CN102883543A - Method for manufacturing conducting circuit by additive process - Google Patents
Method for manufacturing conducting circuit by additive process Download PDFInfo
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- CN102883543A CN102883543A CN2012103758996A CN201210375899A CN102883543A CN 102883543 A CN102883543 A CN 102883543A CN 2012103758996 A CN2012103758996 A CN 2012103758996A CN 201210375899 A CN201210375899 A CN 201210375899A CN 102883543 A CN102883543 A CN 102883543A
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Abstract
The invention belongs to the field of manufacture of printed circuit boards, and particularly discloses a method for manufacturing a conducting circuit by an additive process. The method particularly includes steps of adding fillers, solvents and auxiliaries in epoxy resin and polyester resin which are used as film-forming phase matrix resin to prepare a film-forming phase; printing a graph of a circuit in screen printing, intaglio printing and inkjet printing modes; heating and curing in a heat curing mode; then soaking the circuit in solution containing palladium, platinum, gold, silver, copper, cobalt, nickel and iron nanoparticles or ions; washing the circuit by deionized water to remove excess nanoparticles or metal ions; and placing the circuit in chemical plating solution to perform chemical plating for the circuit so as to achieve the purpose of metallizing the circuit. Compared with the traditional method for manufacturing a printed circuit board, the method has the advantages that the steps are simple, materials are saved, and cost is lowered. Besides, compared with a conducting circuit printed by nano-silver printing ink or silver conductive adhesive, the conducting circuit manufactured by the method has the characteristics that cost is lowered, the electric performance is excellent, and adhesive force to a substrate is high.
Description
Technical field
The invention belongs to the printed electronics field, be specially a kind of method that adopts additive process to prepare the conducting wire.
Background technology
The circuit manufacturing process is to use to subtract into etching method and etch line pattern in copper-clad plate in the traditional printing circuit board, and it exists, and material consumption is high, production process is many, discharging of waste liquid is large, environmental protection pressure heavily waits shortcomings.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 production process few, production cost is low, environmental friendliness, flexible design, the advantages such as functional diversities have broad application prospects.
Use printed electronics technique to make the conducting wire, many uses is ink-jet, silk screen printing Nano Silver printing ink or conductive silver paste now.Use silver to have conductance as conductive unit high, the advantages such as stable in properties, but the high price of silver has also limited the large-scale application of printed electronics technique.Replacing silver with copper can the workout cost problem, but the metallic copper of subparticle is very easily oxidized by the air, and causing is that nano-copper ink or the conductivity of conductive copper paste are not very desirable.
Electroless plating technology is under the catalytic action of metal, by the metallic deposition process of controllable redox reaction.Chemical plating is commonly used solution: chemical silvering, nickel plating, copper facing, cobalt plating, nickel plating phosphorus liquid, nickel plating phosphorus boron liquid etc.In the printed wiring metallization, will use electroless copper, chemical nickel plating and chemical nickel phosphorus plating.Palladium, platinum, gold, silver, copper, cobalt, nickel, iron etc. are the metals with catalytic action, for films such as polyimides, PETGs, realize that chemical plating needs to form the catalytic metal center on its surface first, are called again the activated centre.Use the mode of chemical plating to make the circuit of printed circuit board, active centre must be able to optionally form.
The present invention has used printed electronics technique, mode by printing optionally is printed on film forming agent on the resin substrate, immerse in catalytic metal ion solution or the nanometer particle colloid after solidifying, adsorbent in the film forming agent can adsorbing metal ions or metal nanoparticle, thereby form from the teeth outwards the activated centre, the mode by chemical plating makes the circuit metallization again.
