CN113402923A - 3D laser photosensitive printing conductive ink for integrated circuit and preparation method thereof - Google Patents

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

3D laser photosensitive printing conductive ink for integrated circuit and preparation method thereof

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, also puts higher requirements on the preparation process of the device, has 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 the 3D laser photosensitive printing conductive ink for the integrated circuit, which has good conductive stability and strong adhesion, needs to be developed urgently.

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 preparation method thereof

In a first aspect, the present application provides a 3D laser photosensitive printing conductive ink for integrated circuits, 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, 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).

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 128-140 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 100-500 mPas 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, reduces the viscosity of the conductive ink, is beneficial to printing the conductive ink on a substrate more uniformly, and is beneficial to improving the dispersibility of the conductive slurry and the conductive stability of the conductive ink.

Preferably, the interfacial agent comprises a triazole compound, an aluminate coupling agent and a carboxyl group-containing acrylate; the mass ratio of the triazole compound to the aluminate coupling agent to the carboxyl-containing acrylate is (0.2-0.4) to 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 acrylate containing carboxyl 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 carboxyl-containing acrylate 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.

As used herein, the aluminate coupling agent is selected from one or more of DL-411, NXH-820 and UP-802.

Preferably, the acrylic ester containing a carboxyl group is methacryloyloxyethyl succinate monoester.

By adopting the technical scheme, the viscosity of the monoacid methacrylate is lower, the N-methylpyrrolidone solution of the modified polyurea is more favorable for forming a three-dimensional network structure, and the stability of the three-dimensional network structure is improved, so that the effect of the N-methylpyrrolidone solution of the modified polyurea on the conductive agent is further improved.

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 present application, the N-methylpyrrolidone solution of the modified polyurea is selected from BYK-410, BYK420 and

420.

Preferably, the preparation method of the conductive paste comprises the following steps:

s1, mixing the conductive agent, the oxetane, the cellulose acrylate, the N-methyl pyrrolidone solution of the modified polyurea and the interfacial agent, and mixing to obtain a mixed material;

and S2, adding N-methyl pyrrolidone into the mixed material to carry out 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 4-6 h.

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 Disuper S19, 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 a diphenylmethylether iodonium 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 the 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 carboxyl-containing acrylate, 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 example

Preparation examples 1 to 16 provide a conductive paste, and the following description will be given by taking preparation example 1 as an example.

The conductive paste provided in preparation example 1 is prepared by the following steps:

(1) 7.5g of conductive agent, 0.4g of oxetane (CAS number 503-30-0), 0.4g of cellulose acrylate, 0.5g of N-methylpyrrolidone solution of modified polyurea and 0.4g of interfacial agent were mixed, added to a SY-6212-A laboratory internal mixer and charged with 30min of N₂Removing air in the system, and mixing at 30 deg.C for 30min to obtain mixed material;

(2) taking out the mixture 1, placing the mixture in a closed container, adding 0.5g N-methyl pyrrolidone 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 ultrasonic treatment for each time, 3 times ultrasonic treatment for each time, and 30min intervals 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 formed by mixing graphene (conductive slurry containing graphene), a carbon nano tube and nano silver according to a mass ratio of 0.4:1: 0.4; the model of the graphene (conductive paste containing graphene) is GC-Powder4B, which is purchased from Ningbo ink West company; the carbon nanotube is single-walled carbon nanotube with model of TUBLL^TMPurchased from OCSIAL, russia; the sodiumThe 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, available 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 specific quality is 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 nano tubes to the nano silver is 0.6:1: 0.6.

Preparation 10 differed from preparation 5 only in that: the mass ratio of the graphene to the carbon nano tubes to the nano silver is 0.5:1: 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), 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 the mass ratio of 0.2:1: 0.3.

Preparation 12 differed from preparation 11 only in that: the mass ratio of benzotriazole carboxylic acid (CBT-1 in North China chemical), aluminate coupling agent DL-411 and methacryloyloxyethyl maleic acid monoester is 0.4:1: 0.5.

Preparation 13 differed from preparation 11 only in that: the mass ratio of benzotriazole carboxylic acid (CBT-1 in North China chemical), aluminate coupling agent DL-411 and methacryloyloxyethyl maleic acid monoester is 0.3:1: 0.4.

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 the mass ratio of 0.2: 1.

Preparation 15 differed from preparation 10 only in that: the interface agent is formed by mixing aluminate coupling agent DL-411 and methacryloyloxyethyl maleic acid monoester according to the mass ratio of 1: 0.3.

