CN113402923B - 3D laser photosensitive printing conductive ink for integrated circuit and preparation method thereof - Google Patents
3D laser photosensitive printing conductive ink for integrated circuit and preparation method thereof Download PDFInfo
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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
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C09D11/52—Electrically conductive inks
Abstract
The application belongs to the field of conductive ink, and particularly relates to 3D laser photosensitive printing conductive ink for an integrated circuit and a preparation method thereof. The preparation raw materials of the 3D laser photosensitive printing conductive ink for the integrated circuit comprise, by weight, 70-90 parts of conductive paste, 5-25 parts of epoxy resin composition, 1-10 parts of regulator, 1-5 parts of dispersant, 1-5 parts of photoinitiator and 0.5-2 parts of catalyst; the raw materials for preparing the conductive paste comprise a conductive agent, an N-methyl pyrrolidone solution of modified polyurea, oxetane, cellulose acrylate, an interfacial agent and N-methyl pyrrolidone. The application provides a photosensitive printing conductive ink of 3D laser for integrated circuit, electrically conductive stability is good, adhesive force is strong.
Description
Technical Field
The application belongs to the field of conductive ink, and particularly relates to 3D laser photosensitive printing conductive ink for an integrated circuit and a preparation method thereof.
Background
In recent years, electronic products are increasingly miniaturized, flexible and wearable. The novel electronic device has the characteristics of light weight, integration and the like, and also has higher requirements on the preparation process of the device, low cost, environmental protection, no pollution, cyclic utilization, simple preparation, short production period, large-scale production and the like. Photolithography is the most common method for preparing conductive patterns in traditional flexible microelectronic products, but the method is complicated in process, time-consuming, high in cost and has certain pollution to the environment. The novel 3D laser photosensitive printing technology is simple in process and short in period, and provides possibility for large-scale preparation of integrated circuits.
The conductive ink is a core part influencing the quality of the 3D laser photosensitive printing technology, and the main components comprise a binder and a conductive agent. The binder used in the conductive ink is mainly natural resin such as rosin and amber and synthetic resin such as epoxy resin and phenol resin, and the conductivity of these resin materials is low. The conductive agent mainly comprises metal powder, conductive carbon material and conductive high molecular material, and the conductive agent is mainly dispersed in the adhesive to realize current conduction. The price of the nano silver is high, the nano copper is easy to oxidize, and the nano silver and the nano copper are easy to agglomerate and flocculate, so that the conductivity is reduced. Due to the fact that the graphene and the carbon nano tubes have high specific surface area, a conductive network is easy to form, extremely low resistivity and good flexibility are achieved, and the addition of the graphene and the carbon nano tubes can improve the conductivity and the printability of the conductive ink and can be widely applied. However, due to strong van der waals force and pi-pi interaction between graphene and carbon nanotubes, agglomeration is easy to occur, the dispersibility is poor, and in addition, the surfaces of graphene and carbon nanotubes are inert and have limited dispersibility in solvents and resins, so that the graphene and carbon nanotubes are difficult to disperse in the resins and have poor compatibility with the resins, the conductive stability of the conductive ink is reduced, and the adhesion of the conductive ink is also reduced.
In view of the above technical defects, the applicant believes that it is urgently needed to develop a 3D laser photosensitive printing conductive ink for integrated circuits, which has good conductive stability and strong adhesion.
Disclosure of Invention
In order to improve the conductive stability and the adhesive force, the application provides a 3D laser photosensitive printing conductive ink for an integrated circuit and a first aspect of a preparation method thereof, and the application provides a 3D laser photosensitive printing conductive ink for an integrated circuit, which adopts the following technical scheme:
A3D laser photosensitive printing conductive ink for integrated circuits is prepared from (by weight parts) conductive slurry 70-90, epoxy resin composition 5-25, regulator 1-10, dispersant 1-5, photoinitiator 1-5, and catalyst 0.5-2; the raw materials for preparing the conductive paste comprise a conductive agent, an N-methyl pyrrolidone solution of modified polyurea, oxetane, cellulose acrylate, an interfacial agent and N-methyl pyrrolidone; the mass ratio of the conductive agent to the N-methyl pyrrolidone solution of the modified polyurea to the oxetane to the cellulose acrylate to the interfacial agent to the N-methyl pyrrolidone is (75-85): (5-8): (4-6): (4-6): (4-6): (5-10).
