CN112341866B - Photosensitive spray-type conductive ink and preparation method and application thereof - Google Patents

Photosensitive spray-type conductive ink and preparation method and application thereof Download PDF

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Publication number
CN112341866B
CN112341866B CN202011166463.7A CN202011166463A CN112341866B CN 112341866 B CN112341866 B CN 112341866B CN 202011166463 A CN202011166463 A CN 202011166463A CN 112341866 B CN112341866 B CN 112341866B
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conductive ink
resin
photosensitive
solvent
conductive
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CN112341866A (en
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王晓东
安丰磊
吴来喜
张祝豪
麻帅
查晓英
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Jiangsu Kuangshun Photosensitivity New Material Stock Co ltd
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Jiangsu Kuangshun Photosensitivity New Material Stock Co ltd
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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
    • 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
    • C09D11/30—Inkjet printing inks
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks

Abstract

The invention provides photosensitive spraying type conductive ink and a preparation method and application thereof, and belongs to the field of photosensitive ink. The photosensitive ink comprises the components of modified photosensitive resin, monomer, conductive powder, photoinitiator, high-temperature curing resin, bentonite slurry, auxiliary agent and solvent. The preparation method comprises the following steps: uniformly dispersing modified photosensitive resin, acrylic resin, a photoinitiator, bentonite slurry, a solvent, conductive powder and an auxiliary agent, and then grinding and dispersing to obtain an agent A; uniformly dispersing the high-temperature cured resin and the solvent, and then uniformly grinding to obtain a preparation B; the A, B agent obtained above was mixed with PM and dispersed using a high-speed disperser, thereby obtaining the desired photosensitive spray type conductive ink. The invention improves the production efficiency, reduces the production cost, and simultaneously, the performances in all aspects can meet the requirements of customers.

Description

Photosensitive spray-type conductive ink and preparation method and application thereof
Technical Field
The invention belongs to the field of photosensitive ink, and particularly relates to photosensitive spray-type conductive ink, and a preparation method and application thereof.
Background
In order to adapt to and meet the rapid development of the electronic industry, semi-automatic and automatic production of enterprises is particularly remarkable, and the improvement of production efficiency, the reduction of production cost and labor cost are the first big targets and tasks of various large enterprises at present.
The largest consumer products of the electronic products in the current society, especially in the thin film conductive ink, are increasingly used in this aspect every year, however, the current production process-printing process is far from meeting the production requirement, so how to improve the production efficiency is also a problem to be solved by various large enterprises.
The invention can perform online operation during production, can directly bake after spraying, can greatly improve the production efficiency of enterprises and reduce the labor cost compared with printing (printing first and baking later), and can recycle the spraying residues at the same time, thereby greatly reducing the loss and the production cost. Meanwhile, the conductive paint can meet the requirements of customers on the use of printing type conductive ink.
The existing photosensitive conductive ink application process comprises the following steps: screen printing, baking, para-position exposure, developing and high-temperature curing.
Wherein each device is screen printed to produce only 2-3 sheets per minute. When exposure is carried out, a film negative film is required to be used for alignment exposure, so that the efficiency is low; meanwhile, the negative film is easy to expand and shrink and age, the service life is short, the consumption is large, and the cost is high. It is therefore highly desirable to find a new, simple, efficient, printing-free ink.
Disclosure of Invention
Aiming at the problems existing in the prior art, the applicant provides photosensitive spraying type conductive ink and a preparation method and application thereof. The invention can greatly improve the production efficiency, bring great competitive advantage to enterprises and reduce the production cost, and simultaneously, the performances in all aspects can meet the requirements of clients.
The technical scheme of the invention is as follows:
the photosensitive spray type conductive ink comprises the following raw materials in percentage by mass:
Figure BDA0002745951460000021
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wherein, the modified photosensitive resin is prepared by the following method:
adding 80g-120g of epoxy resin with TG of 35-75 ℃ into DBE filled with 30g-50g, heating to 90-100 ℃ to dissolve for 5h-6h until the epoxy resin is completely dissolved, then adding a polymerization inhibitor and a catalyst, stirring for 10-20min until the epoxy resin is completely dissolved, adding 38-45g of acrylic acid, heating to 110-115 ℃ to react, adding 70-90g of DBE and 60-80g of tetrahydrophthalic anhydride when the acid value is less than 5, reducing the temperature to 94-96 ℃ until the acid value reaches 65-70, then adding 20-40g of 2-acrylamido-2-phenyl ethane sulfonic acid, and cooling after heat preservation for 3-4 hours to obtain the modified photosensitive resin.
