CN104312263B - A kind of 1,4-porphyrin palladium-diacetylene is as the application of micro-contact printing ink - Google Patents
A kind of 1,4-porphyrin palladium-diacetylene is as the application of micro-contact printing ink Download PDFInfo
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- CN104312263B CN104312263B CN201410619962.5A CN201410619962A CN104312263B CN 104312263 B CN104312263 B CN 104312263B CN 201410619962 A CN201410619962 A CN 201410619962A CN 104312263 B CN104312263 B CN 104312263B
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- 238000000813 microcontact printing Methods 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 82
- -1 poly(diacetylene) Polymers 0.000 claims abstract description 52
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 21
- 238000007772 electroless plating Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000007747 plating Methods 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 13
- 229920001721 polyimide Polymers 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 229920000015 polydiacetylene Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 74
- 239000000976 ink Substances 0.000 description 34
- 238000005516 engineering process Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical group COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IKCQWKJZLSDDSS-UHFFFAOYSA-N 2-formyloxyethyl formate Chemical compound O=COCCOC=O IKCQWKJZLSDDSS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BVWZBWABMQXICU-UHFFFAOYSA-N [Zn].C1(=CC=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Zn].C1(=CC=CC=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 BVWZBWABMQXICU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/001—Printing processes to produce particular kinds of printed work, e.g. patterns using chemical colour-formers or chemical reactions, e.g. leuco dyes or acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemically Coating (AREA)
Abstract
本发明公开了一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，先将基底进行预处理，配制1，4-卟啉钯-丁二炔有机溶液，将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔有机溶液中，再将聚二甲基硅氧烷印章盖于预处理后的基底上，从而基底表面则获得印章上的图案，在基底浸泡于化学镀液中，即可获得金属图案。本发明方法简答，容易操作，并且通过将1，4-卟啉钯-丁二炔有机溶液作为微接触印刷墨水在电子行业常用的基底表面制备金属图案，为微接触印刷行业提供了新思路。The invention discloses the application of 1,4-porphyrin palladium-butadiyne as a micro-contact printing ink. First, the substrate is pretreated to prepare a 1,4-porphyrin palladium-butadiyne organic solution, and the poly(diacetylene) The methylsiloxane stamp was soaked in 1,4-porphyrin palladium-diacetylene organic solution, and then the polydimethylsiloxane stamp was covered on the pretreated substrate, so that the surface of the substrate obtained the The metal pattern can be obtained by immersing the substrate in the electroless plating solution. The method of the present invention is simple and easy to operate, and by using 1,4-porphyrin palladium-diacetylene organic solution as micro-contact printing ink to prepare metal patterns on the substrate surface commonly used in the electronics industry, it provides a new idea for the micro-contact printing industry .
Description
技术领域 technical field
本发明属于现代电子技术领域，特别涉及一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用。 The invention belongs to the field of modern electronic technology, and in particular relates to the application of 1,4-porphyrin palladium-diacetylene as micro-contact printing ink.
背景技术 Background technique
表面微构建技术正逐渐体现出在重要应用价值，特别是微接触印刷技术，其能够在小尺寸上微图案化，在多个领域特别是现代电子技术领域具有重要意义。目前可供选择的微接触印刷墨水较少，也局限了表面可进行微接触印刷的材料，大量的材料无法用微接触印刷的方法制备表面图案。因而开发新的、稳定的的墨水具有很大的意义。 Surface micro-structuring technology is gradually showing important application value, especially micro-contact printing technology, which can be micro-patterned on a small scale, which is of great significance in many fields, especially in the field of modern electronic technology. At present, there are few microcontact printing inks to choose from, and the materials that can be printed on the surface are limited. A large number of materials cannot be prepared with surface patterns by microcontact printing. Therefore, it is of great significance to develop new and stable inks.