Summary of the invention
The object of the present invention is to provide the volunteer to adopt additive process to prepare the method for conducting wire, the present invention uses the mode of printing active centre optionally to be formed on the surface of resin matrix, thereby carries out chemical plating metal.Use this technique to prepare the conducting wire and have the characteristics such as technique is simple, with low cost, green high-efficient, can obtain the low resistance circuit, satisfy the instructions for use of printed circuit board.Principle of the present invention is that silane coupler in the film forming agent is as adsorbent, its sulfydryl, amino, epoxy radicals, carbonyl can be used as adsorption group and catalytic metal simple substance or ion by the mode bonding of complexing, carry out thereby catalytic metal is adhered to the catalytic chemistry plating of formation activated centre, film forming agent surface.Because can produce a large amount of hydrogen in the activated centre in the process of electroless copper, chemical nickel plating, chemical nickel phosphorus plating, if the activated centre is positioned at film forming agent inside, the hydrogen of generation will affect membrane integrity and adhesiveness greatly.So the present invention is adsorbed on the film forming agent surface with the activated centre, the hydrogen that produces in the chemical plating process will can not affect the complete of film, thus for a long time high temeperature chemistry plating, thus obtain the more circuit of high conductivity.
A kind of method that adopts additive process to prepare the conducting wire that the present invention proposes, concrete steps are as follows:
(1) with the thickener of 0 ~ 0.9 resin, 0 ~ 0.7 filler, 0.3 ~ 0.6 solvent, 0.01 ~ 0.7 silane coupler and 0 ~ 0.05 500 to turn/the above mix and blend of min 15 ~ 24 hours, obtain film forming agent;
(2) film forming agent that step (1) is obtained is printed as the line pattern of design at substrate, obtain circuit base plate;
(3) circuit base plate that step (2) is obtained heating, drying under 60oC ~ 120oC solidifies, and be 5min ~ 120min curing time;
(4) circuit base plate that step (3) is solidified places catalyst solution or the colloid 1h of 0.1mol/L;
(5) circuit base plate behind step (4) the immersion catalyst is inserted in the deionized water catalyst that flush away is excessive;
(6) with the circuit base plate oven dry after step (5) cleaning, remove deionized water;
(7) place chemical plating bath to carry out chemical plating 5min ~ 120min the circuit base plate after step (6) oven dry;
(8) circuit base plate after step (7) chemical plating is carried out reprocessing, namely get required conducting wire.
Among the present invention, in the step (1) the resin that uses be one or several the mixing in epoxy resin or the mylar.
Among the present invention, employed filler is one or more the mixing in powdered whiting, carbon black, white carbon or the titanium dioxide in the step (1).
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); Alcohols solvent comprises methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, n-hexyl alcohol, ethylene glycol, diglycol or terpinol, ketones solvent comprises acetone, butanone, acetylacetone,2,4-pentanedione, cyclohexanone, methyl iso-butyl ketone (MIBK) or isophorone, the lipid solvent comprises methyl acetate, ethyl acetate, butyl acetate or dibasic ester, and ether solvent comprises ether, oxolane, isopropyl ether, EGME, butyl glycol ether or glycol dimethyl ether.
Among the present invention, employed silane coupler comprises methyltrimethoxy silane in the step (1), phenyltrimethoxysila,e, butyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, the 3-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, diethylenetriamine base propyl trimethoxy silicane, N-aminoethyl-γ-aminopropyltrimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, the 3-aminopropyl triethoxysilane, phenyl triethoxysilane, the urea propyl-triethoxysilicane, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, N-aminoethyl-3-aminopropyl methyl dimethoxysilane, the mixing of one or more in dimethyldiethoxysilane or the 3-aminopropyl methyldiethoxysilane.
Among the present invention, employed thickener comprises one or more the mixing in aerosil, organobentonite, diatomite, CMC, polyacrylamide, polyvinylpyrrolidone or the Sodium Polyacrylate in the step (1).
Among the present invention, the mode of printing that adopts in the step (2) comprises silk screen printing, intaglio printing or ink jet printing.
Among the present invention, employed substrate comprises in polyimides, polyether-ether-ketone, polyphenylene oxide, polypropylene, PETG, fiber reinforced epoxy resin, polytetrafluoroethylene or the paper any in the step (2).
Among the present invention, employed catalyst is palladium, platinum, gold, silver, copper, cobalt, nickel, iron nano-particle colloid in the step (4), or contains the aqueous solution of palladium, platinum, gold, silver, copper, cobalt, nickel, iron ion.