By adopting the technical scheme, the arrangement of the conductive agent in the conductive ink is adjusted under the combined action of the oxetane and the cellulose acrylate, the dispersity of the conductive agent is improved, and the stability of the conductive slurry is improved, so that the conductivity and the conductive stability of the conductive ink are improved. The interfacial agent improves the surface performance of the conductive agent, the N-methylpyrrolidone solution of the modified polyurea effectively prevents the conductive agent from settling by utilizing the three-dimensional network structure of the N-methylpyrrolidone solution of the modified polyurea, and the interfacial agent and the N-methylpyrrolidone solution of the modified polyurea act together, so that the compatibility of the conductive agent and the epoxy resin composition is improved, the osmotic wettability of the conductive slurry is also improved, the shrinkage rate of the epoxy resin composition is reduced, and the adhesive force between the conductive ink and the base material is improved.
Preferably, the epoxy resin composition comprises dicyclopentadiene phenol epoxy resin and neopentyl glycol glycidyl ester epoxy resin; the mass ratio of the dicyclopentadiene phenol epoxy resin to the neopentyl glycol glycidyl ester epoxy resin is (1-2): 1.
by adopting the technical scheme, the dicyclopentadiene phenol epoxy resin and the neopentyl glycol glycidyl ester epoxy resin both have a polycyclic structure, the regularity of the epoxy resin composition is reduced, and the shrinkage rate of the epoxy resin composition is smaller. The dicyclopentadiene phenol epoxy resin and the neopentyl glycol glycidyl ester epoxy resin act together, so that the compatibility of the epoxy resin composition and the conductive agent is improved, the conductive agent is more stably fixed on a carrier of the epoxy resin composition, and the conductive stability of the conductive ink and the adhesive force between the conductive ink and a base material are further improved.
Preferably, the dicyclopentadiene phenol epoxy resin has an epoxy equivalent weight of 128 to 140 g/eq.
By adopting the technical scheme, the dicyclopentadiene phenol epoxy resin with the epoxy equivalent of 128-140 g/eq has small epoxy equivalent, and can improve the curing crosslinking rate and the film-forming crosslinking compactness when the conductive ink is formed into a film, so that the adhesive force of the conductive ink printed on a base material is improved, and especially the adhesive force of the conductive ink in acid, alkali and alcohol solution environments is improved.
Preferably, the neopentyl glycol glycidyl ester epoxy resin has a viscosity of 100 to 500mpa.s at 25 ℃.
By adopting the technical scheme, the neopentyl glycol glycidyl ester epoxy resin with the viscosity of 100-500mPa.s at 25 ℃ has an active dilution effect, the viscosity of the conductive ink is reduced, the conductive ink can be printed on a base material more uniformly, the dispersibility of the conductive slurry can be improved, and the conductive stability of the conductive ink can be improved.
Preferably, the interfacial agent comprises a triazole compound, an aluminate coupling agent and methacryloyloxyethyl succinate monoester; the mass ratio of the triazole compound, the aluminate coupling agent and the methacryloyloxyethyl succinate monoester is (0.2-0.4): 1 (0.3-0.5).
By adopting the technical scheme, the triazole compound can capture copper ions and the like introduced in the manufacturing process of the integrated circuit, the problem of conductivity reduction caused by the copper ions is reduced, and the conductivity stability is improved. The methacrylic acyloxy ethyl succinic acid monoester and the epoxy resin composition act together, so that the bonding performance of the conductive ink is improved, and the adhesive force between the conductive ink and the PI base material is improved. The aluminate coupling agent improves the compatibility of the conductive agent with the epoxy resin composition. The triazole compound, the aluminate coupling agent and the methacryloyloxyethyl succinate monoester have synergistic effect, so that the conductive stability of the conductive ink and the adhesive force between the conductive ink and the PI substrate are further improved, and the acid resistance, alkali resistance and alcohol resistance of the conductive ink are also improved.
The viscosity of the monoacid methacrylate is lower, which is more beneficial for the N-methyl pyrrolidone solution of the modified polyurea to form a three-dimensional network structure and improves the stability of the three-dimensional network structure, thereby further improving the effect of the N-methyl pyrrolidone solution of the modified polyurea on the conductive agent.
As used herein, the aluminate coupling agent is selected from one or more of DL-411, NXH-820 and UP-802.