专利CN102516841B中公开了八(辛烷氧基)-酞菁锌作为墨水在聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯或聚酰亚胺基底进行微接触印刷的应用技术；专利CN102964909B中公开了水溶性的5，10，15，20-四4-(3’-丙氧基吡啶溴化盐)苯基]卟啉锌在聚对苯二甲酸乙二酯基底上进行微接触印刷中的应用技术；专利CN102964910B中公开了水溶性的5，10，15，20-四磺酸钠苯基卟啉锌在聚酰亚胺基底进行微接触印刷的应用技术。为进一步提升微接触印刷质量，丰富微接触印刷墨水和基底的选择性，申请人开发金属卟啉配合物在微接触印刷中的应用。 Patent CN102516841B discloses octa(octyloxy)-zinc phthalocyanine as ink for microcontact printing on polyethylene terephthalate, polyethylene naphthalate or polyimide substrates; patent Disclosed in CN102964909B is water-soluble 5,10,15,20-tetra4-(3'-propoxypyridinium bromide) phenyl]porphyrin zinc on a polyethylene terephthalate substrate for microcontact Application technology in printing; patent CN102964910B discloses the application technology of water-soluble 5,10,15,20-sodium tetrasulfonate phenylporphyrin zinc on polyimide substrate for microcontact printing. In order to further improve the quality of microcontact printing and enrich the selectivity of microcontact printing inks and substrates, the applicant developed the application of metalloporphyrin complexes in microcontact printing.
在微接触印刷中，化学镀是制备精美金属图案的重要步骤，一般在这一步中需要加入氯化钯和氯化锡等催化剂以使化学镀成为自发反应过程，否则化学镀无法进行。为了简化工艺，减少引入催化剂过程可能带来的墨水膨胀、扩散等问题，获得更精细的金属图案，开发一种新的能够对化学镀过程具有催化作用的微接触印刷墨水很有必要。 In microcontact printing, electroless plating is an important step in preparing exquisite metal patterns. Generally, catalysts such as palladium chloride and tin chloride need to be added in this step to make electroless plating a spontaneous reaction process, otherwise electroless plating cannot be performed. In order to simplify the process, reduce ink expansion, diffusion and other problems that may be caused by the introduction of catalysts, and obtain finer metal patterns, it is necessary to develop a new microcontact printing ink that can catalyze the electroless plating process.
发明内容 Contents of the invention
本发明的目的是提供一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，1，4-卟啉钯-丁二炔作为一种新的墨水在基底上进行微接触印刷，获得精美图案，简化了工艺，同时避免催化剂的引入而导致印刷墨水膨胀、扩散的问题，大大提高了微接触印刷质量，丰富微接触印刷墨水和基底的选择。 The purpose of the present invention is to provide a kind of 1,4-porphyrin palladium-butadiyne as the application of microcontact printing ink, 1,4-porphyrin palladium-butadiyne carries out microcontact on the substrate as a kind of new ink Printing can obtain exquisite patterns, simplify the process, and avoid the problems of printing ink expansion and diffusion caused by the introduction of catalysts, greatly improve the quality of microcontact printing, and enrich the selection of microcontact printing inks and substrates.
本发明提供的技术方案是： The technical scheme provided by the invention is:
一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，将1，4-卟啉钯-丁二炔有机溶液涂布于具有图案的印章上，然后转印于基底后进行显影，既得所转印图案。 An application of 1,4-porphyrin palladium-butadiyne as a micro-contact printing ink, coating 1,4-porphyrin palladium-butadiyne organic solution on a stamp with a pattern, and then transferring it to the substrate Develop to obtain the transferred pattern.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，所述基底选自聚四氟乙烯、聚对苯二甲酸乙二酯基底或聚酰亚胺中的一种。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the substrate is selected from polytetrafluoroethylene, polyethylene terephthalate substrate or polyimide One of.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，所述1，4-卟啉钯-丁二炔的结构特征如下： Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the structural characteristics of the 1,4-porphyrin palladium-butadiyne are as follows:
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，还包括以下步骤： Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the following steps are also included:
步骤一、将80-150g的浸泡在1-3％硅烷偶联剂中20-30小时，取出，用60-75％乙醇溶液对基底进行清洗，干燥；将基底放入容器中加入溶液一，在80-100℃下反应1-3小时，得到预处理的基底； Step 1. Soak 80-150g in 1-3% silane coupling agent for 20-30 hours, take it out, clean the substrate with 60-75% ethanol solution, and dry it; put the substrate into the container and add solution 1, React at 80-100°C for 1-3 hours to obtain a pretreated substrate;
步骤二、取1-10g的1，4-卟啉钯-丁二炔溶解于50-100ml有机溶剂中，得到浓度为1-10g/L的1，4-卟啉钯-丁二炔有机溶液； Step 2: Take 1-10g of 1,4-porphyrin palladium-butadiyne and dissolve it in 50-100ml organic solvent to obtain a 1-10g/L 1,4-porphyrin palladium-butadiyne organic solution ;
