CN102883543B - A kind of method adopting additive process to prepare conducting wire - Google Patents
A kind of method adopting additive process to prepare conducting wire Download PDFInfo
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- CN102883543B CN102883543B CN201210375899.6A CN201210375899A CN102883543B CN 102883543 B CN102883543 B CN 102883543B CN 201210375899 A CN201210375899 A CN 201210375899A CN 102883543 B CN102883543 B CN 102883543B
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Abstract
The invention belongs to printed circuit board preparation field, be specially a kind of method adopting additive process to prepare conducting wire.Concrete steps are: adopt epoxy resin, mylar as film forming phase matrix resin; interpolation filler, solvent prepare film forming phase with auxiliary agent; silk screen printing, intaglio printing, ink jet printing mode is adopted to print out line pattern; the mode of hot curing is adopted to be heating and curing; then circuit is immersed in the solution containing palladium, platinum, gold, silver, copper, cobalt, nickel, iron nano-particle or ion; by the deionized water washing excessive nano particle of removing or metal ion; insert in chemical plating fluid and carry out chemical plating, thus reach the object of wired foil.The present invention compared to conventional printed circuit-line preparation method have step simple, save material, cost reduces advantage, has that cost reduces, electrical property is excellent, to the strong advantage of substrate adhesion compared to employing Nano Silver ink or silver conductive adhesive conductive circuit.
Description
Technical field
The invention belongs to printed electronics field, be specially a kind of method adopting additive process to prepare conducting wire.
Background technology
In conventional print-circuit board, trace manufacturing processes uses to subtract into etching method etch line pattern in copper-clad plate, and it exists, and material consumption is high, production process is many, discharging of waste liquid is large, the environmental protection pressure shortcomings such as heavily.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, 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 manufacture technics conducting wire, use ink-jet, silk screen printing Nano Silver ink or conductive silver paste now more.Use silver to have conductance as conductive unit high, the advantages such as stable in properties, but the high price of silver also limit the large-scale application of printed electronics technique.Replacing silver with copper can workout cost problem, but the metallic copper of subparticle is very easily oxidized by the air, and it is not very desirable for causing being nano-copper ink or the conductivity of conductive copper paste.
Electroless plating technology is under the catalytic action of metal, by the metallic deposition process of controllable redox reaction.Chemical plating commonly uses solution: chemical silvering, nickel plating, copper facing, cobalt plating, nickel plating phosphorus liquid, nickel plating phosphorus boron liquid etc.Electroless copper, chemical nickel plating and chemical nickel phosphorus plating will be used in printed wiring metallization.Palladium, platinum, gold, silver, copper, cobalt, nickel, iron etc. are the metals with catalytic action, and for the film such as polyimides, PETG, realize chemical plating needs first to form catalytic metal center on its surface, is also called activated centre.Use the mode of chemical plating to manufacture the circuit of printed circuit board, active centre must be able to optionally be formed.
The present invention has used printed electronics technique, by the mode of printing, film forming agent is optionally printed on resin substrate, immerse after solidification in catalytic metal ion solution or nanometer particle colloid, adsorbent in film forming agent can adsorbing metal ions or metal nanoparticle, thus form activated centre from the teeth outwards, then make wired foil by the mode of chemical plating.
Summary of the invention
The object of the present invention is to provide a kind of method adopting additive process to prepare conducting wire, the present invention uses the mode of printing active centre to be optionally formed in the surface of resin matrix, thus carries out electroless metallization plating.Use this technique to prepare conducting wire and there is the features such as technique is simple, with low cost, green high-efficient, low resistance circuit can be obtained, meet the instructions for use of printed circuit board.Principle of the present invention is that silane coupler in film forming agent is as adsorbent, its sulfydryl, amino, epoxy radicals, carbonyl can as adsorption group and catalytic metal simple substance or the ion mode bondings by complexing, catalytic metal adhered to film forming agent surface thus forms activated centre catalytic chemistry to plate and carry out.Owing to can produce a large amount of hydrogen on activated centre in the process of electroless copper, chemical nickel plating, chemical nickel phosphorus plating, if activated centre is positioned at film forming agent inside, the hydrogen of generation will affect integrality and the adhesiveness of film greatly.So activated centre is adsorbed on film forming agent surface by the present invention, the hydrogen produced in plating process can not affect the complete of film, so can high temeperature chemistry plate for a long time, thus obtain the circuit of more high conductivity.
