CN108148469B - Preparation method of water-based UV conductive ink - Google Patents
Preparation method of water-based UV conductive ink Download PDFInfo
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- CN108148469B CN108148469B CN201810128796.7A CN201810128796A CN108148469B CN 108148469 B CN108148469 B CN 108148469B CN 201810128796 A CN201810128796 A CN 201810128796A CN 108148469 B CN108148469 B CN 108148469B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 50
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
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- 230000008569 process Effects 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000013530 defoamer Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract 3
- 229920000642 polymer Polymers 0.000 claims description 26
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 12
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000007602 hot air drying Methods 0.000 claims description 8
- 238000007641 inkjet printing Methods 0.000 claims description 8
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011231 conductive filler Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000002383 tung oil Substances 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 5
- BBCLXYJRPRRZQW-UHFFFAOYSA-N 2-phenylnaphthalen-1-amine Chemical compound C1=CC2=CC=CC=C2C(N)=C1C1=CC=CC=C1 BBCLXYJRPRRZQW-UHFFFAOYSA-N 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 5
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 claims description 5
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003848 UV Light-Curing Methods 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 17
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- UMHFSEWKWORSLP-UHFFFAOYSA-N thiophene 1,1-dioxide Chemical compound O=S1(=O)C=CC=C1 UMHFSEWKWORSLP-UHFFFAOYSA-N 0.000 description 8
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- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- LWRYDHOHXNQTSK-UHFFFAOYSA-N thiophene oxide Chemical compound O=S1C=CC=C1 LWRYDHOHXNQTSK-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
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- KNOYHJOPRUTPSQ-QHCPKHFHSA-N (4s)-5-amino-5-oxo-4-[3-[4-(4-phenylphenyl)phenyl]propanoylamino]pentanoic acid Chemical compound C1=CC(CCC(=O)N[C@@H](CCC(O)=O)C(=O)N)=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 KNOYHJOPRUTPSQ-QHCPKHFHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 239000000945 filler Substances 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
- 229910002804 graphite Inorganic materials 0.000 description 1
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Conductive Materials (AREA)
Abstract
本发明公开了一种水性UV导电油墨的制备方法，以该导电油墨的总重量为基准，由以下质量百分含量的组分组成：40～60％的导电聚合物PEDOT、10～30％的去离子水、1～8％的氧化剂、10～20％的纳米铜粉、0.2～1.2％的稳定剂、2～5％的粘合剂、1～6％的流平剂、0.2～1.2％的消泡剂、0.2～2％的阻聚剂和10～30％的溶剂。采用本发明的技术方案，由于采用价格相对低廉的导电聚合物PEDOT和纳米铜制备导电油墨，大大降低了成本且操作简单，易于实现工业化生产；同时本发明的技术方案在印刷过程中无需对油墨进行高温烧结不仅简化了工艺同时提高了导电油墨的稳定性和一致性。
The invention discloses a preparation method of water-based UV conductive ink. Based on the total weight of the conductive ink, it is composed of the following components by mass percentage: 40-60% of conductive polymer PEDOT, 10-30% of Deionized water, 1-8% oxidant, 10-20% nano copper powder, 0.2-1.2% stabilizer, 2-5% binder, 1-6% leveling agent, 0.2-1.2% Defoamer, 0.2-2% polymerization inhibitor and 10-30% solvent. By adopting the technical scheme of the present invention, since the conductive ink is prepared by using relatively low-cost conductive polymer PEDOT and nano-copper, the cost is greatly reduced, the operation is simple, and the industrial production is easy to be realized; meanwhile, the technical scheme of the present invention does not require the ink in the printing process. Performing high temperature sintering not only simplifies the process but also improves the stability and consistency of the conductive ink.
Description
The application is a divisional application of a patent application with the application number of 2015107903117, the application date of a parent application is 11/16/2015, and the invention name is as follows: an aqueous UV conductive ink and a preparation method thereof.