步骤三、将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔有机溶液中30-40s，干燥，得到涂有1，4-卟啉钯-丁二炔二有机溶液的聚二甲基硅氧烷印章，并将所述印章盖于预处理后的基底上，轻压10-20s，将聚二甲基硅氧烷印章图案转移至基底表面，得到印有图案的基底； Step 3. Soak the polydimethylsiloxane stamp in the organic solution of 1,4-porphyrin palladium-diacetylene for 30-40s, and dry it to obtain the stamp coated with 1,4-porphyrin palladium-diacetylene Solution polydimethylsiloxane stamp, and cover the stamp on the pretreated substrate, press lightly for 10-20s, transfer the polydimethylsiloxane stamp pattern to the surface of the substrate, and obtain a printed pattern base;
步骤四、化学镀制备金属图案，将印有图案的基底放于化学镀液中，1-10min后取出，即可在基底上得到转印的金属图案。 Step 4: Electroless plating to prepare a metal pattern, put the substrate printed with the pattern in the electroless plating solution, take it out after 1-10 minutes, and the transferred metal pattern can be obtained on the substrate.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，所述，4-卟啉钯-丁二炔的结构特征如下： Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the structural characteristics of the 4-porphyrin palladium-butadiyne are as follows:
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤一中浸泡基底前，先将基底用60-75％的乙醇超声清洗0.5-1.5小时，取出，80-100℃真空干燥。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, before soaking the substrate in step 1, the substrate is ultrasonically cleaned with 60-75% ethanol for 0.5-1.5 hours, Take it out and dry it under vacuum at 80-100°C.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤一所述硅烷偶联剂为乙烯基三(β-甲氧基乙氧基)硅烷溶液或丁二烯基三乙氧基硅烷溶液。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the silane coupling agent in step one is vinyl tris (β-methoxyethoxy) silane solution or butadienyltriethoxysilane solution.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤一中所述溶液一的制备为将1-3g甲基丙烯酸和0.05-0.2g偶氮二异丁腈溶于500-600ml蒸馏水中。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the preparation of the solution one in the step one is to mix 1-3g methacrylic acid and 0.05-0.2g azo Dissolve diisobutyronitrile in 500-600ml distilled water.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤二中所述有机溶剂为二氯甲烷溶液或二甲基亚砜溶液。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the organic solvent in step 2 is a dichloromethane solution or a dimethyl sulfoxide solution.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤三所述干燥为将浸泡于1，4-卟啉钯-丁二炔二氯甲烷溶液的聚二甲基硅氧烷印章取出后于N2气流中干燥30-60s。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the drying described in step 3 is to soak in the 1,4-porphyrin palladium-butadiyne dichloromethane solution The polydimethylsiloxane stamp was taken out and dried in N 2 airflow for 30-60s.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤四所述化学镀液选自化学镀铜液、化学镀银液或化学镀镍液中的一种。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the electroless plating solution described in step 4 is selected from an electroless copper plating solution, an electroless silver plating solution or an electroless nickel plating solution kind of.
本发明的有益效果是：本发明将1，4-卟啉钯-丁二炔有机溶液作为微接触印刷墨水，在电子行业中常用的基底表面上制备金属图案，为微接触印刷行业提供了新思路；本发明中通过硅烷偶联剂引入聚丙烯酸，这种改性方法是在基底表面进行，不影响基底的化学结构，因此与水解得到羧基的方法相比更利于保护基底的性能；同时本发明的方法简单，操作简便，1，4-卟啉钯-丁二炔有机溶液原料易得、成本低、且效果稳定，在工业应用上具有很大的潜力。 The beneficial effects of the present invention are: the present invention uses 1,4-porphyrin palladium-diacetylene organic solution as micro-contact printing ink to prepare metal patterns on the surface of substrates commonly used in the electronics industry, providing a new micro-contact printing industry. Idea; In the present invention, polyacrylic acid is introduced through silane coupling agent. This modification method is carried out on the surface of the substrate without affecting the chemical structure of the substrate. Therefore, it is more beneficial to protect the performance of the substrate than the method of obtaining carboxyl groups by hydrolysis; The inventive method is simple and easy to operate, the raw material of the 1,4-porphyrin palladium-butadiyne organic solution is easy to obtain, the cost is low, and the effect is stable, so it has great potential in industrial application.
