is also
Kirkendall cavity, lowers weld strength；Silvery circuit uses in hot and humid environment for a long time, easily produces ion migration
Phenomenon, leads to negative electrode dendritic growth to cause short circuit, reduces the reliability of product, limit the range of product.Nanometer
Copper conductive ink preparation is difficult, is primarily due to nanometer copper particle easily oxidized.Nanometer copper particle after oxidation is difficult by surface
Activating agent is disperseed, and is difficult to sinter plain conductor into, additionally, copper also has higher surface energy, its nano particle diameter is relatively
Greatly, typically greater than 40 μm, this can lead to copper nano particles to be unable to stable suspersion, and ink free settling is layered.
Content of the invention
The technical problem to be solved is to overcome the defect of prior art, provides one kind to be based on inkjet printing skill
The preparation method of the flexible PCB of art.
The present invention is achieved in that a kind of preparation method of the flexible PCB based on inkjet technology, and it includes
Following steps：
Activated inks containing silver salt are provided；
The activated inks of silver salt are contained described in inkjet printing on matrix；
Matrix after described inkjet printing is sintered, obtains sintered product；
Chemical bronze plating liquid is provided, electroless copper is carried out to described sintered product.
The preparation method of the flexible PCB based on inkjet technology that the present invention provides, conductive for existing Nanometer Copper
The deficiency of ink, with the mixed aqueous solution of silver salt and organic reducing agent as ink, inkjet printing, on flexible substrate film, is formed
" stealthy circuit ", is then sintered to " stealthy circuit ", makes the silver ion reduction in ink become metal silver nano-grain, then enters
Row electroless copper, the silver nano-grain being now reduced as the activator of electroless copper, induces the deposition of copper, formed light,
Uniformly, the strong copper coating of adhesive force, obtains the copper circuit of " dominant ".It is somebody's turn to do the preparation of the flexible PCB based on inkjet technology
Method, Solid Free thing in ink, will not settle, can preserve for a long time；Ink viscosity is low, does not block jet orifice, can use common spray
Black printer prints；Silver-colored consumption very little, low cost；The copper conductive traces that obtain are continuous, fine and close, electrical conductivity is high, wiring precision and
Density is not affected by chemical-copper-plating process.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph of the sample after sintering in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the sample after copper facing in the embodiment of the present invention 1；
Fig. 3 be inkjet printing in the embodiment of the present invention 2 after sample scanning electron microscope (SEM) photograph；
Fig. 4 is the scanning electron microscope (SEM) photograph of the sample after copper facing in the embodiment of the present invention 2.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of preparation method of the flexible PCB based on inkjet technology, and it includes as follows
Step：
S01：Activated inks containing silver salt are provided；
S02：The activated inks of silver salt are contained described in inkjet printing on matrix；
S03：Sample after described step S02 is printed is sintered；
S04：Chemical bronze plating liquid is provided, the sample after step S03 sintering is carried out electroless copper.
In described step S01, the described activated inks containing silver salt, at least include following component：Water, water soluble silver salt,
Wetting agent and organic reducing agent.Described water soluble silver salt is silver nitrate, silver perchlorate, at least one in Argentous fluoride it is preferable that
Described water soluble silver salt is silver nitrate.Described wetting agent is alkylphenol polyoxyethylene（OP-10）, fatty alcohol-polyoxyethylene ether,
At least one in polyoxyethylene carboxylate, polyol fatty acid ester, sucrose fatty acid ester, fatty alcohol amine, alkyl polyglucoside, excellent
Elect OP-10 as.Described organic reducing agent is formaldehyde, acetaldehyde, citric acid, tyrosine, glucose, at least one in aniline, excellent
Elect formaldehyde and/or citric acid as.In described step S01, water soluble silver salt in the described activated inks containing silver salt, wetting agent,
The mass ratio of organic reducing agent is 1：（0.17～0.53）：（0.22～1.6）；The described activated inks containing silver salt are when 25 DEG C
Viscosity controls in 1.22～1.55 centipoises.
In described step S02, described matrix is preferably polyimide matrix, and polyimide matrix needs to carry out surface cleaning
Process, specifically, the NaOH aqueous solution soaking being first 0.5～5M with concentration 3～20 minutes, it is washed with deionized, Ran Houyong
The aqueous solution of nitric acid of 0.1～2M soaks 1～10 minute, and deionized water is cleaned；Finally rinsed with dehydrated alcohol again, be dried.
Specifically, in step S03, sintering temperature is 250～350 DEG C it is preferable that sintering temperature is 300 DEG C；Sintering time
20～40 minutes.