The photosensitive resin is one or more of epoxy resin, polyacrylic resin or polyurethane resin with double bonds; preferably, the photosensitive resin is modified epoxy resin with double bonds or polyacrylate resin; more preferred are epoxy resins with double bonds.
The polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone; the catalyst is one or more of hydrochloric acid, oxalic acid, phosphoric acid, sulfuric acid and metal salts.
The monomer is one or more of acrylic ester resins with single functionality and multiple functionalities; preferably at least one of DPHA, EMPTA or HEMA; more preferably DPHA.
The conductive powder is at least one of silver powder, copper powder, silver-coated copper powder, silver Bao Lvfen, aluminum powder, nickel powder, gold powder, conductive carbon black or conductive graphite powder; silver powder and copper powder are preferred; more preferably silver powder.
The silver powder is prepared by the following steps:
adding 1-6 micron flake silver powder into a planetary ball mill, adding zirconia beads, increasing the rotating speed to 500 rpm, maintaining for 4-8h, increasing to 800 rpm, and maintaining for 4-8h to obtain the required spheroidal spherical silver powder, wherein the particle size distribution of the spheroidal spherical silver powder is 0.05-15 microns.
The photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, methyl benzoate, 2-isopropylthioxanthone or 2, 4-diethylthioxanthone.
The high-temperature curing resin is one or more of epoxy resin, polyacrylate resin, isocyanate resin, imidazole, melamine, TGIC or dicyandiamide; preferably epoxy, melamine or dicyandiamide; more preferably bisphenol A type epoxy resins or melamine with TG 45-75 ℃.
The bentonite slurry is activated bentonite and is prepared by the following method:
one or more of BYK-APA, BYK-1958, BYK-MP100, BENTONE SD-1 or BENTONE 828 are selected, and dispersed by using a tetramethylbenzene solvent, and bentonite: the mass ratio of the tetramethylbenzene is 4:1, a step of; preferred bentonites are BYK-APA or BENTONE SD-1.
The auxiliary agent is at least one of KS-66, KS-538, KS-603, BYK-354, BYK-204 or BYK-405; preferably at least one of KS-66, KS-583 or BYK-354; more preferably KS-66.
The solvent is at least one of dimethyl nylon acid (DBE), dipropylene glycol methyl ether (DPM), diethylene glycol diethyl ether acetate (DCAC), propylene glycol methyl ether (PM), ethylene glycol butyl ether (white water prevention) or tetramethylbenzene; preferably at least one of DBE, DPM or PM; more preferably at least one of DPM or PM.
A preparation method of photosensitive spraying conductive ink comprises the following steps:
s1, uniformly dispersing modified photosensitive resin, a monomer, a photoinitiator, bentonite slurry, a solvent, an auxiliary agent and conductive powder for 15-20 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing the high-temperature cured resin and the solvent for 10-15 minutes, grinding the mixture by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding 30-50% PM, and dispersing by using a high-speed dispersing machine to obtain the photosensitive spray type conductive ink.
The application of the conductive ink in preparing the spray-type conductive circuit is characterized in that the specific application method of the conductive ink is as follows:
step 1: flatly placing a substrate to be sprayed on a table top, and vacuumizing to fix the substrate;
step 2: placing the printing ink into a closed tank, pressurizing to 0.06-0.15mpa, and then spraying the base material in the step 1 by using a nozzle, wherein the thickness of the printing ink is different according to the requirement;
step 3: directly placing the sprayed base material obtained in the step 2 into a tunnel furnace for pre-baking, wherein the pre-baking parameters are as follows: baking at 70-80 ℃ for 30-50 minutes, naturally cooling after finishing, and then placing a UV or LED lamp source for para-position exposure, wherein the energy of the lamp source is controlled as follows: 100-500mj/cm 2 Based on the energy grid 6-12;
step 4: and (3) placing the base material subjected to illumination obtained in the step (3) into a developing machine filled with sodium carbonate solution with the concentration of 0.8-1.2%, developing, washing with water, drying, controlling the developing pressure to be 0.05-0.15mpa, placing into an oven with the temperature of 120-160 ℃ after drying, and curing at high temperature for 30-70 minutes, thus obtaining the conductive circuit.