具体实施方式 detailed description
下面对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。 The present invention will be described in further detail below, so that those skilled in the art can implement it with reference to the description.
一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，将1，4-卟啉钯-丁二炔有机溶液涂布于具有图案的印章上，然后转印于基底后进行显影，既得所转印图案。 An application of 1,4-porphyrin palladium-butadiyne as a micro-contact printing ink, coating 1,4-porphyrin palladium-butadiyne organic solution on a stamp with a pattern, and then transferring it to the substrate Develop to obtain the transferred pattern.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，所述基底选自聚四氟乙烯、聚对苯二甲酸乙二酯基底或聚酰亚胺中的一种。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the substrate is selected from polytetrafluoroethylene, polyethylene terephthalate substrate or polyimide One of.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，所述1，4-卟啉钯-丁二炔的结构特征如下： Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the structural characteristics of the 1,4-porphyrin palladium-butadiyne are as follows:
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，还包括以下步骤： Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the following steps are also included:
步骤一、先将80-150g基底用60-75％的乙醇超声清洗0.5-1.5小时，取出，在80-100℃真空度为0.2-0.5MPa的条件下干燥，将基底浸泡在1-3％硅烷偶联剂中20-30小时，取出，用60-75％乙醇溶液清洗，在80-100℃0.1MPa的条件下干燥；然后将基底放入容器中，加入溶液一，所述溶液一为将1-3g甲基丙烯酸和0.05-0.2g偶氮二异丁腈溶于500-600ml蒸馏水中得到的溶液，在80-100℃下反应1-3小时，得到预处理的基底；通过硅烷偶联剂的化学键合作用在聚四氟乙烯基底表面引入丙烯酸聚合物，与通过水解反应得到的羧基化表面相比，其具有的大量羧基可以吸附结合更多的1，4-卟啉钯-丁二炔，为下一步化学镀提供更强的催化作用，得到结合更紧密的金属线路；且通过改变聚合反应的参数，可以调整引入的丙烯酸单元数量，因此可以很容易地根据产物要求对参数进行调整。 Step 1: Clean 80-150g of the substrate with 60-75% ethanol ultrasonically for 0.5-1.5 hours, take it out, dry it at 80-100°C under a vacuum of 0.2-0.5MPa, soak the substrate in 1-3% silane coupling agent for 20-30 hours, take it out, wash it with 60-75% ethanol solution, and dry it under the condition of 80-100℃0.1MPa; then put the substrate into the container, add solution one, the solution one is Dissolve 1-3g of methacrylic acid and 0.05-0.2g of azobisisobutyronitrile in 500-600ml of distilled water and react at 80-100°C for 1-3 hours to obtain a pretreated substrate; through a silane coupling agent The chemical bonding effect introduced acrylic polymer on the surface of polytetrafluoroethylene substrate, compared with the carboxylated surface obtained by hydrolysis reaction, it has a large number of carboxyl groups that can adsorb and bind more 1,4-porphyrin palladium-butadiyne , to provide a stronger catalytic effect for the next step of electroless plating, and to obtain a tighter metal circuit; and by changing the parameters of the polymerization reaction, the number of acrylic acid units introduced can be adjusted, so the parameters can be easily adjusted according to the product requirements.