Preferably, the triazole compound is benzotriazole carboxylic acid.
Preferably, the conductive agent comprises graphene, carbon nanotubes and nano silver; the mass ratio of the graphene to the carbon nano tube to the nano silver is (0.4-0.6) to 1 (0.4-0.6).
By adopting the technical scheme, the graphene, the carbon nano tube and the nano silver are jointly used as the conductive agent, so that the production cost can be reduced, the contact resistance of the carbon nano tube and the graphene can be reduced by adding the nano silver, and the acid resistance, the alkali resistance and the alcohol resistance of the conductive ink are greatly improved by adding the carbon nano tube and the graphene.
In the application, the graphene can be graphene powder or conductive slurry containing graphene.
In the present application, the nano silver includes nano silver with a particle size of 40nm and nano silver with a particle size of 800 nm; the mass ratio of the nano silver with the grain diameter of 40nm to the nano silver with the grain diameter of 800nm is 1:1. The 40nm nano silver and the 800nm nano silver are mixed, so that the nano silver can be better doped in the carbon nano tube and the graphene, the contact resistance of the carbon nano tube and the graphene is reduced, and the conductivity of the conductive graphite is improved.
In the application, the N-methylpyrrolidone solution of the modified polyurea is selected from one or more of BYK-410, BYK420 and VOK-AL 420.
Preferably, the preparation method of the conductive paste comprises the following steps:
s1, mixing a conductive agent, oxetane, cellulose acrylate, N-methyl pyrrolidone solution of modified polyurea and an interfacial agent, and mixing to obtain a mixed material;
s2, adding N-methyl pyrrolidone into the mixed material for ultrasonic dispersion to obtain the conductive slurry.
By adopting the technical scheme, the conductive agent, the oxetane, the cellulose acrylate, the N-methyl pyrrolidone solution of the modified polyurea and the interface agent are mixed, the arrangement of the conductive agent can be adjusted, and the N-methyl pyrrolidone is added for ultrasonic dispersion, so that the stability of the conductive slurry can be better improved, and the conductive stability is improved.
Preferably, in the step S2, the temperature of the ultrasonic dispersion is 15-20 ℃, the power is 960-1100W, and the time is 4-6h.
By adopting the technical scheme, the dispersibility of the graphene and the carbon nano tube is good, and the compatibility of the conductive agent and the epoxy resin composition can be improved.
In the application, the regulator is oxetane, and can better regulate shrinkage, viscosity and adhesive force.
Herein, the dispersant is selected from one or more of a hyperdispersant DisuperS19, a dispersant HAPBI, polyvinyl alcohol and cyclodextrin.
Herein, the photoinitiator is selected from one or more of a photoinitiator 819, a photoinitiator 907, a photoinitiator 369, a photoinitiator 184, a photoinitiator TPO, a triphenylsulfonium chloride salt, and an iodonium diphenylmethylether tetrafluoroborate.
Herein, the catalyst is selected from one or more of hydrated zinc acetylacetonate, zinc acetate and metal complex B219.
In a second aspect, the present application provides a method for preparing a 3D laser photosensitive printing conductive ink for an integrated circuit, which adopts the following technical scheme:
a preparation method of 3D laser photosensitive printing conductive ink for integrated circuits comprises the following steps:
and mixing the epoxy resin composition and the conductive slurry, adding a dispersing agent in the nitrogen atmosphere, continuously mixing, adding a catalyst, a photoinitiator and a regulator, and uniformly mixing to obtain the conductive ink.
By adopting the technical scheme, the epoxy resin composition and the conductive agent are hermetically mixed, and then the dispersing agent is added, so that the compatibility of the epoxy resin composition and the conductive agent can be improved, and the conductive stability is improved.
In summary, the present application has the following beneficial effects:
1. according to the conductive paste, the oxetane and the cellulose acrylate are added into the conductive paste, and under the combined action of the oxetane and the cellulose acrylate, the arrangement of the conductive agent in the conductive ink is adjusted, the dispersity of the conductive agent is improved, and the stability of the conductive paste is improved, so that the conductivity and the conductive stability of the conductive ink are improved. The interfacial agent improves the surface performance of the conductive agent, the N-methylpyrrolidone solution of the modified polyurea effectively prevents the conductive agent from settling by utilizing the three-dimensional network structure of the N-methylpyrrolidone solution of the modified polyurea, and the interfacial agent and the N-methylpyrrolidone solution of the modified polyurea act together, so that the compatibility of the conductive agent and the epoxy resin composition is improved, and the adhesive force between the conductive ink and the PI base material is also improved.