Technical Field
The invention belongs to the field of high-molecular conductive materials, and particularly relates to a preparation method of water-based UV conductive ink.
Background
The water-based UV (ultraviolet curing) conductive ink is a novel ink developed in recent years, is high in drying speed, low in environmental pollution and low in energy consumption, becomes a novel ink variety generally accepted by the current ink industry, is mainly applied to the fields of Radio Frequency Identification (RFID), Printed Circuit Boards (PCBs), electronic screen displays, sensors, electronic paper, solar cells, thin film switches and the like, represents the development direction of thin film printed electronic materials and even the whole printed electronic industry, and is expected to become a leading-edge technology for changing the life style of human beings in the future. At present, the conductive ink applied to the printed electronic industry is mainly filled conductive ink, and most of the used conductive fillers are inorganic fillers such as gold, silver, copper, nickel, carbon black, graphite, carbon fibers and the like, wherein the metal silver is most widely applied with good conductivity and stability. The water-based UV conductive ink is prepared by taking water-based light-cured resin as a connecting material, adding nano silver powder as a filler and assisting other components. The printing principle is that the silver conductive ink is printed on the base materials such as the printed circuit board, and the like, and is firstly placed in an oven for drying, and then is solidified by an ultraviolet curing machine, and is sintered at the temperature of about 150-350 ℃, and is cooled to the normal temperature. The conductivity of the sintered silver conductive layer can reach 2.4 multiplied by 10 < -5 > omega cm, the surface resistance can reach below 0.1 omega/□ (□ is a square resistor printing process, which means the resistance between the edges of a square thin film conductive material, and the square resistor is characterized in that the resistances between the edges of any square are the same and are only related to the thickness of a conductive film and other factors), and the application requirements of RFID antennas, PCB circuit boards and the like can be completely met.
But the following reasons restrict the industrial application of the water-based UV conductive ink: (1) chemical reaction occurs during printing, and the sintering temperature is high. As shown in the paper "Triggering the sintering of silver nanoparticles from room temperature" by Shlomo Magdassi et al, American chemical society, the nano silver particles spontaneously form metal bonds upon contact with the reverse charged polyelectrolyte, thereby achieving normal temperature sintering of the conductive ink, but the experimental setup is complicated. (2) Silver is the metal with the best conductivity at normal temperature, but the expensive price of the nano silver powder is the main reason for restricting the wide industrial application of the water-based UV conductive ink. The research on the novel water-based UV conductive ink capable of solving the problems is a research hotspot in the printing ink industry at home and abroad, so that the research and development of the water-based UV conductive ink have very important practical significance.
Therefore, it is necessary to provide a solution to the above-mentioned drawbacks in the prior art.
Disclosure of Invention
In view of the above, there is a need to provide a method for preparing an aqueous UV conductive ink, which can simplify the process and improve the stability and consistency of the conductive ink.
In order to overcome the defects in the prior art, the invention provides the following technical scheme:
a preparation method of water-based UV conductive ink comprises the following steps:
step S1: taking the total weight of the conductive ink as a reference, uniformly mixing the following components in percentage by mass to form a mixed solution:
conductive polymer PEDOT (poly 3, 4-ethylenedioxythiophene): 40-60%; the PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer);
deionized water: 10-30%;
oxidizing agent: 1-8%; the oxidant is one or more of calcium hypochlorite, magnesium hypochlorite, sodium hypochlorite or potassium hypochlorite;
10-30% of a solvent; the solvent is one or more of diethylene glycol monobutyl ether, tung oil or n-propanol;
10-20% of nano copper powder conductive filler;
a stabilizer: 0.2-1.2%; the stabilizer is one or more of cetyl trimethyl ammonium bromide, 2-hydroxy-4-n-octoxy benzophenone, dodecyl trimethyl ammonium bromide or polyvinylpyrrolidone;
adhesive: 2-5%; the adhesive is one or more of 2, 2-dimethylolpropionic acid, dimethylolbutyric acid or polyacrylamide;
leveling agent: 1-6%; the leveling agent is one or more of TEGO Glide100, a pure acrylic leveling agent, ethylene oxide or propylene oxide;
defoaming agent: 0.2-1.2%; the defoaming agent is one or more of a defoaming agent 6800, a defoaming agent 810, a defoaming agent D105, a defoaming agent T-20GA or a defoaming agent DF-100;
polymerization inhibitor: 0.2-2%; the polymerization inhibitor is one or more of hydroquinone, phenothiazine, beta-phenyl naphthylamine, methyl hydroquinone THQ or methylene blue;
step S2: heating the mixed solution to 65-80 ℃, continuously stirring for 1 hour, and then cooling for 2 hours at normal temperature to obtain an ink mixture;
step S3: printing the ink mixture obtained in the step S2 on a substrate preheated to 60-95 ℃ in an ink-jet printing mode to form an ink pattern, and then putting the substrate into a hot air drying oven for drying and forming for 30 minutes;
step S4: and carrying out ultraviolet curing on the ink pattern on the substrate.
