CN114189983A - Flexible conductive paste and flexible circuit board - Google Patents
Flexible conductive paste and flexible circuit board Download PDFInfo
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- CN114189983A CN114189983A CN202010966520.3A CN202010966520A CN114189983A CN 114189983 A CN114189983 A CN 114189983A CN 202010966520 A CN202010966520 A CN 202010966520A CN 114189983 A CN114189983 A CN 114189983A
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- flexible
- polymer
- conductive paste
- flexible conductive
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- 229920000642 polymer Polymers 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000011231 conductive filler Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 239000002518 antifoaming agent Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- 239000002318 adhesion promoter Substances 0.000 claims description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 238000007639 printing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 17
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 17
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 16
- 239000006087 Silane Coupling Agent Substances 0.000 description 16
- -1 xylylene isocyanate Chemical class 0.000 description 14
- 239000004642 Polyimide Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229920005749 polyurethane resin Polymers 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- JONNRYNDZVEZFH-UHFFFAOYSA-N 2-(2-butoxypropoxy)propyl acetate Chemical compound CCCCOC(C)COC(C)COC(C)=O JONNRYNDZVEZFH-UHFFFAOYSA-N 0.000 description 1
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 description 1
- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- GWQAFGZJIHVLGX-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethyl acetate Chemical compound CCCOCCOCCOC(C)=O GWQAFGZJIHVLGX-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- UFBBZQDFWTVNGP-UHFFFAOYSA-N 2-(2-propoxypropoxy)propyl acetate Chemical compound CCCOC(C)COC(C)COC(C)=O UFBBZQDFWTVNGP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- QMAQLCVJIYANPZ-UHFFFAOYSA-N 2-propoxyethyl acetate Chemical compound CCCOCCOC(C)=O QMAQLCVJIYANPZ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920005883 amine-based polyether polyol Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
The invention provides flexible conductive paste and a flexible circuit board, and relates to the technical field of functional materials. The invention provides flexible conductive paste which comprises the following components: the conductive coating comprises a first polymer, a solvent, a conductive filler, a second polymer and a curing agent, wherein the first polymer, the second polymer and the curing agent react in the heating and curing process to form a flexible three-dimensional network structure. The technical scheme of the invention can improve the flexibility of the flexible conductive circuit.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to flexible conductive paste and a flexible circuit board.
Background
A flexible printed circuit board (FPC) is a flexible printed circuit board that is made of polyimide, polyester film, or the like as a flexible substrate and has high reliability and excellent characteristics. The high-density printed circuit board has the characteristics of high wiring density, light weight, thin thickness and good bending property, and is widely applied to various daily electronic products.
At present, a flexible circuit in a flexible circuit board is mainly made of copper foil, and the flexible circuit can be made by electrodeposition (ED for short) or plating, and the process is complex and the cost is high. In recent years, a method of forming a conductive circuit on a flexible substrate by using conductive ink or conductive ink through a printing or printing method is proposed to manufacture a flexible circuit board, but the conductive circuit manufactured by using the conductive ink on the market at present has poor flexibility and poor bending resistance, and is difficult to meet the higher and higher application requirements of the flexible circuit board.
Disclosure of Invention
The invention provides flexible conductive paste and a flexible circuit board, which can improve the flexibility of a flexible conductive circuit.
In a first aspect, the invention provides a flexible conductive paste, which adopts the following technical scheme:
the flexible conductive paste includes: the conductive coating comprises a first polymer, a solvent, a conductive filler, a second polymer and a curing agent, wherein the first polymer, the second polymer and the curing agent react in the heating and curing process to form a flexible three-dimensional network structure.
Optionally, the first polymer is epoxy resin, or polyurethane, or a mixture of epoxy resin and one or more of polyolefin, linear polyester, vinyl chloride-vinyl acetate copolymer and polyurethane, or a mixture of polyurethane and one or more of polyester resin, acrylic resin and cellulose.