Among the present invention, employed chemical plating fluid is chemical bronze plating liquid, chemical nickel-plating liquid, chemical nickel phosphorus plating liquid, chemical plating liquid, chemical gold plating liquid or chemical tin plating liquor in the step (7).
Beneficial effect of the present invention:
1, the present invention uses the mode of addition printing to prepare the printed circuit board wire line, has saved material, has simplified step, has reduced environmental pollution.
2, the line resistance that obtains of the present invention is low, can satisfy the requirement of printed circuit board circuit fully.
3, the circuit that obtains of the present invention is good to polyimides, polyether-ether-ketone, polyphenylene oxide, polypropylene, PETG, fiber reinforced epoxy resin, polytetrafluoroethylene, paper base plate adhesion.
4, the present invention produces equipment needed thereby and existing PCB Hole Metallization unit affinity, has reduced the expense of equipment improvement.
5, production efficiency of the present invention is high, and is with short production cycle, is beneficial to the production that realizes printed circuit " volume to volume ".
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(1) gets the 10g polyurethane resin, add the 5g nano-calcium carbonate, 0.5g γ-mercaptopropyl trimethoxysilane, 0.6g methyltrimethoxy silane, 0.3g γ-glycidyl ether oxygen propyl trimethoxy silicane, 10g mixed solvent (water 0.5g, methyl alcohol 0.2g, ethanol 0.3g, acetylacetone,2,4-pentanedione 0.1g, acetone 0.1g, butyl acetate 7.5g, EGME 0.5g, butyl glycol ether 0.8g), 0.1g polyvinylpyrrolidone mix and blend 500 turns/min24 hour, measure viscosity greater than 6000 centipoises, and the film forming agent preparation is finished;
(2) take polyimides as substrate, before using, substrate soaks 10min with the 1mol/L sodium hydroxide solution, use again washed with de-ionized water;
(3) adopt 500 purpose silk screens to print out circuitous pattern with film forming agent at substrate;
(4) to the heat treatment 1 hour under 80oC of the circuit that produces;
(5) substrate after processing immersed in the palladium chloride solution of 0.1mol/L 1 hour;
(6) fall unnecessary catalyst with the deionized water soaking and washing;
(7) under 50oC, dried 10 minutes;
(8) configuration chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed carry out at normal temperatures electroless copper 30min in the chemical bronze plating liquid;
(10) with the circuit board washed with de-ionized water, oven dry obtained the metallic copper conducting wire after copper facing finished.
Measuring sheet resistance with the four point probe instrument is 0.03 Ω.Adhesion is 4B(ASTM D3359).
Embodiment 2:
(1) gets 5g diethylenetriamine base propyl trimethoxy silicane, the 5g methyltrimethoxy silane, 15g mixed solvent (water 3g, methyl alcohol 2g, ethanol 1g, acetylacetone,2,4-pentanedione 1g, EGME 1g, butyl glycol ether 2g isopropyl alcohol 3.5g, acetone 1.5g), mix and blend 500 turns/min24 hour, measure viscosity less than 100 centipoises, and the film forming agent preparation is finished;
(2) take PETG as substrate, before using, substrate soaks 10min with the 1mol/L sodium hydroxide solution, use again washed with de-ionized water;
(3) adopt 50um shower nozzle ink-jet printer to print out circuitous pattern;
(4) to the heat treatment 1 hour under 70oC of the circuit that produces;
(5) substrate after processing immersed in the liquor argenti nitratis ophthalmicus of 0.1mol/L 1 hour;
(6) fall unnecessary catalyst with the deionized water soaking and washing;
(7) under 50oC, dried 10 minutes;
(8) configuration chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed carry out at normal temperatures electroless copper 30min in the chemical bronze plating liquid;
(10) with the circuit board washed with de-ionized water, oven dry obtained the metallic copper conducting wire after copper facing finished.
Measuring sheet resistance with the four point probe instrument is 0.08 Ω.Adhesion is 5B(ASTM D3359).