步骤二、取1-10g的1，4-卟啉钯-丁二炔溶解于50-100ml有机溶剂中，得到浓度为1-10g/L的1，4-卟啉钯-丁二炔二有机溶液；相对于单一卟啉配合物，1，4-卟啉钯-丁二炔具有一些特殊性质，其结构中的两个卟啉配合物和起桥联作用的丁二炔都在同一平面上，形成更大的共轭体系，其π-π键作用更强，所以在成膜时具有很强的稳定性；同时可反应的位点更多，可以根据需要引入新的基团调节其物理化学性能。 Step 2: Dissolve 1-10g of 1,4-porphyrin palladium-butadiyne in 50-100ml of organic solvent to obtain 1-10g/L 1,4-porphyrin palladium-butadiyne diorganic Solution; Compared with a single porphyrin complex, 1,4-porphyrin palladium-diacetylene has some special properties, and the two porphyrin complexes in its structure and the bridging diacetylene are all on the same plane , form a larger conjugated system, and its π-π bond is stronger, so it has strong stability when forming a film; at the same time, there are more reactive sites, and new groups can be introduced to adjust its physical properties. chemical properties.
步骤三、将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔有机溶液中30-40s，取出后于N2气流中干燥30-60s，得到涂有1，4-卟啉钯-丁二炔有机溶液的聚二甲基硅氧烷印章，并将所述印章盖于预处理后的基底上，轻压10-20s，将聚二甲基硅氧烷印章图案转移至基底表面，得到印有图案的基底； Step 3. Soak the polydimethylsiloxane stamp in 1,4-porphyrin palladium-diacetylene organic solution for 30-40s, take it out and dry it in N 2 airflow for 30-60s to obtain 1,4-coated -Polydimethylsiloxane stamp of porphyrin palladium-diacetylene organic solution, and cover the stamp on the pretreated substrate, press lightly for 10-20s, and the polydimethylsiloxane stamp pattern Transfer to the substrate surface to obtain a patterned substrate;
步骤四、化学镀制备金属图案，将印有图案的基底放于化学镀液中，1-10min后取出，即可在基底上得到转印的金属图案。 Step 4: Electroless plating to prepare a metal pattern, put the substrate printed with the pattern in the electroless plating solution, take it out after 1-10 minutes, and the transferred metal pattern can be obtained on the substrate.
所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤一所述硅烷偶联剂为乙烯基三(β-甲氧基乙氧基)硅烷溶液或丁二烯基三乙氧基硅烷溶液。 In the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the silane coupling agent in step one is vinyl tris (β-methoxyethoxy) silane solution or butadiene Triethoxysilane solution.
优选的是，所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤二中所述有机溶剂为二氯甲烷溶液或二甲基亚砜溶液。 Preferably, in the application of the 1,4-porphyrin palladium-butadiyne as a microcontact printing ink, the organic solvent in step 2 is a dichloromethane solution or a dimethyl sulfoxide solution.
所述1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用中，步骤四所述化学镀液选自化学镀铜液、化学镀银液或化学镀镍液中的一种。其中，所述化学镀铜液由4-6wt％硫酸铜、6-8wt％酒石酸钾钠、5-7wt％氢氧化钠、30-33wt％甲醛和46-55wt％蒸馏水制备得到；所述化学镀银液由5-7wt％溴化银、20-28wt％硫代硫酸铵、3-4wt％醋酸铵、7-9wt％亚硫酸钠和52-65wt％蒸馏水制备得到；化学镀镍液由4-8wt％硫酸镍、4-8wt％次磷酸钠、30-35wt％柠檬酸和49-51wt％蒸馏水制备得到。 In the application of the 1,4-porphyrin palladium-diacetylene as microcontact printing ink, the electroless plating solution in step 4 is selected from one of electroless copper plating solution, electroless silver plating solution or electroless nickel plating solution. Wherein, the electroless copper plating solution is prepared by 4-6wt% copper sulfate, 6-8wt% potassium sodium tartrate, 5-7wt% sodium hydroxide, 30-33wt% formaldehyde and 46-55wt% distilled water; the electroless plating The silver solution is prepared from 5-7wt% silver bromide, 20-28wt% ammonium thiosulfate, 3-4wt% ammonium acetate, 7-9wt% sodium sulfite and 52-65wt% distilled water; the electroless nickel plating solution is prepared from 4-8wt% It is prepared by nickel sulfate, 4-8wt% sodium hypophosphite, 30-35wt% citric acid and 49-51wt% distilled water.