As a preferred technical solution, the step S1 further includes the steps of:
firstly preparing a conductive polymer PEDOT aqueous solution and then forming a mixed solution, wherein the steps of preparing the conductive polymer PEDOT aqueous solution are as follows:
placing 40-60% by mass of PEDOT into a round-bottom flask, adding 10-30% by mass of deionized water, mechanically stirring at the speed of 400r/min for 10 minutes, and pouring 1-8% by mass of an oxidant;
and heating the round-bottom flask, keeping the temperature between 50 and 80 ℃, mechanically stirring the round-bottom flask for 50 minutes at the speed of 800r/min, and then cooling the round-bottom flask for 1 hour at normal temperature to form the conductive polymer PEDOT aqueous solution.
Preferably, the oxidizing agent is calcium hypochlorite (Ca (ClO))2) In step S1, the oxidation reaction process of PEDOT and the calcium hypochlorite is as follows:
as a preferable technical solution, in the step S3, the substrate is a PET plate reinforced by glass fiber.
According to a preferable technical scheme, the particle diameter of the nano copper powder is less than 50nm, and the purity is more than 99.9%.
Compared with the prior art, the conductive ink is prepared from the conductive polymers PEDOT and the nano copper which are relatively low in price and high in specific capacity, and compared with the conductive ink prepared from the nano silver particles in the prior art, the conductive ink is greatly reduced in cost, simple to operate and easy to realize industrial production; according to the technical scheme, high-temperature sintering of the ink is not needed in the printing process, the substrate to be printed is preheated to 60-95 ℃, the water-based UV conductive ink prepared by the method is printed on the preheated substrate in an ink-jet printing mode, the preheated substrate can accelerate printing and forming of the ink on the substrate, and finally the substrate is dried, formed and cured by ultraviolet light. Therefore, the invention not only simplifies the process, but also improves the stability and consistency of the conductive ink.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of the aqueous UV conductive ink of the invention.
Fig. 2 is an SEM photograph of the aqueous UV conductive ink of example 1 of the present invention.
Fig. 3 is an SEM photograph of the aqueous UV conductive ink of example 2 of the present invention.
Fig. 4 is an SEM photograph of the aqueous UV conductive ink of example 3 of the present invention.
Fig. 5 is an SEM photograph of the aqueous UV conductive ink of example 4 of the present invention.
The following specific embodiments will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The invention will be further explained with reference to the drawings.
The printing principle in the prior art is that silver conductive ink is printed on a base material such as a printed circuit board, and the like, and the base material is firstly placed in an oven for drying, then is cured by an ultraviolet curing machine, is sintered at the temperature of about 150-350 ℃, and is cooled to the normal temperature. The expensive price of the nano silver powder greatly restricts the industrial application of the conductive ink; meanwhile, uncertain chemical reactions can be introduced by high-temperature sintering, so that the stability and consistency of the conductive ink cannot be ensured, and uncertainty is increased in practical application.