Embodiment 3:
(1) gets the 5g3-aminopropyl trimethoxysilane, 3g dimethyldimethoxysil,ne, 2g phenyltrimethoxysila,e, 15g mixed solvent (water 3g, methyl alcohol 2g, ethanol 1g, acetylacetone,2,4-pentanedione 1g, EGME 1g, butyl glycol ether 2g isopropyl alcohol 3.5g, acetone 1.5g), mix and blend 500 turns/min24 hour, measure viscosity less than 100 centipoises, the film forming agent preparation is finished;
(2) take PETG as substrate, before using, substrate soaks 10min with the 1mol/L sodium hydroxide solution, use again washed with de-ionized water;
(3) adopt 50um shower nozzle ink-jet printer to print out circuitous pattern;
(4) to the heat treatment 1 hour under 70oC of the circuit that produces;
(5) substrate after processing immersed in the liquor argenti nitratis ophthalmicus of 0.1mol/L 1 hour;
(6) fall unnecessary catalyst with the deionized water soaking and washing;
(7) under 50oC, dried 10 minutes;
(8) configuration chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed carry out at normal temperatures electroless copper 30min in the chemical bronze plating liquid;
(10) with the circuit board washed with de-ionized water, oven dry obtained the metallic copper conducting wire after copper facing finished.
Measuring sheet resistance with the four point probe instrument is 0.02 Ω.Adhesion is 5B(ASTM D3359).
Claims (10)
1. method that adopts additive process to prepare the conducting wire is characterized in that concrete steps are as follows:
(1), the resin with 0 ~ 0.9,0 ~ 0.7 filler, 0.3 ~ 0.6 solvent, 0.01 ~ 0.7 silane coupler and 0 ~ 0.05 thickener to be 500 to turn/the above mix and blend of min 15 ~ 24 hours, obtains film forming agent;
(2), film forming agent that step (1) is obtained is printed as the line pattern of design at substrate, obtain circuit base plate;
(3), circuit base plate heating, drying under 60oC ~ 120oC that step (2) is obtained solidifies, be 5min ~ 120min curing time;
(4), the circuit base plate that step (3) is solidified places catalyst solution or the colloid 1h of 0.1mol/L;
(5), the circuit base plate behind step (4) the immersion catalyst is inserted in the deionized water catalyst that flush away is excessive;
(6), the circuit base plate oven dry after step (5) cleaned, remove deionized water;
(7), place chemical plating bath to carry out chemical plating 5min ~ 120min the circuit base plate after step (6) oven dry;
(8), the circuit base plate after step (7) chemical plating is carried out reprocessing, namely get required conducting wire.
2. method according to claim 1 is characterized in that: in the step (1) the resin that uses be one or several the mixing in epoxy resin or the mylar.
3. method according to claim 1 is characterized in that: employed filler is one or more the mixing in powdered whiting, carbon black, white carbon or the titanium dioxide in the step (1).
4. method according to claim 1 is characterized in that: employed solvent is one or more the mixing in water, alcohols solvent, ketones solvent, lipid solvent or the ether solvent in the step (1).
5. method according to claim 1, it is characterized in that: employed silane coupler is methyltrimethoxy silane in the step (1), phenyltrimethoxysila,e, butyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, the 3-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, diethylenetriamine base propyl trimethoxy silicane, N-aminoethyl-γ-aminopropyltrimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, the 3-aminopropyl triethoxysilane, phenyl triethoxysilane, the urea propyl-triethoxysilicane, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, N-aminoethyl-3-aminopropyl methyl dimethoxysilane, the mixing of one or more in dimethyldiethoxysilane or the 3-aminopropyl methyldiethoxysilane.
6. method according to claim 1 is characterized in that: employed thickener is one or more the mixing in aerosil, organobentonite, diatomite, CMC, polyacrylamide, polyvinylpyrrolidone or the Sodium Polyacrylate in the step (1).
7. method according to claim 1 is characterized in that: the mode of printing that adopts in the step (2) be in silk screen printing, intaglio printing or the ink jet printing any.