The application process of the spray-type photosensitive conductive ink comprises the following steps: spraying, baking, exposing, developing and high-temperature curing.
Wherein, the spraying can produce 10-12 tablets per minute, which is 4-6 times of the old technology. During exposure, a film negative is not needed, a pattern can be directly put into a computer by programming, DI exposure is carried out, the cost of the film negative is completely saved, the production efficiency is improved, and the consumable cost is reduced.
Meanwhile, the invention also well solves the technical defects and difficulties existing in the prior ink. 1. Since there is no such ink in the market at present, how to prepare and produce becomes the biggest problem. 2. The use of DI equipment to produce this type of ink can result in low sensitivity during exposure, resulting in line narrowing and even line open and short problems after development. The invention adopts photoinitiators with different wave bands for matching (low wave band and high wave band are mixed and matched for use), thereby solving the problems of low sensitivity and the like. 3. When spraying, how to adapt to the spraying equipment and how to make the sprayed ink uniformly and stably coat on the substrate is also a great difficulty. Therefore, the preparation method and the production process of the spray photosensitive conductive ink solve the problems and the defects well and fill the blank in the field.
The beneficial technical effects of the invention are as follows:
1, it is known how to spray ink well and uniformly on a substrate without causing problems such as running oil, matt, little sun, poor running and the like when the ink is very thin. 2-acrylamide is an excellent active dispersant, can achieve effective activation and dispersion effects on difficult-to-disperse powder materials and the like, but 2-acrylamide is extremely unstable, is extremely easy to precipitate (get back) at low temperature, has toxicity and has a narrow application range. In order to exert the effective effect, the 2-acrylamide is grafted on the epoxy resin by utilizing the 2-acrylamide-2-phenyl ethane sulfonic acid, so that the problem that the 2-acrylamide has high activity but is unstable can be well solved, the synthetic resin is nontoxic, bentonite can be better activated, the bentonite has excellent thickening and dispersing effects on printing ink, the water resistance is high, the coating strength and adhesive force can be improved, and the 2-acrylamide is an excellent active dispersing agent, so that the bentonite can be more uniformly dispersed in the printing ink to achieve the optimal effect, and further the excellent spraying effect can be achieved. The conductive ink can be added into the conductive ink to effectively solve the problems, so that the conductive ink can exert the best effect.
2, DI exposure is a trend of photo-curing ink in the future, however, the current use of DI equipment for exposure has problems of low sensitivity, incomplete exposure and the like. The photoinitiator used in the invention has the advantages of good matching with a DI equipment light source, high sensitivity of exposure and high line precision.
And 3, the types and the particle sizes of the conductive silver powder are many, and poor selection can greatly influence the conductive effect. The silver powder used in the invention can be treated by different parameters of the ball mill to obtain the conductive silver powder with excellent conductive effect, thereby greatly reducing sheet resistance and improving conductivity.
Detailed Description
The present invention will be specifically described with reference to examples.
Examples
1, the preparation method of the modified epoxy resin with double bonds comprises the following steps:
80g of epoxy resin with TG of 35 ℃ is added into DBE with 30g, the temperature is raised to 90-100 ℃ to dissolve for 5H until the epoxy resin is completely dissolved, then a certain amount of polymerization inhibitor and catalyst are added and stirred for 10min until the epoxy resin is completely dissolved, 38g of acrylic acid is added and the temperature is raised to 110-115 ℃ to react, and the acid value is measured once per hour until the acid value is less than 5. 70g of DBE and 60g of tetrahydrophthalic anhydride are added, the temperature is reduced to 94-96 ℃ at the same time, the acid value is measured once per hour until the acid value reaches 65, then 20g of 2-acrylamido-2-phenyl ethane sulfonic acid is added, and the temperature is reduced after 3 hours of heat preservation, thus obtaining the modified photosensitive resin GXCL-01;
100g of epoxy resin with TG of 55 ℃ is added into DBE with 40g, the temperature is raised to 90-100 ℃ to dissolve for 5.5H until the epoxy resin is completely dissolved, then a certain amount of polymerization inhibitor and catalyst are added, stirring is carried out for 15min until the epoxy resin is completely dissolved, 40g of acrylic acid is added, the temperature is raised to 110-115 ℃ for reaction, and the acid value is measured once per hour until the acid value is less than 5. Then 80g DBE and 70g tetrahydrophthalic anhydride are added, the temperature is reduced to 94-96 ℃ at the same time, the acid value is measured once per hour until the acid value reaches 68, 30g, 2-acrylamido-2-phenyl ethane sulfonic acid is added, and the temperature is reduced after 3.5 hours of heat preservation, thus obtaining the modified photosensitive resin GXCL-02;
120g of epoxy resin with TG of 75 ℃ is added into DBE with 50g, the temperature is raised to 90-100 ℃ to dissolve for 6H until the epoxy resin is completely dissolved, then a certain amount of polymerization inhibitor and catalyst are added, stirring is carried out for 20min until the epoxy resin is completely dissolved, 45g of acrylic acid is added, the temperature is raised to 110-115 ℃ for reaction, and the acid value is measured once per hour until the acid value is less than 5. Then 90g DBE and 80g tetrahydrophthalic anhydride are added, the temperature is reduced to 94-96 ℃ at the same time, the acid value is measured once per hour until the acid value reaches 70, then 40g, 2-acrylamido-2-phenyl ethane sulfonic acid is added, and the temperature is reduced after the heat preservation is carried out for 4 hours, thus obtaining the modified photosensitive resin GXCL-03.