Optionally, the epoxy resin has a softening point above 100 ℃ and an epoxy equivalent weight above 5000.
Alternatively, the second polymer has a molecular weight of less than 2000 and a melting point of less than 50 ℃.
Optionally, the second polymer comprises one or both of polyethylene glycol, polypropylene glycol.
Optionally, the curing agent is a blocked polyisocyanate.
Optionally, the flexible conductive paste further comprises one or both of a defoaming agent and an adhesion promoter.
Optionally, the flexible conductive paste comprises, by weight: 3 to 15 percent of first polymer, 5 to 20 percent of solvent, 60 to 85 percent of conductive filler, 3 to 15 percent of second polymer, 1 to 10 percent of curing agent, 0.1 to 5 percent of defoaming agent and 0.1 to 5 percent of adhesion promoter.
In a second aspect, the present invention provides a flexible conductive circuit, which adopts the following technical scheme:
the flexible conductive circuit is formed by printing the flexible conductive paste and heating and curing.
Optionally, the resistance change rate of the flexible conductive circuit is less than 40% after being bent 10000 times.
The invention provides flexible conductive paste and a flexible circuit board, wherein the flexible conductive paste comprises: after the flexible conductive paste is printed on the flexible substrate, the first polymer, the second polymer and the curing agent react in the heating and curing process to form a flexible three-dimensional net-shaped structure in the heating and curing process, so that the flexibility of the flexible conductive circuit can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the technical features in the embodiments of the present invention may be combined with each other without conflict.
The embodiment of the invention provides flexible conductive paste, which specifically comprises the following components: the conductive coating comprises a first polymer, a solvent, a conductive filler, a second polymer and a curing agent, wherein the first polymer, the second polymer and the curing agent satisfy the following conditions: in the process of heating and curing the flexible conductive paste, the first polymer, the second polymer and the curing agent react to form a flexible three-dimensional network structure.
It should be noted that, during the heating and curing process of the flexible conductive paste, the first polymer and the second polymer react with the curing agent, which may include various cases, for example, the active group of the first polymer and the active group of the second polymer react with the active group of the curing agent, respectively, or the active group of the second polymer and the active group of the curing agent react with the active group of the first polymer, respectively, or the active group of the first polymer and the active group of the curing agent react with the active group of the second polymer, respectively, or the active group of the first polymer, the active group of the second polymer, and the active group of the curing agent may react with each other. In each of the above cases, the first polymer, the second polymer and the curing agent can form a flexible three-dimensional network structure after reaction.
The flexible conductive paste in the embodiment of the invention can be suitable for forming processes such as screen printing, flexography, pad printing, extrusion type dispensing, steel mesh printing and the like, and can be cured by heating after forming.
After the flexible conductive paste is printed on the flexible substrate, in the heating and curing process, the first polymer, the second polymer and the curing agent react to form a flexible three-dimensional net-shaped structure, so that the flexibility of the flexible conductive circuit can be improved.
Optionally, the preparation method of the flexible conductive paste in the embodiment of the invention may include the following steps:
step 1, preparing an organic carrier: heating and dissolving the first polymer, the second polymer, the solvent and the curing agent to obtain an organic carrier;
in the process, the heating can be carried out in an oil bath mode, the stirring is carried out while the heating is carried out, the oil bath temperature can be 70-120 ℃, and the stirring speed can be 300-800 rpm.
Step 2, preparing flexible conductive slurry: and stirring and dispersing the conductive filler and the organic carrier, and then carrying out three-roll rolling to obtain the flexible conductive slurry.
In the process, the stirring speed can be selected from 500rpm to 2500 rpm; after being stirred and dispersed, the mixture can be placed for a certain time, such as half an hour (the wetting effect of the organic carrier on the conductive filler can be enhanced, the subsequent rolling effect is improved), and then three-roll rolling is carried out. The viscosity of the finally obtained flexible conductive paste may range from 10Pa · s to 40Pa · s.