Preparation 16 differed from preparation 13 only in that: the methacryloyloxyethyl maleic acid monoester was replaced by methacryloyloxyethyl succinic acid monoester in equal mass (CAS number 20882-04-6, viscosity 160 mPas 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 equivalent mass is replaced by cellulose acrylate JL 106E.

Comparative example 4 was prepared, differing from preparation example 1 only in that: the cellulose acrylate JL106E is 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 integrated circuits provided in embodiment 1 is prepared by the steps of:

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 (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 the mass ratio of 1: 1; the dicyclopentadiene phenol epoxy resin has the trade name of HP-7200H, the epoxy equivalent of 128-140 g/eq, and is purchased from DIC in Japan; the neopentyl glycol glycidyl ester epoxy resin has the brand number of NPG, the viscosity of 500mPa & s at 25 ℃ and the epoxy equivalent of 265 g/eq at 210 ℃ 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 Dispenser S19, purchased from Guangzhou core New Material science and technology, Inc.

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 specific quality is shown in table 3.

Table 3 examples 1-5 quality of raw materials for preparation of conductive inks

Quality of the preparation raw materials	Example 1	Example 2	Example 3	Example 4	Example 5
						Photoinitiator	1g	5g	3g	2g	4g
Conditioning agents	1g	10g	5g	3g	8g
						Epoxy resin composition	5g	25g	15g	10g	20g
Catalyst and process for preparing same	0.5g	2g	1g	0.7g	1.5g
						Conductive paste	70g	90g	80g	80g	80g
Dispersing agent	1g	5g	3g	2g	4g

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 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: 1.

Example 8, which differs from example 1 only in that: the dicyclopentadiene phenol epoxy resin has a trade name of DPNE1501L and an epoxy equivalent of 253-268 g/eq, and is purchased from Jiashend materials science and technology Limited in Hunan.

Example 9, which differs from example 1 only in that: the quality of the neopentyl glycol glycidyl ester epoxy resin NPG and the like is replaced by dicyclopentadiene phenol epoxy resin DPNE 1501L.

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	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
					Source of conductive paste	Preparation of comparative example 1	Preparation of comparative example 2	Preparation of comparative example 3	Preparation of comparative example 4

Comparative example 5, which differs from example 9 only in that: the quality of the neopentyl glycol glycidyl ester epoxy resin NPG is 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 mass of the regulator (oxetane) and the like are replaced by a hyperdispersant Dispenser S19.

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 (untreated) 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 10 wt% aqueous sodium hydroxide solution, a 10 wt% 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, which improves the adhesion of the conductive ink printed on the PI substrate.

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.

Comparing the test data of examples 21 and 24 of the present application, it can be seen that, compared with methacryloyloxyethyl maleic acid monoester, methacryloyloxyethyl succinic acid monoester has a certain improvement in weather resistance to conductive ink, and has a higher adhesion after treatment with alkali and isopropanol solution. Meanwhile, the resistance hardly increases after placing 1d, 7d and 30 d.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

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 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 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).

2. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 1, wherein 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.

3. the conductive ink for 3D laser photosensitive printing of integrated circuits as claimed in claim 2, wherein the epoxy equivalent of the dicyclopentadiene phenol epoxy resin is 128-140 g/eq.

4. The 3D laser photosensitive printing conductive ink for the integrated circuit according to claim 2, wherein the viscosity of the neopentyl glycol glycidyl ester epoxy resin at 25 ℃ is 100-500 mPa.s.

5. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 1, wherein the interfacial agent comprises a triazole compound, an aluminate coupling agent, and a carboxyl group-containing acrylate; the mass ratio of the triazole compound to the aluminate coupling agent to the carboxyl-containing acrylate is (0.2-0.4) to 1 (0.3-0.5).

6. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 5, wherein the acrylic ester containing carboxyl groups is methacryloyloxyethyl succinate monoester.

7. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 5, wherein the triazole compound is benzotriazole carboxylic acid.

8. The 3D laser photosensitive printing conductive ink for integrated circuits according to claim 1, wherein the preparation method of the conductive paste comprises the following steps:

s1, mixing the conductive agent, the oxetane, the cellulose acrylate, the N-methyl pyrrolidone solution of the modified polyurea and the interfacial agent, and mixing to obtain a mixed material;

and S2, adding N-methyl pyrrolidone into the mixed material to carry out ultrasonic dispersion to obtain the conductive slurry.

9. The method as claimed in claim 8, wherein the temperature of the ultrasonic dispersion in the step S2 is 15-20 ℃, the power is 960-.

10. The method for preparing the conductive ink for 3D laser photosensitive printing of the integrated circuit according to any one of claims 1 to 8, comprising the steps of:

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.