A kind of method adopting additive process to prepare conducting wire that the present invention proposes, concrete steps are as follows:
(1) by the thickener of the solvent of the filler of the resin of 0 ~ 0.9 mass parts, 0 ~ 0.7 mass parts, 0.3 ~ 0.6 mass parts, the silane coupler of 0.01 ~ 0.7 mass parts and 0 ~ 0.05 mass parts with 500 turns/more than min mix and blend 15 ~ 24 hours, obtain film forming agent;
(2) film forming agent that step (1) obtains is printed as on substrate the line pattern of design, obtains circuit base plate;
(3) circuit base plate step (2) obtained is heating, drying solidification under 60oC ~ 120oC, and curing time is 5min ~ 120min;
(4) circuit base plate that step (3) is solidified is placed in catalyst solution or the colloid 1h of 0.1mol/L;
(5) circuit base plate after step (4) being immersed catalyst is inserted in deionized water, washes away excessive catalyst;
(6) circuit base plate after step (5) being cleaned is dried, removing deionized water;
(7) circuit base plate after step (6) being dried is placed in chemical plating bath and carries out chemical plating 5min ~ 120min;
(8) circuit base plate after step (7) chemical plating is carried out reprocessing, obtain required conducting wire.
In the present invention, in step (1) use resin for the mixing of one or several in epoxy resin or mylar.
In the present invention, the filler used in step (1) is powdered whiting, the mixing of one or more in carbon black, white carbon or titanium dioxide.
In the present invention, the solvent used in step (1) is the mixing of one or more in water, alcohols solvent, ketones solvent, lipid solvent or ether solvent; 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, 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.
In the present invention, the silane coupler used in step (1) comprises methyltrimethoxy silane, phenyltrimethoxysila,e, butyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, 3-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, diethylenetriamine base propyl trimethoxy silicane, N-aminoethyl-γ-aminopropyltrimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, 3-aminopropyl triethoxysilane, phenyl triethoxysilane, urea propyl-triethoxysilicane, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, N-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, the mixing of one or more in dimethyldiethoxysilane or 3-aminopropyltriethoxy diethoxy silane.
In the present invention, the thickener used in step (1) comprises the mixing of one or more in aerosil, organobentonite, diatomite, CMC, polyacrylamide, polyvinylpyrrolidone or Sodium Polyacrylate.
In the present invention, the mode of printing adopted in step (2) comprises silk screen printing, intaglio printing or ink jet printing.
In the present invention, the substrate used in step (2) comprises any one in polyimides, polyether-ether-ketone, polyphenylene oxide, polypropylene, PETG, fiber reinforced epoxy resin, polytetrafluoroethylene or paper.
In the present invention, the catalyst used in step (4) is palladium, platinum, gold, silver, copper, cobalt, nickel, iron nano-particle colloid, or the aqueous solution containing palladium, platinum, gold, silver, copper, cobalt, nickel, iron ion.
In the present invention, the chemical plating fluid used in step (7) 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.
Beneficial effect of the present invention:
1, the mode that the present invention uses addition to print prepares printed circuit board wire line, has saved material, has simplified step, decreased environmental pollution.
2, the line resistance that obtains of the present invention is low, can meet the requirement of printed circuit board circuit completely.
3, the circuit that obtains of the present invention is to polyimides, polyether-ether-ketone, polyphenylene oxide, polypropylene, PETG, fiber reinforced epoxy resin, polytetrafluoroethylene, paper base plate good adhesion.
4, the present invention produces equipment needed thereby and existing PCB Hole Metallization unit affinity, decreases the expense of equipment improvement.