The following examples of the present invention illustrate the materials in the flexible conductive paste in detail.
A first polymer
The first polymer in the embodiment of the invention may include one or more of epoxy resin, polyolefin, linear polyester, vinyl chloride-vinyl acetate resin, polyurethane (including polyurethane prepolymer), polyester resin, acrylic resin, and cellulose. For example, the first polymer is an epoxy resin; or the first polymer is a polyurethane; or the first polymer is a mixture of epoxy resin and one or more of polyolefin, linear polyester, vinyl chloride-vinyl acetate copolymer and polyurethane; or the mixture of the first polymer and one or more of polyurethane, polyester resin, acrylic resin and cellulose. The first polymer in the last two examples includes a resin with better toughness and a resin with better flexibility, so that the flexible conductive circuit made of the flexible conductive paste has better toughness and flexibility at the same time.
Alternatively, when the first polymer comprises an epoxy resin, the epoxy resin has a softening point above 100 ℃ and an epoxy equivalent above 5000. When the softening point of the epoxy resin is higher than 100 ℃, the manufactured flexible conducting circuit can endure a welding process, and the application is wider and more convenient; when the epoxy equivalent of the epoxy resin is higher than 5000, the epoxy resin has fewer reactive groups, and the second polymer and the curing agent are relatively excessive, so that the epoxy resin has a better flexible extension effect.
Second Polymer
In embodiments of the present invention, the second polymer may be selected from polyether polyols, such as one or more of sugar-based polyether polyols, alcohol-based polyether polyols, amine-based polyether polyols, phenol-based polyether polyols, and the like.
In addition, in the embodiment of the invention, the molecular weight of the second polymer is lower than 2000, and the melting point is lower than 50 ℃, so that the second polymer is in the forms of liquid, viscous and wax at room temperature, can be easily mixed with other materials without additional dissolution in the process of preparing the flexible conductive paste, and can participate in reaction in the subsequent heating and curing process. Optionally, the second polymer comprises one or both of polyethylene glycol, polypropylene glycol.
Curing agent
In the embodiment of the invention, the curing agent can be selected from blocked polyisocyanates. The polyisocyanate can be one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate and polyphenyl methane polyisocyanate or a mixture of at least two of the toluene diisocyanate, the hexamethylene diisocyanate, the diphenylmethane diisocyanate and the polyphenyl methane polyisocyanate.
Solvent(s)
In the embodiment of the present invention, the solvent may be one or a mixture of at least two selected from ethanol, isopropanol, n-propanol, ethylene glycol, propylene glycol, glycerol, n-butanol, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, isophorone and terpineol.
Conductive filler
The conductive filler is one or a mixture of at least two of gold, silver, copper, iron, nickel, aluminum, graphene, carbon black, graphite, silver-coated copper powder and the like. The shape of the conductive filler is one of sheet, sphere, line, rod, needle, dendritic and the like or a mixture of at least two of the sheet, the sphere, the line, the rod, the needle and the dendritic. The size of the conductive filler is 0.1-6 μm.
Other auxiliaries
In the embodiment of the invention, the flexible conductive paste further comprises one or two of a defoaming agent and an adhesion promoter. The defoaming agent can be one of polysiloxane defoaming agent, organic silicon defoaming agent and polyether defoaming agent or a mixture of at least two of the polysiloxane defoaming agent, the organic silicon defoaming agent and the polyether defoaming agent. The adhesion promoter may be a silane coupling agent type adhesion promoter.
Optionally, in the flexible conductive paste in the embodiment of the present invention, the weight percentage of the first polymer is 3% to 15%, such as 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%; the solvent is 5-20% by weight, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%; the weight percentage of the conductive filler is 60% to 85%, such as 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, or 84%; the second polymer is present in an amount of 3% to 15%, such as 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14% by weight; the weight percentage of the curing agent is 1-10%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%; the weight percentage of the defoaming agent is 0.1-5%, such as 0.2%, 0.5%, 1%, 2%, 3% or 4%; the adhesion promoter is 0.1-5 wt%, such as 0.2%, 0.5%, 1%, 2%, 3% or 4%.