In order to overcome the defects of the prior art, the invention provides a preparation method of an aqueous UV conductive ink, which is shown in figure 1 and comprises the following steps:
step S1: taking the total weight of the conductive ink as a reference, uniformly mixing the following components in percentage by mass to form a mixed solution:
conductive polymer PEDOT (poly 3, 4-ethylenedioxythiophene): 40-60%; the PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer);
deionized water: 10-30%;
oxidizing agent: 1-8%; the oxidant is one or more of calcium hypochlorite, magnesium hypochlorite, sodium hypochlorite or potassium hypochlorite;
10-30% of a solvent; the solvent is one or more of diethylene glycol monobutyl ether, tung oil or n-propanol;
10-20% of nano copper powder conductive filler;
a stabilizer: 0.2-1.2%; the stabilizer is one or more of cetyl trimethyl ammonium bromide, 2-hydroxy-4-n-octoxy benzophenone, dodecyl trimethyl ammonium bromide or polyvinylpyrrolidone;
adhesive: 2-5%; the adhesive is one or more of 2, 2-dimethylolpropionic acid, dimethylolbutyric acid or polyacrylamide;
leveling agent: 1-6%; the leveling agent is one or more of TEGO Glide100, a pure acrylic leveling agent, ethylene oxide or propylene oxide;
defoaming agent: 0.2-1.2%; the defoaming agent is one or more of a defoaming agent 6800, a defoaming agent 810, a defoaming agent D105, a defoaming agent T-20GA or a defoaming agent DF-100;
polymerization inhibitor: 0.2-2%; the polymerization inhibitor is one or more of hydroquinone, phenothiazine, beta-phenyl naphthylamine, methyl hydroquinone THQ or methylene blue;
wherein, the step S1 further comprises the following steps:
firstly preparing a conductive polymer PEDOT aqueous solution and then forming a mixed solution, wherein the steps of preparing the conductive polymer PEDOT aqueous solution are as follows:
placing 40-60% by mass of PEDOT into a round-bottom flask, adding 10-30% by mass of deionized water, mechanically stirring at the speed of 400r/min for 10 minutes, and pouring 1-8% by mass of an oxidant;
and heating the round-bottom flask, keeping the temperature between 50 and 80 ℃, mechanically stirring the round-bottom flask for 50 minutes at the speed of 800r/min, and then cooling the round-bottom flask for 1 hour at normal temperature to form the conductive polymer PEDOT aqueous solution.
When the oxidizing agent is calcium hypochlorite (ca (clo)2), the oxidation reaction process of the PEDOT and the calcium hypochlorite in the step S1 is as follows:
PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer), and the oxidation mechanism of PEDOT (3, 4-ethylenedioxythiophene polymer) under calcium hypochlorite ca (clo) 2: wherein OCl- (hypochlorous acid) is an oxidizing agent which oxidizes thiophene (a) in PEDOT (3, 4-ethylenedioxythiophene polymer) to its corresponding thiophene-1-oxide (b). Similarly, thiophene-1-oxide (b) is oxidized to its corresponding thiophene-1, 1-dioxide (c). In this reaction, the thiophene-1-oxide (b) is assumed to be one reaction intermediate in the thiophene-1, 1-dioxide (c). Finally, the thiophene-1, 1-dioxide (c) is further oxidized to remove SO2 in the compound, and a hydroxyl group is attached to the thiophene-1, 1-dioxide (c) by a nucleophilic reaction of water, thereby forming an aqueous polymer solution having high conductivity.
Step S2: heating the mixed solution to 65-80 ℃, continuously stirring for 1 hour, and then cooling for 2 hours at normal temperature to obtain an ink mixture;
step S3: printing the ink mixture obtained in the step S2 on a substrate preheated to 60-95 ℃ in an ink-jet printing mode to form an ink pattern, and then putting the substrate into a hot air drying oven for drying and forming for 30 minutes;
step S4: and carrying out ultraviolet curing on the ink pattern on the substrate.