实施例1 Example 1
一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，包括以下步骤： A kind of 1, the application of 4-porphyrin palladium-butadiyne as microcontact printing ink, comprises the following steps:
步骤一、先将80g聚四氟乙烯基底用75％的乙醇超声清洗1小时，取出，在80℃真空度为0.2MPa的条件下干燥，将聚四氟乙烯基底浸泡在1％乙烯基三(β-甲氧基乙氧基)硅烷溶液中30小时，取出，用75％乙醇溶液清洗，在80℃0.1MPa的条件下干燥；然后将聚四氟乙烯基底放入容器中，加入溶液一，所述溶液一为将1g甲基丙烯酸和0.1g偶氮二异丁腈溶于500m1蒸馏水中得到的溶液，在80℃下反应3小时，得到预处理的聚四氟乙烯基底； Step 1, first 80g polytetrafluoroethylene substrate is ultrasonically cleaned with 75% ethanol for 1 hour, taken out, dried under the condition of 0.2MPa vacuum degree at 80°C, soaking the polytetrafluoroethylene substrate in 1% vinyl tri( β-methoxyethoxy)silane solution for 30 hours, take it out, wash it with 75% ethanol solution, and dry it at 80°C at 0.1MPa; then put the polytetrafluoroethylene substrate into the container, add solution one, The first solution is a solution obtained by dissolving 1 g of methacrylic acid and 0.1 g of azobisisobutyronitrile in 500 ml of distilled water, and reacting at 80° C. for 3 hours to obtain a pretreated polytetrafluoroethylene substrate;
步骤二、取1-10g的1，4-卟啉钯-丁二炔溶解于50-100ml二氯甲烷溶液中，得到浓度为1-10g/L的1，4-卟啉钯-丁二炔二氯甲烷溶液； Step 2: Take 1-10g of 1,4-porphyrin palladium-butadiyne and dissolve it in 50-100ml of dichloromethane solution to obtain 1,4-porphyrin palladium-butadiyne with a concentration of 1-10g/L Dichloromethane solution;
步骤三、将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔二氯甲烷溶液中40s，取出后于N2气流中干燥40s，得到涂有1，4-卟啉钯-丁二炔二氯甲烷溶液的聚二甲基硅氧烷印章，并将所述印章盖于预处理后的聚四氟乙烯基底上，轻压20s，将聚二甲基硅氧烷印章图案转移至聚四氟乙烯基底表面，得到印有图案的聚四氟乙烯基底； Step 3. Soak the polydimethylsiloxane stamp in 1,4-porphyrin palladium-diacetylene dichloromethane solution for 40s, take it out and dry it in N2 airflow for 40s to obtain the stamp coated with 1,4-porphyrin The polydimethylsiloxane stamp of palladium phylloline-diacetylene dichloromethane solution, and cover the stamp on the pretreated polytetrafluoroethylene substrate, press lightly for 20s, and the polydimethylsiloxane The stamp pattern is transferred to the surface of the polytetrafluoroethylene substrate to obtain a patterned polytetrafluoroethylene substrate;
步骤四、化学镀制备金属铜图案，将印有图案的聚四氟乙烯基底放于化学镀铜液中，所述化学镀铜液由6wt％硫酸铜溶液、7wt％酒石酸钾钠溶液、6wt％氢氧化钠溶液、31wt％甲醛溶液和余量的蒸馏水制备得到；5min后取出聚四氟乙烯基底，即可在聚四氟乙烯基底上得到金属铜图案。 Step 4, electroless plating prepares metallic copper pattern, puts the polytetrafluoroethylene substrate printed with pattern in chemical copper plating solution, described chemical copper plating solution consists of 6wt% copper sulfate solution, 7wt% potassium sodium tartrate solution, 6wt% Sodium hydroxide solution, 31wt% formaldehyde solution and the rest of distilled water were prepared; after 5 minutes, the polytetrafluoroethylene substrate was taken out, and a metal copper pattern could be obtained on the polytetrafluoroethylene substrate.