2. The dicyclopentadiene phenol epoxy resin and the neopentyl glycol glycidyl ester epoxy resin are preferably compounded, the regularity of the epoxy resin composition is reduced, and the shrinkage rate of the epoxy resin composition is smaller. The curing crosslinking rate and the film-forming crosslinking compactness of the conductive ink during film forming can be improved by controlling the epoxy equivalent of the dicyclopentadiene phenol epoxy resin to be 128-140 g/eq, so that the adhesive force of the conductive ink printed on a PI base material is improved, and the adhesive force is especially improved in acid, alkali and alcohol solution environments.
3. The conductive ink adopts the synergistic effect of the triazole compound, the aluminate coupling agent and the methacryloyloxyethyl succinate, so that the conductive stability of the conductive ink and the adhesive force between the conductive ink and the PI substrate are further improved, and the acid resistance, alkali resistance and alcohol resistance of the conductive ink are also improved.
4. The application mixes the conductive agent, the oxetane, the cellulose acrylate, the N-methyl pyrrolidone solution of the modified polyurea and the interface agent, can adjust the arrangement of the conductive agent, and then adds the N-methyl pyrrolidone for ultrasonic dispersion, so that the stability of the conductive slurry can be better improved, and the conductive stability is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the present application are commercially available, and if not otherwise specified, the raw materials not mentioned in the preparation examples, examples and comparative examples of the present application are purchased from national pharmaceutical group chemical agents limited.
Preparation examples
Preparation examples 1 to 16 provide an electroconductive paste, and preparation example 1 is described below as an example.
The conductive paste provided in preparation example 1 is prepared by the following steps:
(1) 7.5g of a conductive agent, 0.4g of oxetane (CAS No. 503-30-0), 0.4g of cellulose acrylate, 0.5g of a solution of modified polyurea in N-methylpyrrolidone and 0.4g of a surfactant were mixed, added to a SY-6212-A laboratory internal mixer, and charged with 30minN 2 The air in the system is removed at 30 DEG CMixing for 30min to obtain a mixed material;
(2) Taking out the mixture 1, placing the mixture in a closed container, adding 0.5g of N-methylpyrrolidone into the mixture 1, placing a beaker in an FS-RD2030GL type ultrasonic nano dispersion machine, cooling to 15 ℃, controlling the ultrasonic power to be 960W under the nitrogen atmosphere, carrying out ultrasonic treatment for 6h (2 h for each ultrasonic treatment, 3 times for each ultrasonic treatment and 30min for each time), filtering by using a 1-micron filter element after ultrasonic treatment, and taking filtrate to obtain conductive slurry;
the conductive agent is prepared by mixing graphene (conductive slurry containing graphene), carbon nanotubes and nano silver according to a mass ratio of 0.4; the model of the graphene (the conductive paste containing the graphene) is GC-Powder4B, purchased from Ningbo Moxi company; the carbon nanotubes are single-walled carbon nanotubes with a model of TUBALL, and are purchased from OCSIAL, russia; the nano silver is formed by mixing nano silver with the grain diameter of 40nm and nano silver with the grain diameter of 800nm according to the mass ratio of 1:1;
the cellulose acrylate is model JL106E, purchased from DYMAX, USA;
the model of the N-methyl pyrrolidone solution of the modified polyurea is BYK-410, and the N-methyl pyrrolidone solution is purchased from Wake company of Germany;
the interfacial agent is an aluminate coupling agent DL-411, purchased from Nanjing Pining coupling agent, inc.
Preparation examples 2 to 3 differed from preparation example 1 only in that: the preparation process parameters of the conductive paste are different, and are specifically shown in table 1.
TABLE 1 preparation examples 1-3 preparation Process parameters of electroconductive pastes
Preparation examples 4 to 8 differed from preparation example 3 only in that: the quality of the raw materials for preparing the conductive paste is different, and the raw materials are shown in table 2.
TABLE 2 preparation examples 3 to 8 quality of raw materials for preparation of electroconductive paste
Preparation 9 differed from preparation 5 only in that: the mass ratio of the graphene to the carbon nanotubes to the nano silver is 0.6.