In addition, the embodiment of the invention also provides a flexible circuit board, which comprises a flexible substrate and a flexible conductive circuit positioned on the flexible substrate, wherein the flexible conductive circuit is formed by printing the flexible conductive paste and heating and curing.
For example, the flexible conductive paste is printed on a flexible substrate by screen printing, and then placed in a forced air drying oven to be heated, sintered and cured. The heating sintering temperature of the flexible conductive slurry is 120-200 ℃, and the sintering time is 10-80 min.
The flexible conductive circuit in the embodiment of the invention has better flexibility and electrical property at the same time, and can have better flexibility even under the condition of high film thickness (more than 30 mu m). Tests prove that the resistance change rate of the flexible conductive circuit after being bent for 10000 times is lower than 40%. The sheet resistance of the flexible conductive circuit is 5-12 m omega/sq/mil.
The thickness of the flexible conductive tracks may be between 10 μm and 60 μm, such as 20 μm, 30 μm, 40 μm or 50 μm.
The flexible substrate may be one of films of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), Polyimide (PI), Polyamide (PA), and the like.
It should be added that, according to actual needs, the flexible circuit board may further include other electronic components, such as a switch, a power supply, a light emitting device, a sensor, a chip, and the like, and the flexible circuit board may also include other film layers, such as an encapsulation layer, and this is not limited in the embodiment of the present invention.
The following examples of the present invention illustrate the advantages of the flexible conductive paste in a number of specific examples and comparative examples.
Example one
The flexible conductive paste comprises the following components in percentage by weight: 7% of epoxy resin, 14% of diethylene glycol ethyl ether acetate, 65% of spherical silver powder, 6% of polyethylene glycol, 6% of hexamethylene diisocyanate, 1% of polysiloxane defoaming agent and 1% of silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring epoxy resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, a polysiloxane antifoaming agent and a silane coupling agent adhesion promoter in an oil bath at 70 ℃ to dissolve to obtain an organic carrier;
preparing flexible conductive slurry: and stirring and dispersing the spherical silver powder and the organic carrier in a stirring tank at 2000rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the viscous flexible conductive slurry.
And printing the flexible conductive paste on a PI film flexible substrate through a screen printer, and placing the PI film flexible substrate in a forced air drying oven to be heated to 160 ℃ for sintering and curing to obtain the flexible circuit board.
Example two
The flexible conductive paste comprises the following components in percentage by weight: 5% of polyurethane resin, 5% of diethylene glycol ethyl ether acetate, 55% of spherical silver powder, 25% of flake silver powder, 4% of polyethylene glycol, 4% of hexamethylene diisocyanate, 1% of polysiloxane defoaming agent and 1% of silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring polyurethane resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, a polysiloxane antifoaming agent and a silane coupling agent adhesion promoter in an oil bath at the temperature of 80 ℃ to dissolve the polyurethane resin, the diethylene glycol ethyl ether acetate, the polyethylene glycol, the hexamethylene diisocyanate, the polysiloxane antifoaming agent and the silane coupling agent adhesion promoter to obtain an organic carrier;
preparing flexible conductive slurry: and (2) stirring and dispersing the spherical silver powder, the flaky silver powder and the organic carrier in a stirring tank at 2000rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the flexible conductive paste.
And printing the flexible conductive paste on a PI film flexible substrate through a screen printer, and placing the PI film flexible substrate in a forced air drying oven to be heated to 160 ℃ for sintering and curing to obtain the flexible circuit board.