5, production efficiency of the present invention is high, with short production cycle, is beneficial to the production realizing printed circuit " volume to volume ".
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1:
(1) 10g polyurethane resin is got, add 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 and be greater than 6000 centipoises, prepared by film forming agent;
(2) take polyimides as substrate, soak 10min with 1mol/L sodium hydroxide solution before substrate uses, then use washed with de-ionized water;
(3) 500 object silk screen film forming agents are adopted to print out circuitous pattern on substrate;
(4) to the circuit produced heat treatment 1 hour under 80oC;
(5) process after substrate immerse 0.1mol/L palladium chloride solution in 1 hour;
(6) unnecessary catalyst is fallen by deionized water soaking and washing;
(7) dry 10 minutes under 50oC;
(8) configure chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed in chemical bronze plating liquid carry out electroless copper 30min at normal temperatures;
(10) copper facing terminate after by circuit board washed with de-ionized water, dry, obtain metallic copper conducting wire.
Measuring sheet resistance with four point probe instrument is 0.03 Ω.Adhesion is 4B(ASTMD3359).
Embodiment 2:
(1) 5g diethylenetriamine base propyl trimethoxy silicane is got, 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 and be less than 100 centipoises, prepared by film forming agent;
(2) take PETG as substrate, soak 10min with 1mol/L sodium hydroxide solution before substrate uses, then use washed with de-ionized water;
(3) 50um shower nozzle ink-jet printer is adopted to print out circuitous pattern;
(4) to the circuit produced heat treatment 1 hour under 70oC;
(5) process after substrate immerse 0.1mol/L liquor argenti nitratis ophthalmicus in 1 hour;
(6) unnecessary catalyst is fallen by deionized water soaking and washing;
(7) dry 10 minutes under 50oC;
(8) configure chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed in chemical bronze plating liquid carry out electroless copper 30min at normal temperatures;
(10) copper facing terminate after by circuit board washed with de-ionized water, dry, obtain metallic copper conducting wire.
Measuring sheet resistance with four point probe instrument is 0.08 Ω.Adhesion is 5B(ASTMD3359).
Embodiment 3:
(1) 5g3-aminopropyl trimethoxysilane is got, 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 and be less than 100 centipoises, prepared by film forming agent;
(2) take PETG as substrate, soak 10min with 1mol/L sodium hydroxide solution before substrate uses, then use washed with de-ionized water;
(3) 50um shower nozzle ink-jet printer is adopted to print out circuitous pattern;
(4) to the circuit produced heat treatment 1 hour under 70oC;
(5) process after substrate immerse 0.1mol/L liquor argenti nitratis ophthalmicus in 1 hour;
(6) unnecessary catalyst is fallen by deionized water soaking and washing;
(7) dry 10 minutes under 50oC;
(8) configure chemical bronze plating liquid, fill a prescription as follows:
(9) substrate is immersed in chemical bronze plating liquid carry out electroless copper 30min at normal temperatures;
(10) copper facing terminate after by circuit board washed with de-ionized water, dry, obtain metallic copper conducting wire.
Measuring sheet resistance with four point probe instrument is 0.02 Ω.Adhesion is 5B(ASTMD3359).