2. The preparation method of the unmodified epoxy resin with double bonds comprises the following steps:
80g of epoxy resin with TG of 35 ℃ is added into DBE with 30g, the temperature is raised to 90-100 ℃ to dissolve for 5H until the epoxy resin is completely dissolved, then a certain amount of polymerization inhibitor and catalyst are added and stirred for 10min until the epoxy resin is completely dissolved, 38g of acrylic acid is added and the temperature is raised to 110-115 ℃ to react, and the acid value is measured once per hour until the acid value is less than 5. 70g of DBE and 60g of tetrahydrophthalic anhydride are added, the temperature is simultaneously reduced to 94-96 ℃, the acid value is measured once per hour until the acid value reaches 65, the temperature is kept for 3 hours, and the temperature is reduced, thus obtaining photosensitive resin GXCL-04;
120g of epoxy resin with TG of 75 ℃ is added into DBE with 50g, the temperature is raised to 90-100 ℃ to dissolve for 6H until the epoxy resin is completely dissolved, then a certain amount of polymerization inhibitor and catalyst are added, stirring is carried out for 20min until the epoxy resin is completely dissolved, 45g of acrylic acid is added, the temperature is raised to 110-115 ℃ for reaction, and the acid value is measured once per hour until the acid value is less than 5. And then 90g of DBE and 80g of tetrahydrophthalic anhydride are added, the temperature is simultaneously reduced to 94-96 ℃, the acid value is measured once per hour until the acid value reaches 70, the temperature is reduced after the temperature is kept for 4 hours, and the modified photosensitive resin GXCL-05 is obtained.
2, the preparation method of the spheroidal ball silver powder comprises the following steps:
adding 1-2 micron flake silver powder into a planetary ball mill, adding zirconia beads, increasing the rotating speed to 500 rpm, maintaining for 4 hours, increasing to 800 rpm, and maintaining for 4 hours to obtain the required spheroidal silver powder YF-01;
adding 3-4 μm flake silver powder into a planetary ball mill, adding zirconia beads, increasing the rotating speed to 500 r/min, maintaining for 6H, increasing to 800 r/min, and maintaining for 6H to obtain the required spheroidal silver powder YF-02;
adding 5-6 μm flake silver powder into planetary ball mill, adding zirconia beads, increasing rotation speed to 500 rpm, maintaining 8H, increasing to 800 rpm, and maintaining 8H to obtain spherical silver powder YF-03
Selecting 3-4 microns of flake silver powder as common silver powder YF-04;
3, the bentonite is activated,
bentonite is activated, and the bentonite is BYK-APA, BYK-1958 and BYK-MP100 of Pick company, BENTONE SD-1 and BENTONE 828 of Hamming company. The activation method comprises the steps of dispersing the solvent according to different proportions, wherein BYK-APA is named APA-20, and the ratio of the BYK-APA to the tetramethylene=4:1; BENTONE SD-1: p112=4: 1, named APB-20; BYK-APA, tetramethylene=4:1, designated APA-20.