实施例2 Example 2
一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，包括以下步骤： A kind of 1, the application of 4-porphyrin palladium-butadiyne as microcontact printing ink, comprises the following steps:
步骤一、先将100g聚对苯二甲酸乙二酯基底用75％的乙醇超声清洗1小时，取出，在80℃真空度为0.1MPa的条件下干燥，将聚对苯二甲酸乙二酯基底浸泡在1％乙烯基三(β-甲氧基乙氧基)硅烷溶液中24小时，取出，用75％乙醇溶液清洗，在80℃真空度为0.1MPa的条件下干燥；然后将聚对苯二甲酸乙二酯基底放入容器中，加入溶液一，所述溶液一为将1.5g甲基丙烯酸和0.1g偶氮二异丁腈溶于500ml蒸馏水中制备得到的溶液，在80℃下反应1小时，得到预处理的聚对苯二甲酸乙二酯基底； Step 1: Clean 100g of polyethylene terephthalate substrate with 75% ethanol ultrasonically for 1 hour, take it out, and dry it at 80°C under a vacuum of 0.1MPa, and then clean the polyethylene terephthalate substrate Soak in 1% vinyl tris (β-methoxyethoxy) silane solution for 24 hours, take it out, wash it with 75% ethanol solution, and dry it at 80°C under a vacuum of 0.1MPa; then polypylene Put the ethylene glycol diformate substrate into the container, add solution 1, the solution 1 is a solution prepared by dissolving 1.5g of methacrylic acid and 0.1g of azobisisobutyronitrile in 500ml of distilled water, and react at 80°C for 1 hour , to obtain a pretreated polyethylene terephthalate substrate;
步骤二、取10g的1，4-卟啉钯-丁二炔溶解于100ml二氯甲烷溶液中，得到浓度为10g/L的1，4-卟啉钯-丁二炔二氯甲烷溶液； Step 2, take 10g of 1,4-porphyrin palladium-butadiyne and dissolve it in 100ml of dichloromethane solution to obtain a 1,4-porphyrin palladium-butadiyne dichloromethane solution with a concentration of 10g/L;
步骤三、将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔二氯甲烷溶液中40s，取出后于N2气流中干燥60s，得到涂有1，4-卟啉钯-丁二炔二氯甲烷溶液的聚二甲基硅氧烷印章，并将所述印章盖于预处理后的聚对苯二甲酸乙二酯基底上，轻压20s，将聚二甲基硅氧烷印章图案转移至聚对苯二甲酸乙二酯基底表面，得到印有图案的聚对苯二甲酸乙二酯基底； Step 3. Soak the polydimethylsiloxane stamp in 1,4-porphyrin palladium-diacetylene dichloromethane solution for 40s, take it out and dry it in N2 airflow for 60s to obtain the stamp coated with 1,4-porphyrin The polydimethylsiloxane stamp of the palladium morphine-diacetylene dichloromethane solution, and the stamp is covered on the pretreated polyethylene terephthalate substrate, and lightly pressed for 20s, the polydimethylsiloxane The base siloxane stamp pattern is transferred to the surface of the polyethylene terephthalate substrate to obtain the polyethylene terephthalate substrate printed with the pattern;
步骤四、化学镀制备金属银图案，将印有图案的聚对苯二甲酸乙二酯基底放于化学镀镍液中，所述化学镀银液由6wt％溴化银、25wt％硫代硫酸铵、3wt％醋酸铵、8wt％亚硫酸钠和60wt％蒸馏水制备得到制备得到；8min后取出聚对苯二甲酸乙二酯基底，即可在聚对苯二甲酸乙二酯基底上得到金属银图案。 Step 4, electroless plating prepares metallic silver pattern, puts the polyethylene terephthalate base printed with pattern in chemical nickel plating solution, and described chemical silver plating solution is made of 6wt% silver bromide, 25wt% thiosulfuric acid Ammonium, 3wt% ammonium acetate, 8wt% sodium sulfite and 60wt% distilled water were prepared; after 8 minutes, the polyethylene terephthalate substrate was taken out to obtain a metallic silver pattern on the polyethylene terephthalate substrate.