Preferably, in the above technical solution, of course, the water-based UV conductive ink without the pigment may also be gloss oil according to the actual requirement of the water-based UV conductive ink; the type of the pigment to be added is any color to be added, and the pigment can be one or two of organic pigment or inorganic pigment, and the mass percentage of the pigment to be added is 5-10%.
Preferably, the substrate is a PET plate reinforced by glass fiber, because pure PET has low heat resistance, the thermal deformation temperature is only about 90 ℃, but the mechanical property of the PET reinforced by glass fiber is similar to that of engineering plastics such as PC, PA and the like, and the thermal deformation temperature can reach 225 ℃.
In order to overcome the defects of the prior art, the invention provides the water-based UV conductive ink which is low in cost, simple in process and excellent in performance, and the water-based UV conductive ink mainly comprises the following components in percentage by weight based on the total weight of the ink:
40-60% of conductive polymer, 10-30% of deionized water, 1-8% of oxidant, 10-20% of conductive filler, 0.2-1.2% of stabilizer, 2-5% of adhesive, 1-6% of flatting agent, 0.2-1.2% of defoaming agent, 0.2-2% of polymerization inhibitor and 10-30% of solvent, wherein the conductive polymer is 40-60% of PEDOT (poly (3, 4-ethylenedioxythiophene)), and has the characteristics of relatively low price and high specific capacity. The conductive polymer is the key to determining the performance of the aqueous UV conductive ink. The conductive polymer PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer), has special electrical and optical properties, and has the characteristics of simple molecular structure, small energy gap, high conductivity (600S/cm) and the like.
Since PEDOT itself is an insoluble polymer, its specific conductivity properties cannot be directly utilized. However, it was found in the experiments that the addition of an oxidizing agent to carry out the oxidation reaction allows PEDOT to form a water-soluble polymer and has high conductivity. The oxidant is one or more of calcium hypochlorite, magnesium hypochlorite, sodium hypochlorite or potassium hypochlorite, and is used for generating a chemical reaction with PEDOT to generate a polymer aqueous solution with high conductivity.
In several experiments, calcium hypochlorite (Ca (ClO))2) After the polymer is subjected to oxidation reaction with PEDOT, the conductivity of the polymer aqueous solution is greatly improved, and the specific reaction process is as follows:
PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer), PEDOT (3, 4-ethylenedioxythiophene polymer) in calcium hypochlorite Ca (ClO)2The following oxidation reaction mechanism: wherein OCl- (hypochlorous acid) is an oxidizing agent which oxidizes thiophene (a) in PEDOT (3, 4-ethylenedioxythiophene polymer) to its corresponding thiophene-1-oxide (b). Similarly, thiophene-1-oxide (b) is oxidized to its corresponding thiophene-1, 1-dioxide (c). In this reaction, the thiophene-1-oxide (b) is assumed to be one reaction intermediate in the thiophene-1, 1-dioxide (c). Finally, the further oxidation of the thiophene-1, 1-dioxide (c) removes SO from the compound2And allowing the hydroxyl group to be attached to the thiophene-1, 1-dioxide (c) by a nucleophilic reaction of water, thereby forming an aqueous polymer solution having high conductivity.
Although the conductive polymer formed in the way has good conductivity in a water-soluble state, the conductivity is greatly reduced after the polymer is solidified. In order to improve the conductivity of the aqueous UV conductive ink, the conductive polymer is added with the nano copper powder conductive filler, so that the conductivity of the ink is greatly improved.
Preferably, the particle diameter of the nano copper powder is less than 50nm, and the purity is more than 99.9%, so that the nano copper powder can be uniformly mixed in the ink.
The nanometer copper powder is easy to oxidize at normal temperature, and the electric conductivity of the oxidized nanometer copper powder is greatly reduced. Therefore, the stabilizer is added in the formula of the invention to prevent the oxidation of the nano copper powder, and further, the stabilizer is one or more of cetyl trimethyl ammonium bromide, 2-hydroxy-4-n-octoxy benzophenone, dodecyl trimethyl ammonium bromide or polyvinylpyrrolidone.