EXAMPLE III
The flexible conductive paste comprises the following components in percentage by weight: 6% of epoxy resin, 10% of diethylene glycol ethyl ether acetate, 70% of spherical silver powder, 8% of polyethylene glycol, 4% of hexamethylene diisocyanate, 0.5% of polysiloxane defoaming agent and 1.5% of silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring epoxy resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, a polysiloxane antifoaming agent and a silane coupling agent adhesion promoter in an oil bath at 90 ℃ to dissolve to obtain an organic carrier;
preparing flexible conductive slurry: and stirring and dispersing the spherical silver powder and the organic carrier in a stirring tank at 2500rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the flexible conductive paste.
And printing the flexible conductive paste on a PET flexible substrate through a screen printer, and placing the PET flexible substrate in a forced air drying oven to be heated to 200 ℃ for sintering and curing to obtain the flexible circuit board.
Example four
The flexible conductive paste comprises the following components in percentage by weight: 4% of epoxy resin, 4% of polyurethane resin, 16% of diethylene glycol ethyl ether acetate, 65% of spherical silver powder, 4% of polyethylene glycol, 5% of hexamethylene diisocyanate, 1% of polysiloxane defoaming agent and 1% of silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating, stirring and dissolving epoxy resin, polyurethane resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, a polysiloxane antifoaming agent and a silane coupling agent adhesion promoter in an oil bath at 90 ℃ to obtain an organic carrier;
preparing flexible conductive slurry: and stirring and dispersing the flaky silver powder and the organic carrier in a stirring tank at 2500rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the flexible conductive paste.
And printing the flexible conductive paste on a PET flexible substrate through a screen printer, and placing the PET flexible substrate in a forced air drying oven to be heated to 180 ℃ for sintering and curing to obtain the flexible circuit board.
EXAMPLE five
The flexible conductive paste comprises the following components in percentage by weight: 8% of epoxy resin, 20% of diethylene glycol ethyl ether acetate, 50% of spherical silver powder, 10% of silver-coated copper powder, 4% of polyethylene glycol, 5% of hexamethylene diisocyanate, 1% of an organic silicon defoamer and 2% of a silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring epoxy resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, an organic silicon defoamer and a silane coupling agent adhesion promoter in an oil bath at the temperature of 80 ℃ to dissolve to obtain an organic carrier;
preparing flexible conductive slurry: and (3) stirring and dispersing the spherical silver powder, the silver-coated copper powder and the organic carrier in a stirring tank at 2000rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the flexible conductive paste.
And printing the flexible conductive paste on a PET flexible substrate through a screen printer, and placing the PET flexible substrate in a forced air drying oven to be heated to 160 ℃ for sintering and curing to obtain the flexible circuit board.
Comparative example 1
The conductive paste comprises the following components in percentage by weight: 8% of epoxy resin, 16% of diethylene glycol ethyl ether acetate, 70% of spherical silver powder, 2% of polyethylene glycol, 2% of hexamethylene diisocyanate, 1% of an organic silicon defoaming agent and 1% of a silane coupling agent type adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring epoxy resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, an organic silicon defoamer and a silane coupling agent adhesion promoter in an oil bath at the temperature of 80 ℃ to dissolve to obtain an organic carrier;
preparing conductive slurry: and stirring and dispersing the spherical silver powder and the organic carrier in a stirring tank at 2000rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the conductive paste.
And printing the conductive paste on a PI flexible substrate through a screen printer, and placing the PI flexible substrate in a forced air drying oven to be heated to 160 ℃ for sintering and curing to obtain the circuit board.
Comparative example No. two
The flexible conductive paste comprises the following components in percentage by weight: 8% of epoxy resin, 17% of diethylene glycol ethyl ether acetate, 70% of spherical silver powder, 3% of hexamethylene diisocyanate, 1% of an organic silicon defoaming agent and 1% of a silane coupling agent adhesion promoter.