8. method according to claim 1 is characterized in that: in the step (2) employed substrate be in polyimides, polyether-ether-ketone, polyphenylene oxide, polychloroprene, PETG, fiber reinforced epoxy resin, polytetrafluoroethylene or the paper any.
9. method according to claim 1, it is characterized in that: employed catalyst is palladium, platinum, gold, silver, copper, cobalt, nickel, iron nano-particle colloid in the step (4), or contains the aqueous solution of palladium, platinum, gold, silver, copper, cobalt, nickel, iron ion.
10. method according to claim 1, it is characterized in that: employed chemical plating fluid is chemical bronze plating liquid, chemical nickel-plating liquid, chemical nickel phosphorus plating liquid, chemical plating liquid, chemical gold plating liquid or chemical tin plating liquor in the step (7).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210375899.6A CN102883543B (en) | 2012-10-08 | 2012-10-08 | A kind of method adopting additive process to prepare conducting wire |
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| CN201210375899.6A CN102883543B (en) | 2012-10-08 | 2012-10-08 | A kind of method adopting additive process to prepare conducting wire |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103249255A (en) * | 2013-04-17 | 2013-08-14 | 复旦大学 | Method for directly preparing conducting circuit on resin baseplate |
| CN104789949A (en) * | 2015-04-27 | 2015-07-22 | 电子科技大学 | Compounding method of epoxy resin solution with autocatalysis chemical copper plating activity and chemical copper plating method |
| CN108866516A (en) * | 2018-08-27 | 2018-11-23 | 合肥学院 | A method of selective chemical plating polymeric substrate is prepared using base metal |
| CN111010821A (en) * | 2019-12-31 | 2020-04-14 | 广州京写电路板有限公司 | Manufacturing method of printed circuit board meeting high-precision requirement of pad position |
| CN113118234A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
| CN113141719A (en) * | 2021-04-22 | 2021-07-20 | 江西新华盛电子电路科技有限公司 | Addition preparation method of LED double-sided board |
| CN115261832A (en) * | 2022-08-04 | 2022-11-01 | 电子科技大学 | Preparation method for surface pattern metallization of polyimide flexible substrate |
| US11655381B2 (en) * | 2017-04-28 | 2023-05-23 | Daicel Corporation | Solvent composition for electronic device production |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103249255A (en) * | 2013-04-17 | 2013-08-14 | 复旦大学 | Method for directly preparing conducting circuit on resin baseplate |
| CN103249255B (en) * | 2013-04-17 | 2016-01-20 | 复旦大学 | A kind of method directly preparing conducting wire on resin substrate |
| CN104789949A (en) * | 2015-04-27 | 2015-07-22 | 电子科技大学 | Compounding method of epoxy resin solution with autocatalysis chemical copper plating activity and chemical copper plating method |
| CN104789949B (en) * | 2015-04-27 | 2017-03-01 | 电子科技大学 | The collocation method of self-catalysis electroless copper epoxy resin solution and electroless copper plating method |
| US11655381B2 (en) * | 2017-04-28 | 2023-05-23 | Daicel Corporation | Solvent composition for electronic device production |
| CN108866516A (en) * | 2018-08-27 | 2018-11-23 | 合肥学院 | A method of selective chemical plating polymeric substrate is prepared using base metal |
| CN111010821A (en) * | 2019-12-31 | 2020-04-14 | 广州京写电路板有限公司 | Manufacturing method of printed circuit board meeting high-precision requirement of pad position |
| CN113118234A (en) * | 2021-04-16 | 2021-07-16 | 江西富鸿金属有限公司 | Production process of tinned alloy wire for medical equipment |
| CN113141719A (en) * | 2021-04-22 | 2021-07-20 | 江西新华盛电子电路科技有限公司 | Addition preparation method of LED double-sided board |
| CN115261832A (en) * | 2022-08-04 | 2022-11-01 | 电子科技大学 | Preparation method for surface pattern metallization of polyimide flexible substrate |
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