The printing viscosity of the ink is a key factor for ensuring the quality of a printed product, and the adhesive in the formula can control the viscosity of the ink. Further, the adhesive is one or more of 2, 2-dimethylolpropionic acid, dimethylolbutyric acid or polyacrylamide; it is particularly preferable to use Polyacrylamide (PAM) having good flocculation property. The adhesive has flocculation and thickening effects, and can prevent separation between the ink and the mixed solvent.
The solvent in the formula is an additive for diluting the ink, and the PEDOT is subjected to chemical reaction to generate a polymer aqueous solution with high conductivity and other additives for dilution. Further, the solvent is one or more of diethylene glycol butyl ether, tung oil or n-propanol.
The leveling agent in the formula is mainly used for improving the fluidity of the ultraviolet curing ink so that the ink can be leveled on a substrate. If the leveling property is poor, the printed product has the phenomena of orange peel, sagging, shrinkage cavity and the like, so that the printed product not only has poor conductive effect, but also has reduced other performances. Further, the flatting agent is one or more of TEGO Glide100, a pure acrylic flatting agent, ethylene oxide or propylene oxide;
the defoaming agent in the formula is an auxiliary agent capable of eliminating bubbles generated in the stirring of the ultraviolet light curing conductive ink. Because some auxiliary agents in the ink such as surfactant, leveling agent, etc. can generate bubbles during the ink stirring and grinding process. Further, the defoaming agent is one or more of a defoaming agent 6800, a defoaming agent 810, a defoaming agent D105, a defoaming agent T-20GA or a defoaming agent DF-100;
the polymerization inhibitor in the formula is an auxiliary agent for blocking or delaying the curing reaction, can inhibit the thermal polymerization of unsaturated substances, and can avoid equipment from being caked and blocked in the printing process. Further, the polymerization inhibitor is one or more of hydroquinone, phenothiazine, beta-phenyl naphthylamine, methyl hydroquinone THQ or methylene blue.
In a preferred embodiment of the invention, the ink further comprises 5-10% of pigment by mass, and different types of pigments are added, so that the ink can have multiple colors, and the application requirements of occasions can not be met. Whether the pigment is added or not can be determined according to the actual requirement of the water-based UV conductive ink, and the water-based UV conductive ink without the pigment is gloss oil; it may be required to be either or both of an organic pigment and an inorganic pigment.
The invention is further illustrated by the following examples in the course of specific experiments.
Example 1
Step one, synthesis of PEDOT: PEDOT, 40% by mass, was placed in a 1000ml round bottom flask, deionized water, 28% by weight, was added, mechanical stirring was performed at a speed of 400r/min for 10 minutes, then an oxidizing agent, 1% calcium hypochlorite, was poured, the round bottom flask was heated and maintained at 80 ℃ and mechanical stirring was performed at a speed of 800r/min for 50 minutes, and then cooling was performed at normal temperature for 1 hour, thereby producing an aqueous polymer solution having high conductivity.
And secondly, mixing the produced high-conductivity polymer aqueous solution containing 40 mass percent of PEDOT and other additives according to a certain proportion, putting the mixture into a vessel, putting the vessel on an HJ-6A type digital display constant-temperature multi-head magnetic stirrer, heating and stirring the mixture for 1 hour at 65 ℃, and then cooling the mixture for 2 hours at normal temperature to obtain the ink to be prepared. Wherein the auxiliary agent is selected from the following components in percentage by mass: (50nm of 10.9 percent of nano copper powder, 1 percent of hexadecyl trimethyl ammonium bromide serving as a stabilizer, 2-dimethylolpropionic acid serving as an adhesive, 2 percent of TEGO Glide serving as a flatting agent, 100 and 1 percent of TEGO Glide serving as a defoaming agent, 6800 and 0.2 percent of a defoaming agent, 1 percent of hydroquinone serving as a polymerization inhibitor and 15.8 percent of diethylene glycol monobutyl ether serving as a solvent), and no pigment is added to prepare the aqueous UV conductive ink gloss oil.