The preparation method comprises the following steps:
preparing an organic carrier: heating and stirring epoxy resin, diethylene glycol ethyl ether acetate, polyethylene glycol, hexamethylene diisocyanate, an organic silicon defoamer and a silane coupling agent adhesion promoter in an oil bath at the temperature of 80 ℃ to dissolve to obtain an organic carrier;
preparing flexible conductive slurry: and (3) stirring and dispersing the spherical silver powder, the silver-coated copper powder and the organic carrier in a stirring tank at 2000rpm, then placing for half an hour, and then carrying out three-roll rolling to finally obtain the conductive paste.
And printing the conductive paste on a PI flexible substrate through a screen printer, and placing the PI flexible substrate in a forced air drying oven to be heated to 160 ℃ for sintering and curing to obtain the circuit board.
TABLE 1 tables of results of performance tests on conductive pastes and circuit boards prepared in examples and comparative examples
| Sheet resistance/m omega/sq/mil | Thickness/mum | Bending 10000 times change rate of sheet resistance/%) | |
| Example one | 9 | 35±2 | 22 |
| Example two | 6 | 35±2 | 37 |
| EXAMPLE III | 8 | 35±2 | 16 |
| Example four | 9 | 35±2 | 20 |
| EXAMPLE five | 12 | 35±2 | 22 |
| Comparative example 1 | 8 | 35±2 | 170 |
| Comparative example No. two | 9 | 35±2 | 220 |
From the above test results, it can be seen that the resistance change rate of the flexible circuit board made of the flexible conductive pastes in the examples of the present invention during bending is substantially lower than the sheet resistance change rate of the circuit board made of the conductive paste in the comparative examples, and the flexible circuit board has very excellent flexibility.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A flexible conductive paste, comprising: the conductive coating comprises a first polymer, a solvent, a conductive filler, a second polymer and a curing agent, wherein the first polymer, the second polymer and the curing agent react in the heating and curing process to form a flexible three-dimensional network structure.
2. The flexible conductive paste according to claim 1, wherein the first polymer is one of epoxy resin and polyurethane, or a mixture of epoxy resin and one or more of polyolefin, linear polyester, vinyl chloride-vinyl acetate resin and polyurethane, or a mixture of polyurethane and one or more of polyester resin, acrylic resin and cellulose.
3. The flexible conductive paste according to claim 2, wherein the epoxy resin has a softening point higher than 100 ℃ and an epoxy equivalent higher than 5000.
4. The flexible conductive paste according to claim 1, wherein the second polymer has a molecular weight of less than 2000 and a melting point of less than 50 ℃.
5. The flexible conductive paste according to claim 4, wherein the second polymer comprises one or both of polyethylene glycol and polypropylene glycol.
6. The flexible conductive paste according to claim 1, wherein the curing agent is a blocked polyisocyanate.
7. The flexible conductive paste according to claim 1, further comprising one or both of a defoaming agent and an adhesion promoter.
8. The flexible conductive paste according to claim 7, wherein the flexible conductive paste comprises, in weight percent: 3 to 15 percent of first polymer, 5 to 20 percent of solvent, 60 to 85 percent of conductive filler, 3 to 15 percent of second polymer, 1 to 10 percent of curing agent, 0.1 to 5 percent of defoaming agent and 0.1 to 5 percent of adhesion promoter.
9. A flexible circuit board comprising a flexible substrate and a flexible conductive circuit on the flexible substrate, wherein the flexible conductive circuit is formed by printing the flexible conductive paste according to any one of claims 1 to 8 and heating and curing the printed paste.
10. The flexible circuit board of claim 9, wherein the flexible conductive traces are bent 10000 times with a resistance change rate of less than 40%.
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| WO2023124283A1 (en) * | 2021-12-31 | 2023-07-06 | 北京梦之墨科技有限公司 | Conductive ink and electronic device |
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| JP2002260442A (en) * | 2001-03-06 | 2002-09-13 | Toyobo Co Ltd | Conductive paste |
| JP2013149596A (en) * | 2011-12-21 | 2013-08-01 | Shoei Chem Ind Co | Heat-curable conductive paste |
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