In described step S04, electroless copper plating solution at least contains following component：Mantoquita, chelating agent, organic reducing agent and
PH adjusting agent.Described mantoquita preferably sulfuric acid copper（CuSO4）Or copper sulphate pentahydrate（CuSO4·5H2O）；The preferred second two of described chelating agent
Amine tetraacethyl disodium（EDTA-2Na）, the preferred formalin of described organic reducing agent；Described pH adjusting agent preferably ten water four boron
Sour sodium（Na2B4O7·10H2O）And sodium hydroxide（NaOH）.The preferred formula of electroless copper plating solution is：Every liter of plating solution contains five water sulfur
Sour copper（CuSO4·5H2O）5g, sodium tetraborate decahydrate（Na2B4O7·10H2O）10g, disodiumedetate（EDTA-2Na）
10g, formaldehyde（HCHO）20mL, Yu Weishui.Chemical-copper-plating process is：With 5M NaOH aqueous solution, the pH value of plating solution is adjusted to 10～
14, it is warming up to 55～70 DEG C and carries out electroless copper, during electroless copper, Deca 37wt% formalin makees organic reducing agent, simultaneously
Deca 5M NaOH aqueous solution, to keep bath pH value stable, 10～50 minutes electroless copper time.
To illustrate the preparation side of the above-mentioned flexible PCB based on inkjet technology below by way of specific embodiment
Method.
Embodiment one：
S11：Activated inks containing silver salt are provided：Select silver nitrate as water soluble silver salt, citric acid as organic reducing agent,
OP-10, as wetting agent, first prepares 0.5M AgNO3Aqueous solution, 0.1M aqueous citric acid solution and 15wt%OP-10 aqueous solution, so
Press 1 afterwards：1：1 volume ratio mixing, obtains final product activated inks, and recording viscosity is 1.33 centipoises.
S12：The activated inks of silver salt are contained described in inkjet printing on matrix：Area is first taken to be 210 × 297mm（A4 paper is big
Little）, the thick polyimide film for 70mm, as stock, the NaOH aqueous solution soaking being 3M with concentration 10 minutes, uses deionization
Water washing, then 1M aqueous solution of nitric acid soak 3 minutes, after being washed with deionized, then with dehydrated alcohol rinse, drying treat
With；Activated inks are injected in the print cartridge of HP Deskjet1000 type ink-jet printer, and polyimide film loading ink-jet is beaten
In the paper feed mechanism of print machine.By computer, the CAD designing wiring map file is exported to printing of inkjet printer.
S13：Sample after described step S12 is printed is sintered：After polyimide film after inkjet printing is done, put
In clean enamel pallet, it is placed in 350 DEG C of sintering furnace and is incubated 30 minutes, so that silver salt is decomposed, be reduced to argent
Grain.Electron micrograph, Argent grain is securely attached on stock polyimide film matrix, as shown in Figure 1.
S14：Electroless copper plating solution is provided：Weigh 50g CuSO4·5H2O, 100g Na2B4O7·10H2O, 100g EDTA-
2Na, 2L37wt%HCHO aqueous solution is put in glass container, plus a small amount of deionized water dissolving, is configured to solution, then plus deionization
Water is settled to 10L, Deca 5M NaOH aqueous solution regulation pH value to 12；Polyimide film after step S13 sintering is immersed in
In described electroless copper plating solution, it is warming up to 60 DEG C, electroless copper 40 minutes.The PCB of described design is obtained final product after taking-up.Electron microscopic
Spectroscopy, after electroless copper, copper coating uniform ground, as shown in Figure 2.
The resistivity that four probe method records copper conductive traces in gained PCB is 2.14 × 10-7Ω·m.Copper wire and polyamides
The adhesive force of imine matrix is assessed as 1 grade by the regulation of GB GB/T9286-1998.
Embodiment two：
S21：Activated inks containing silver salt are provided：Select silver nitrate as water soluble silver salt, citric acid as organic reducing agent,
OP-10, as wetting agent, first prepares 0.5M AgNO3Aqueous solution, 0.5M formalin and 15wt%OP-10 aqueous solution, then
By 1：1：2 volume ratio mixing, obtains final product activated inks, and recording viscosity is 1.45 centipoises.
S22：The activated inks of silver salt are contained described in inkjet printing on matrix：Area is taken to be 210 × 297mm（A4 paper is big
Little）, the thick polyimide film for 70mm, as stock, the NaOH aqueous solution soaking being 3M with concentration 10 minutes, uses deionization
Water washing, then 1M aqueous solution of nitric acid soak 3 minutes, after being washed with deionized, then with dehydrated alcohol rinse, drying treat
With.Activated inks are injected in the print cartridge of HP Deskjet1000 type ink-jet printer, and polyimide film loading ink-jet is beaten
In the paper feed mechanism of print machine.By computer, the CAD designing wiring map file is exported to printing of inkjet printer.Electron microscopic
Spectroscopy, Argent grain is tiny, uniform, is securely attached on stock polyimide film matrix, as shown in Figure 3.
S23：Sample after described step S22 is printed is sintered：After polyimide film after inkjet printing is done, put
In clean enamel pallet, it is placed in 300 DEG C of sintering furnace and is incubated 30 minutes, so that silver salt is decomposed, be reduced to nano metal
Silver.