And thirdly, preheating the glass fiber reinforced PET plate to be printed to 60 ℃, then printing the prepared water-based UV conductive ink on the glass fiber reinforced PET sample strip in an ink-jet printing mode, then putting the printed sample strip into a hot air drying oven for drying and molding for 30 minutes, and finally carrying out ultraviolet curing.
Example 2
Step one, synthesis of PEDOT: PEDOT, 45% by mass, was placed in a 1000ml round bottom flask, deionized water, 10% by weight, was added, mechanical stirring was performed at a speed of 400r/min for 10 minutes, an oxidizing agent, 2% magnesium hypochlorite, was further poured, the round bottom flask was heated and maintained at 60 ℃ and mechanical stirring was performed at a speed of 800r/min for 50 minutes, and then, cooling was performed at normal temperature for 1 hour, thereby producing an aqueous polymer solution having high conductivity.
And secondly, mixing the generated PEDOT high-conductivity polymer aqueous solution and other additives according to a certain proportion, putting the mixture into a vessel, putting the vessel on an HJ-6A type digital display constant-temperature multi-head magnetic stirrer, heating and stirring the mixture for 1 hour at 75 ℃, and then cooling the mixture for 2 hours at normal temperature to obtain the ink to be prepared. Wherein the auxiliary agent is selected from the following components in percentage by mass: (50nm of 16 percent of 99.9 percent of nano copper powder, 0.2 percent of dodecyl trimethyl ammonium bromide serving as a stabilizer, 1 percent of dimethylolbutyric acid serving as an adhesive, 1.8 percent of pure acrylic acid leveling agent serving as a leveling agent, 0.5 percent of defoaming agent 810 serving as a defoaming agent, 0.8 percent of phenothiazine serving as a polymerization inhibitor and 16 percent of tung oil serving as a solvent), and 6.7 percent of organic pigment red 146 is added.
And thirdly, preheating the glass fiber reinforced PET plate to be printed to 85 ℃, then printing the prepared water-based UV conductive ink on the glass fiber reinforced PET sample strip in an ink-jet printing mode, then putting the printed sample strip into a hot air drying oven for drying and molding for 30 minutes, and finally carrying out ultraviolet curing.
Example 3
Step one, synthesis of PEDOT: PEDOT, 45.2% by mass, was placed in a 1000ml round bottom flask, 10% by weight of deionized water was added, mechanical stirring was performed at a speed of 400r/min for 10 minutes, then sodium hypochlorite, 5% by weight of an oxidizing agent, was poured, the round bottom flask was heated and maintained at 70 ℃, mechanical stirring was performed at a speed of 800r/min for 50 minutes, and then, cooling was performed at normal temperature for 1 hour, thereby producing an aqueous polymer solution having high conductivity.
And secondly, mixing the generated PEDOT high-conductivity polymer aqueous solution and other additives according to a certain proportion, putting the mixture into a vessel, putting the vessel on an HJ-6A type digital display constant-temperature multi-head magnetic stirrer, heating and stirring the mixture for 1 hour at the temperature of 80 ℃, and then cooling the mixture for 2 hours at normal temperature to obtain the ink to be prepared. Wherein the auxiliary agent is selected from the following components in percentage by mass: (50nm of 12.9 percent of nano copper powder, 0.5 percent of hexadecyl trimethyl ammonium bromide serving as a stabilizer, 1.5 percent of polyacrylamide serving as an adhesive, 1.5 percent of ethylene oxide serving as a flatting agent, 1 percent of defoaming agent D105 and 0.8 percent of defoaming agent, 1 percent of beta-phenyl naphthylamine serving as a polymerization inhibitor, 18 percent of tung oil serving as a solvent, and 5 percent of phthalocyanine blue simultaneously.