Preparation 10 differed from preparation 5 only in that: the mass ratio of the graphene to the carbon nanotubes to the nano silver is 0.5.
Preparation 11 differed from preparation 10 only in that: the interface agent is prepared by mixing benzotriazole carboxylic acid (CBT-1 in North China chemical), an aluminate coupling agent DL-411 and methacryloyloxyethyl maleic acid monoester (CAS number is 26560-94-1, viscosity is 280-320mPa.s at 25 ℃) according to a mass ratio of 0.2.
Preparation 12 differed from preparation 11 only in that: the mass ratio of the benzotriazole carboxylic acid (CBT-1 in North China chemical), the aluminate coupling agent DL-411 and the methacryloyloxyethyl maleic acid monoester is 0.4.
Preparation 13, which differs from preparation 11 only in that: the mass ratio of the benzotriazole carboxylic acid (CBT-1 in North China chemical), the aluminate coupling agent DL-411 and the methacryloyloxyethyl maleic acid monoester is 0.3.
Preparation 14 differed from preparation 10 only in that: the interface agent is prepared by mixing benzotriazole carboxylic acid (CBT-1 in North China chemical) and an aluminate coupling agent DL-411 according to a mass ratio of 0.2.
Preparation 15 differed from preparation 10 only in that: the interface agent is formed by mixing an aluminate coupling agent DL-411 and methacryloyloxyethyl maleic acid monoester according to the mass ratio of 1.
Preparation 16, which differs from preparation 13 only in that: the methacryloyloxyethyl maleic acid monoester is replaced by methacryloyloxyethyl succinic acid monoester (CAS number 20882-04-6, viscosity 160mPa. S at 25 ℃).
Preparation of comparative example
Comparative example 1 was prepared, differing from preparation example 1 only in that: the N-methyl pyrrolidone solution BYK-410 of the modified polyurea and other mass are replaced by an aluminate coupling agent DL-411.
Comparative example 2 was prepared, differing from preparation example 1 only in that: the mass of the aluminate coupling agent DL-411 and the like is replaced by N-methyl pyrrolidone solution BYK-410 of modified polyurea.
Comparative example 3 was prepared, differing from preparation example 1 only in that: the oxetane and the like are replaced by cellulose acrylate JL106E.
Comparative example 4 was prepared, differing from preparation example 1 only in that: the cellulose acrylate JL106E and the like are replaced by oxetane.
Examples
Examples 1-24, which are described below as example 1, provide a 3D laser photosensitive printing conductive ink for integrated circuits.
The 3D laser photosensitive printing conductive ink for the integrated circuit provided by the embodiment 1 comprises the following preparation steps:
adding 5g of epoxy resin composition and 70g of conductive paste into a closed reaction kettle, adding 1g of dispersing agent under the nitrogen atmosphere, uniformly mixing, finally adding 0.5g of catalyst, 1g of photoinitiator and 1g of regulator (the photoinitiator and the regulator are uniformly mixed in advance), uniformly stirring, filtering by using a 1-micron filter element, and taking filtrate to obtain 3D laser photosensitive printing conductive ink for integrated circuits;
wherein the photoinitiator is triphenyl sulfonium chloride salt (CAS number 4270-70-6);
the regulator is oxetane;
the epoxy resin composition is prepared by mixing dicyclopentadiene phenol epoxy resin and neopentyl glycol glycidyl ester epoxy resin according to a mass ratio of 1:1; the dicyclopentadiene phenol epoxy resin is HP-7200H, has an epoxy equivalent of 128-140 g/eq, and is purchased from DIC of Japan; the neopentyl glycol glycidyl ester epoxy resin is NPG, has the viscosity of 100-500mPa.s at 25 ℃ and the epoxy equivalent of 210-265 g/eq, and is purchased from Nippon synthetic chemical industry Co;
the catalyst is zinc acetylacetonate monohydrate (CAS number 14363-15-6);
the conductive paste is derived from preparation example 1;
the dispersant is a hyperdispersant DisuperS19, purchased from Guangzhou core New Material science and technology Co.
Examples 2-5, which differ from example 1 only in that: the quality of the raw materials for preparing the conductive ink is different, and the quality is shown in table 3.
Table 3 examples 1-5 quality of raw materials for preparation of conductive inks
Example 6 differs from example 3 only in that: the mass ratio of the dicyclopentadiene phenol epoxy resin to the neopentyl glycol glycidyl ester epoxy resin is 2:1.