实施例3 Example 3
一种1，4-卟啉钯-丁二炔作为微接触印刷墨水的应用，包括以下步骤： A kind of 1, the application of 4-porphyrin palladium-butadiyne as microcontact printing ink, comprises the following steps:
步骤一、先将150g聚酰亚胺基底用65％的乙醇超声清洗1.5小时，取出，在100℃真空度为0.4MPa的条件下干燥，将聚酰亚胺基底浸泡在2％丁二烯基三乙氧基硅烷溶液中30小时，取出，用65％乙醇溶液清洗，在90℃真空度为0.1MPa的条件下干燥；然后将聚酰亚胺基底放入容器中，加入溶液一，所述溶液一为将2g甲基丙烯酸和0.2g偶氮二异丁腈溶于600ml蒸馏水中得到的溶液，在90℃下反应2小时，得到预处理的聚酰亚胺基底； Step 1. First, ultrasonically clean 150g of polyimide substrate with 65% ethanol for 1.5 hours, take it out, and dry it at 100°C under a vacuum of 0.4MPa. Soak the polyimide substrate in 2% butadiene In the triethoxysilane solution for 30 hours, take it out, wash it with 65% ethanol solution, and dry it at 90°C under a vacuum of 0.1 MPa; then put the polyimide substrate into the container, add solution 1, and Solution 1 is a solution obtained by dissolving 2 g of methacrylic acid and 0.2 g of azobisisobutyronitrile in 600 ml of distilled water, and reacting at 90° C. for 2 hours to obtain a pretreated polyimide substrate;
步骤二、取5g的1，4-卟啉钯-丁二炔溶解于80ml二甲基亚砜溶液中，得到浓度为5g/L的1，4-卟啉钯-丁二炔二甲基亚砜溶液； Step 2, get 5g of 1,4-porphyrin palladium-butadiyne and dissolve it in 80ml dimethyl sulfoxide solution to obtain 1,4-porphyrin palladium-butadiyne dimethyl sulfoxide with a concentration of 5g/L Sulfone solution;
步骤三、将聚二甲基硅氧烷印章浸泡于1，4-卟啉钯-丁二炔二甲基亚砜溶液中35s，取出后于N2气流中干燥50s，得到涂有1，4-卟啉钯-丁二炔二甲基亚砜溶液的聚二甲基硅氧烷印章，并将所述印章盖于预处理后的聚酰亚胺基底上，轻压15s，将聚二甲基硅氧烷印章图案转移至聚聚酰亚胺基底表面，得到印有图案的聚酰亚胺基底； Step 3. Soak the polydimethylsiloxane stamp in 1,4-porphyrin palladium-diacetylene dimethyl sulfoxide solution for 35s, take it out and dry it in N2 air flow for 50s to obtain a 1,4-coated stamp. -Polydimethylsiloxane stamp of porphyrin palladium-diacetylene dimethyl sulfoxide solution, and cover the stamp on the pretreated polyimide substrate, press lightly for 15s, and polydimethylsiloxane The base siloxane stamp pattern is transferred to the surface of the polyimide substrate to obtain a patterned polyimide substrate;
步骤四、化学镀制备金属镍图案，将印有图案的聚四氟乙烯基底放于化学镀铜液中，化学镀镍液由7wt％硫酸镍、8wt％次磷酸钠、35wt％柠檬酸和50wt％蒸馏水制备得到；10min后取出聚四氟乙烯基底，即可在聚酰亚胺基底上得到金属镍图案。 Step 4, electroless plating prepares metallic nickel pattern, the polytetrafluoroethylene substrate that is printed with pattern is placed in electroless copper plating solution, and electroless nickel plating solution is made of 7wt% nickel sulfate, 8wt% sodium hypophosphite, 35wt% citric acid and 50wt% % distilled water; take out the polytetrafluoroethylene substrate after 10 minutes, and the metal nickel pattern can be obtained on the polyimide substrate.
本发明制备方法简单，操作简便，降低成本，为微接触印刷技术提供了一种新型墨水，扩大微接触印刷技术的使用范围，在工业应用上具有很大的潜力。 The invention has the advantages of simple preparation method, convenient operation and low cost, provides a new type of ink for the micro-contact printing technology, expands the application range of the micro-contact printing technology, and has great potential in industrial application.
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。 Although the embodiment of the present invention has been disclosed as above, it is not limited to the use listed in the specification and implementation, it can be applied to various fields suitable for the present invention, and it can be easily understood by those skilled in the art Therefore, the invention is not limited to the specific details without departing from the general concept defined by the claims and their equivalents.
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