And thirdly, preheating the glass fiber reinforced PET plate to be printed to 90 ℃, then printing the prepared water-based UV conductive ink on the glass fiber reinforced PET sample strip in an ink-jet printing mode, then putting the printed sample strip into a hot air drying oven for drying and molding for 30 minutes, and finally carrying out ultraviolet curing.
Example 4
Step one, synthesis of PEDOT: PEDOT, 50% by mass, was placed in a 1000ml round bottom flask, deionized water, 10% by weight, was added, mechanical stirring was performed at a speed of 400r/min for 10 minutes, an oxidizing agent, 3% calcium hypochlorite, was further poured, the round bottom flask was heated and maintained at 65 ℃ and mechanical stirring was performed at a speed of 800r/min for 50 minutes, and then, cooling was performed at normal temperature for 1 hour, thereby producing an aqueous polymer solution having high conductivity.
And secondly, mixing the generated PEDOT high-conductivity polymer aqueous solution and other additives according to a certain proportion, putting the mixture into a vessel, putting the vessel on an HJ-6A type digital display constant-temperature multi-head magnetic stirrer, heating and stirring the mixture for 1 hour at the temperature of 80 ℃, and then cooling the mixture for 2 hours at normal temperature to obtain the ink to be prepared. Wherein the auxiliary agent is selected from the following components in percentage by mass: (50nm of 99.9 percent of nano copper powder, 18 percent of stabilizer, 1 percent of polyvinylpyrrolidone, 1 percent of polyacrylamide as adhesive, 1 percent of pure acrylic acid leveling agent as leveling agent, 0.2 percent of defoamer DF-100, 0.2 percent of polymerization inhibitor, 0.2 percent of methylene blue and 10.6 percent of n-propanol as solvent) and 5 percent of pigment orange 36 (Kelai HL) are added at the same time.
And thirdly, preheating the glass fiber reinforced PET plate to be printed to 95 ℃, then printing the prepared water-based UV conductive ink on the glass fiber reinforced PET sample strip in an ink-jet printing mode, then putting the printed sample strip into a hot air drying oven for drying and molding for 30 minutes, and finally carrying out ultraviolet curing.
The performance of the aqueous UV conductive ink of the above examples was examined below.
In order to measure the conductivity of the aqueous UV conductive ink, the aqueous UV conductive ink prepared by the embodiment of the invention is respectively inkjet-printed on a circuit board, is put into a hot air drying oven for 30 minutes for drying and forming, is finally cured by ultraviolet light, and is cooled to normal temperature. SEM photographs of the ink film layer of the above example after scanning with a JSM-6460 type scanning electron microscope are specifically SEM photographs of example 1, example 2, example 3, and example 4, as shown in fig. 2, fig. 3, fig. 4, and fig. 5, respectively. Meanwhile, the conductivity of the ink film layer was tested by using the portable conductivity of sensION + EC5, and the conductivity of the ink film layer after tearing was measured after the ink film layer was torn off 30 times by using 4M adhesive tape for each of the above 4 examples.
In example 1, the particles in the ink were large and not dense, and there were large gaps, so the resistance of the film was large, its conductivity was only 0.15X 10-5. omega. cm, and the sheet resistance was 203.1. omega./□ (□ is a sheet resistance printing process, which refers to the edge-to-edge resistance of a square thin film conductive material); in example 3, the conductive polymer particles in the ink are uniform and compact, and a good conductive path can be formed, so that the conductivity of the composite film reaches 5.62X 10-5. omega. cm, the resistance is low, and the square resistance is only 0.23. omega./□. Examples 2 and 4 have conductivities intermediate those of examples 1 and 3, the values of which are detailed in table 1. The experimental results are shown in table 1, and the square resistance and the conductivity of the ink film before and after tearing do not change much, which indicates that the ink has good adhesion.
TABLE 1 Square resistance and conductivity test results before and after 30 times tearing of aqueous UV conductive ink
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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