Example 7, which differs from example 3 only in that: the mass ratio of the dicyclopentadiene phenol epoxy resin to the neopentyl glycol glycidyl ester epoxy resin is 1.5.
Example 8, which differs from example 1 only in that: the dicyclopentadiene phenol epoxy resin has a trademark of DPNE1501L, an epoxy equivalent weight of 253-268 g/eq, and is purchased from Jiashend materials science and technology Limited, hunan.
Example 9, which differs from example 1 only in that: the neopentyl glycol glycidyl ester epoxy resin NPG and other qualities are replaced by dicyclopentadiene phenol epoxy resin DPNE1501L.
Examples 10 to 24 differ from example 7 only in that: the conductive paste sources are different, and the specific results are shown in table 4.
Table 4 examples 7, 10-24 conductive paste sources
Comparative example
Comparative examples 1 to 4, differing from example 9 only in that: the conductive paste sources are different, and the specific results are shown in table 5.
Table 5 comparative examples 1-4 conductive paste sources
Comparative example 5, which differs from example 9 only in that: the neopentyl glycol glycidyl ester epoxy resin NPG and other mass are replaced by dicyclopentadiene phenol epoxy resin HP-7200H.
Comparative example 6, which differs from example 9 only in that: the dicyclopentadiene phenol epoxy resin HP-7200H and the like are replaced by neopentyl glycol glycidyl ester epoxy resin NPG.
Comparative example 7, which differs from example 9 only in that: the quality of the regulator (oxetane) and the like is replaced by a hyperdispersant DisuperS19.
Performance test
The following performance tests were performed on the 3D laser photosensitive printing conductive inks for integrated circuits provided in examples 1 to 24 of the present application and comparative examples 1 to 7.
1. Conductivity: the prepared conductive inks (no treatment) described in examples 1-24 and comparative examples 1-7 were printed on a PI substrate to a thickness of 10 μm, and the resistance was measured using a four-probe tester FT-361, and the results are shown in table 6.
2. Conductive stability: the conductive inks described in examples 1 to 24 and comparative examples 1 to 7 were set at 25 ℃ for 1d, 7d and 30d, respectively, and then the set conductive inks were printed on a PI substrate at a thickness of 10 μm, and the resistance was measured using a four-probe tester FT-361, and the results are shown in Table 6.
Table 6 conductivity and conductivity stability test results
3. Adhesion force: the prepared conductive inks of examples 1-24 and comparative examples 1-7 were printed onto a PI substrate to a thickness of 10 μm and tested for adhesion by the surface Bainite method, the results of which are shown in Table 7.
4. Weather resistance: the prepared conductive inks of examples 1 to 24 and comparative examples 1 to 7 were printed on a PI substrate with a printing thickness of 10 μm, and the PI substrate was placed in a 10wt% aqueous sodium hydroxide solution, a 10wt% aqueous sulfuric acid solution, and isopropyl alcohol for 120min, and then dried after being taken out, and finally the adhesion force after drying was measured by a surface check method, and the test results are shown in Table 7.
Table 7 adhesion and weatherability test results
The present application is described in detail below with reference to the test data provided in tables 6 and 7.
Comparing the test data of example 9 and comparative examples 1-2, it is known that the combined action of the aluminate coupling agent DL-411 and the N-methylpyrrolidone solution BYK-410 of the modified polyurea not only improves the adhesion between the conductive ink and the PI substrate, especially the adhesion after acid, alkali and alcohol treatment, but also improves the conductive stability, and the resistance increase value is small after the conductive ink is placed for 1d, 7d and 30 d.
Comparing the test data of example 9 and comparative examples 3-4, it can be seen that the combined action of oxetane and cellulose acrylate greatly improves the conductivity and conductivity stability of the conductive ink, and also improves the adhesion after acid, alkali and alcohol treatment.
Comparing the test data of example 9 and comparative examples 5-6, it can be seen that the epoxy resin composition of the present invention has different epoxy equivalent, greatly improves the adhesion of the conductive ink, and improves the conductive stability of the conductive ink.
Comparing the test data of example 9 and comparative example 7 in the present application, it can be seen that the present application uses oxetane as a modifier, which can act together with a dispersant to improve the conductive stability and the alkali, acid and alcohol resistance of the conductive ink.