Claims (9)
1. adopt additive process to prepare a method for conducting wire, it is characterized in that concrete steps are as follows:
(1), by the thickener of the solvent of the filler of the resin of 0 ~ 0.9 mass parts, 0 ~ 0.7 mass parts, 0.3 ~ 0.6 mass parts, the silane coupler of 0.01 ~ 0.7 mass parts and 0 ~ 0.05 mass parts with 500 turns/more than min mix and blend 15 ~ 24 hours, film forming agent is obtained;
(2), the film forming agent that step (1) obtains is printed as on substrate the line pattern of design, obtains circuit base plate; Substrate is any one in polyimides, polyether-ether-ketone, polyphenylene oxide, polychloroprene, PETG, fiber reinforced epoxy resin or polytetrafluoroethylene;
(3) circuit base plate, by step (2) obtained is heating, drying solidification under 60oC ~ 120oC, and curing time is 5min ~ 120min;
(4), the circuit base plate that step (3) is solidified is placed in catalyst solution or the colloid 1h of 0.1mol/L;
(5), the circuit base plate after step (4) immersion catalyst is inserted in deionized water, wash away excessive catalyst;
(6), by the circuit base plate after step (5) cleaning dry, removing deionized water;
(7) circuit base plate after, step (6) being dried is placed in chemical plating bath and carries out chemical plating 5min ~ 120min;
(8), by the circuit base plate after step (7) chemical plating carry out reprocessing, obtain required conducting wire.
2. method according to claim 1, is characterized in that: in step (1) use resin for the mixing of one or several in epoxy resin or mylar.
3. method according to claim 1, is characterized in that: the filler used in step (1) is powdered whiting, the mixing of one or more in carbon black, white carbon or titanium dioxide.
4. method according to claim 1, is characterized in that: the solvent used in step (1) is the mixing of one or more in water, alcohols solvent, ketones solvent, lipid solvent or ether solvent.
5. method according to claim 1, it is characterized in that: the silane coupler used in step (1) is methyltrimethoxy silane, phenyltrimethoxysila,e, butyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, 3-aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, diethylenetriamine base propyl trimethoxy silicane, N-aminoethyl-γ-aminopropyltrimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, 3-aminopropyl triethoxysilane, phenyl triethoxysilane, urea propyl-triethoxysilicane, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, N-aminoethyl-3-aminopropyltriethoxy dimethoxysilane, the mixing of one or more in dimethyldiethoxysilane or 3-aminopropyltriethoxy diethoxy silane.
6. method according to claim 1, is characterized in that: the thickener used in step (1) is aerosil, the mixing of one or more in organobentonite, diatomite, CMC, polyacrylamide, polyvinylpyrrolidone or Sodium Polyacrylate.
7. method according to claim 1, is characterized in that: the mode of printing adopted in step (2) is any one in silk screen printing, intaglio printing or ink jet printing.
8. method according to claim 1, it is characterized in that: the catalyst used in step (4) is palladium, platinum, gold, silver, copper, cobalt, nickel, iron nano-particle colloid, or the aqueous solution containing palladium, platinum, gold, silver, copper, cobalt, nickel, iron ion.
9. method according to claim 1, is characterized in that: the chemical plating fluid used in step (7) 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.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103249255B (en) * | 2013-04-17 | 2016-01-20 | 复旦大学 | A kind of method directly preparing conducting wire on resin substrate |
| 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 |
| KR102560882B1 (en) * | 2017-04-28 | 2023-07-31 | 주식회사 다이셀 | Solvent composition for electronic device manufacturing |
| CN108866516B (en) * | 2018-08-27 | 2020-08-04 | 合肥学院 | Method for preparing selective electroless plating polymer base material by 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 |
| CN113118234B (en) * | 2021-04-16 | 2022-09-27 | 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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| CN1630458A (en) * | 2003-12-19 | 2005-06-22 | 财团法人工业技术研究院 | Method for forming plain conductor pattern by means of ink-jet |
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| JP4837703B2 (en) * | 2007-05-10 | 2011-12-14 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Wiring formation method for printed circuit board |
| JP5060250B2 (en) * | 2007-11-13 | 2012-10-31 | セーレン株式会社 | Method for forming conductive thin wire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1630458A (en) * | 2003-12-19 | 2005-06-22 | 财团法人工业技术研究院 | Method for forming plain conductor pattern by means of ink-jet |
| CN102199763A (en) * | 2011-04-01 | 2011-09-28 | 广东工业大学 | Preparation method for electroless plating activator capable of screen printing, and activating treatment process using same |
| CN102300414A (en) * | 2011-08-22 | 2011-12-28 | 电子科技大学 | Addition preparation method of printed circuit |
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