S24：Electroless copper plating solution is provided：Weigh 50g CuSO4·5H2O, 100g Na2B4O7·10H2O, 100g EDTA-
2Na, 2L37wt%HCHO aqueous solution is put in glass container, plus a small amount of deionized water dissolving, is configured to solution, then plus deionization
Water is settled to 10L, Deca 5M NaOH aqueous solution regulation pH value to 10.Polyimide film after step S23 sintering is immersed in
In the plating solution of electroless copper, it is warming up to 55 DEG C, electroless copper 50 minutes.The PCB of described design is obtained final product after taking-up.Ultramicroscope
Check, after electroless copper, copper coating uniform ground, as shown in Figure 4.
The resistivity that four probe method records copper conductive traces in gained PCB is 8.53 × 10-7Ω·m.Copper wire and polyamides
The adhesive force of imine matrix is assessed as 1 grade by the regulation of GB GB/T9286-1998.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of the flexible PCB based on inkjet technology is it is characterised in that comprise the steps：
Activated inks containing silver salt are provided；
The activated inks of silver salt are contained described in inkjet printing on matrix；
Matrix after described inkjet printing is sintered, obtains sintered product；
Chemical bronze plating liquid is provided, electroless copper is carried out to described sintered product；Solid Free thing in described activated inks；
The described activated inks containing silver salt at least include water, water soluble silver salt, wetting agent and organic reducing agent；
Described water soluble silver salt is silver perchlorate, at least one in Argentous fluoride, or：In silver perchlorate, Argentous fluoride at least one
Plant and silver nitrate；
Described organic reducing agent is at least one in formaldehyde, acetaldehyde, citric acid, tyrosine, glucose and aniline；
Described wetting agent is alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, polyol fat
At least one in acid esters, sucrose fatty acid ester, fatty alcohol amine and alkyl polyglucoside；Water solublity in the described activated inks containing silver salt
Silver salt, wetting agent, the mass ratio of organic reducing agent are 1：(0.17～0.53)：(0.22～1.6).
2. the preparation method of the flexible PCB based on inkjet technology as claimed in claim 1 is it is characterised in that described
The viscosity when 25 DEG C for the activated inks containing silver salt controls in 1.22～1.55 centipoises.
3. the preparation method of the flexible PCB based on inkjet technology as claimed in claim 1 is it is characterised in that described
Matrix is polyimide matrix, using front carrying out cleaning treatment.
4. the preparation method of the flexible PCB based on inkjet technology as claimed in claim 1 is it is characterised in that described
The temperature of sintering is 250～350 DEG C, 20～40 minutes time of sintering.
5. the preparation method of the flexible PCB based on inkjet technology as claimed in claim 1 is it is characterised in that described
Electroless copper plating solution contains mantoquita, chelating agent, organic reducing agent and pH adjusting agent.
6. the preparation method of the flexible PCB based on inkjet technology as claimed in claim 1 is it is characterised in that described
The technique of electroless copper is：With 5M NaOH aqueous solution, the pH value of plating solution is adjusted to 10～14, is warming up to 55～70 DEG C and carries out chemistry
Copper facing, during electroless copper, Deca formalin makees organic reducing agent, 10～50 minutes electroless copper time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105489265B (en) * | 2015-12-03 | 2017-03-22 | 佛山市首诺新能源材料有限公司 | Ink-jet printing transparent nano silver conductive solution for conducting circuit and preparation method and construction method of ink-jet printing transparent nano silver conductive solution |
| CN105436515B (en) * | 2015-12-03 | 2017-09-29 | 佛山市首诺新能源材料有限公司 | A kind of preparation method of ultrafine electricity conductive circuit Nano silver solution |
| CN106455303B (en) * | 2016-11-15 | 2019-02-05 | 中国科学院力学研究所 | A kind of extendable inkjet printing flexible circuit board 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 |
| CN108441844B (en) * | 2018-04-03 | 2020-11-17 | 广东东硕科技有限公司 | Activating solution for electroless plating of non-conductive substrate and preparation method thereof |
| CN110876255A (en) * | 2018-08-31 | 2020-03-10 | 德州迈特新材料研究中心 | Preparation technology of microwave band metamaterial wave absorber |
| CN112351594B (en) * | 2020-10-13 | 2023-02-07 | 厦门大学 | Combined method for preparing flexible circuit on surface of biological material |
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| CN101591488A (en) * | 2008-05-26 | 2009-12-02 | 富葵精密组件(深圳)有限公司 | Printing ink and utilize the method for this printing ink to manufacture electric conduction line |
| CN101754585A (en) * | 2008-11-27 | 2010-06-23 | 富葵精密组件(深圳)有限公司 | Method for manufacturing conductive circuit |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100649445B1 (en) * | 2005-10-17 | 2006-11-27 | 삼성전기주식회사 | Wiring forming method and device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591488A (en) * | 2008-05-26 | 2009-12-02 | 富葵精密组件(深圳)有限公司 | Printing ink and utilize the method for this printing ink to manufacture electric conduction line |
| CN101754585A (en) * | 2008-11-27 | 2010-06-23 | 富葵精密组件(深圳)有限公司 | Method for manufacturing conductive circuit |
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