The test data of this application embodiment 1 and 9 of contrast can know, dicyclopentadiene phenol epoxy and neopentyl glycol glycidyl ester epoxy combined action have improved conductive ink's adhesive force, have reduced conductive ink's resistance, and long-time back of using simultaneously, the increment value of resistance is less, and conductive ink's electrically conductive stability is good.
Comparing the test data of examples 1 and 8 of the present application, it can be seen that the epoxy equivalent of the dicyclopentadiene phenol epoxy resin is small, and the adhesion of the conductive ink printed on the PI substrate is improved.
Compared with the test data of the examples 18 to 23, the benzotriazole carboxylic acid, the aluminate coupling agent DL-411 and the methacryloyloxyethyl maleic acid monoester have synergistic effect, so that the resistance is reduced, the resistance is slightly increased after the coating is placed for 1d, 7d and 30d, and the adhesive force is improved, especially the adhesive force after alkali and acid treatment.
As can be seen from comparison of the test data of examples 21 and 24 of the present application, the monoacetyloxyethyl succinate has a certain improvement in the weather resistance of the conductive ink corresponding to the monoacetyloxyethyl succinate, and a higher adhesion force after treatment with an alkali and isopropanol solution, as compared with monoacetyloxyethyl maleate. Meanwhile, the resistance hardly increases after placing 1d, 7d and 30 d.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (6)
1. A3D laser photosensitive printing conductive ink for integrated circuits is characterized in that preparation raw materials comprise, by weight, 70-90 parts of conductive paste, 5-25 parts of epoxy resin composition, 1-10 parts of oxetane, 1-5 parts of dispersant, 1-5 parts of photoinitiator and 0.5-2 parts of catalyst;
the epoxy resin composition comprises dicyclopentadiene phenol epoxy resin and neopentyl glycol glycidyl ester epoxy resin; the mass ratio of the dicyclopentadiene phenol epoxy resin to the neopentyl glycol glycidyl ester epoxy resin is (1-2): 1; the epoxy equivalent of the dicyclopentadiene phenol epoxy resin is 128-140 g/eq;
the raw materials for preparing the conductive paste comprise a conductive agent, an N-methyl pyrrolidone solution of modified polyurea, oxetane, cellulose acrylate, an interfacial agent and N-methyl pyrrolidone; the mass ratio of the conductive agent, the N-methyl pyrrolidone solution of the modified polyurea, the oxetane, the cellulose acrylate, the interfacial agent and the N-methyl pyrrolidone is (75-85): (5-8): (4-6): (4-6): (4-6): (5-10);
the conductive agent comprises graphene, carbon nano tubes and nano silver; the mass ratio of the graphene to the carbon nano tubes to the nano silver is (0.4-0.6) to 1 (0.4-0.6);
the interfacial agent comprises a triazole compound, an aluminate coupling agent and methacryloyloxyethyl succinate monoester; the mass ratio of the triazole compound, the aluminate coupling agent and the methacryloyloxyethyl succinate monoester is (0.2-0.4): 1 (0.3-0.5).
2. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 1, wherein the neopentyl glycol glycidyl ester epoxy resin has a viscosity of 100 to 500mpa.s at 25 ℃.
3. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 1, wherein the triazole compound is benzotriazole carboxylic acid.
4. The 3D laser photosensitive printing conductive ink for the integrated circuit according to claim 1, wherein the preparation method of the conductive paste comprises the following steps:
s1, mixing a conductive agent, oxetane, cellulose acrylate, N-methyl pyrrolidone solution of modified polyurea and an interfacial agent, and mixing to obtain a mixed material;
s2, adding N-methyl pyrrolidone into the mixed material for ultrasonic dispersion to obtain the conductive slurry.
5. The method for preparing the conductive ink for 3D laser photosensitive printing of the integrated circuit according to claim 4, wherein in the step S2, the temperature of the ultrasonic dispersion is 15-20 ℃, the power is 960-1100W, and the time is 4-6h.
6. The method for preparing the conductive ink for 3D laser photosensitive printing of the integrated circuit according to any one of claims 1 to 5, comprising the steps of:
and mixing the epoxy resin composition and the conductive slurry, adding a dispersing agent in a nitrogen atmosphere, continuously mixing, adding a catalyst, a photoinitiator and oxetane, and uniformly mixing to obtain the conductive ink.
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