Examples 1-3 and comparative examples 1-3 the raw materials used in the preparation of the conductive ink are shown in Table 1
TABLE 1
Figure BDA0002745951460000071
Example 1
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing modified photosensitive resin GXCL-01, a monomer, a photoinitiator, a solvent, an auxiliary agent, conductive silver powder YF-03 and activated bentonite APA-20 for 20 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 15 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Example 2
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing modified photosensitive resin GXCL-02, a monomer, a photoinitiator, a solvent, an auxiliary agent, conductive silver powder YF-02 and activated bentonite APA-20 for 15 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 10 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Example 3
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing modified photosensitive resin GXCL-02, a monomer, a photoinitiator, a solvent, an auxiliary agent, conductive silver powder YF-03 and activated bentonite AP B-20 for 18 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 12 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Comparative example 1 (comparative modified resin with example 1)
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing photosensitive resin GXCL-04, a monomer, a photoinitiator, a solvent, an auxiliary agent, conductive silver powder YF-03 and activated bentonite AP A-20 for 20 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 15 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Comparative example 2 (comparative modified resin with example 3)
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing photosensitive resin GXCL-05, a monomer, a photoinitiator, 1.78 parts of a solvent, an auxiliary agent and conductive silver powder YF-01, activated bentonite APA-20 for 18 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 12 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Comparative example 3 (comparison with example 2, difference in conductive powder)
The preparation process of the conductive ink comprises the following steps: s1, uniformly dispersing modified photosensitive resin GXCL-02, a monomer, a photoinitiator, a solvent, an auxiliary agent, conductive silver powder YF-04, activated bentonite APA-20 for 15 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing epoxy resin, melamine and a solvent for 10 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding PM, and dispersing by using a high-speed dispersing machine to obtain the required photosensitive spray type conductive ink.
Conductive lines were prepared from the inks prepared in examples 1 to 3 and comparative examples 1 to 3, and specific preparation processes of the conductive lines were as follows:
step 1: flatly placing a substrate to be sprayed on a table top, and vacuumizing;
step 2: placing the printing ink into a closed tank, pressurizing to 0.06-0.15mpa, and then spraying the base material in the step 1 by using a nozzle, wherein the thickness of the printing ink is different according to the requirement;
step 3: directly placing the sprayed base material obtained in the step 2 into a tunnel furnace for pre-baking, wherein the pre-baking parameters are as follows: baking at 75deg.C for 45 min, naturally cooling, and placing into UV or LED lamp source for alignmentBit exposure, the energy control of the lamp source is as follows: 100-500mj/cm 2 Based on the energy grid 6-12;
step 4: and (3) placing the base material subjected to illumination obtained in the step (3) into a developing machine filled with sodium carbonate solution with the concentration of 0.8-1.2%, developing, washing with water, drying, controlling the developing pressure to be 0.05-0.15mpa, placing into an oven with the temperature of 120-160 ℃ after drying, and curing at high temperature for 30-70 minutes, thus obtaining the conductive circuit.
Test case
The conductive traces prepared in examples 1-3 and comparative examples 1-3 were subjected to performance testing, and the results are shown in Table 2 below:
TABLE 2
Test item Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Square resistance (mΩ/≡) 22 23 20 26 25 35
Hardness of 4H 5H 6H 4H 5H 4H
Bending resistance 12 11 14 10 10 11
Resolution (micron) 40 30 20 50 30 30
Spraying efficiency (tablet/min) 10-11 10-11 11-12 4-5 4-5 10-11
Drying property 6 7 8 5 5 6
Note that: the dryness was indicated as 0-10, the higher the number indicated the better the dryness.
From table 2 it can be derived that: compared with comparative example 1 and comparative example 3 and comparative example 2, the modified photosensitive resin has significantly better spraying efficiency than the unmodified photosensitive resin, thereby obtaining better bentonite wetting effect of the modified photosensitive resin. Example 2 compared with comparative example 3, the conductive silver powder after passing through the ball mill has better conductive effect than the common silver powder.
The traditional silk screen printing can only print 2-3 pieces per minute, the spraying type conductive ink can reach 10-12 pieces per minute, the production efficiency is greatly improved, meanwhile, the pre-baking and surface drying can be carried out through the online operation, the personnel are reduced, and the cost is reduced. I.e. the object of the present invention.

Claims (18)

1. The photosensitive spray type conductive ink is characterized by comprising the following raw materials in percentage by mass:
10-50% of modified photosensitive resin
1 to 10 percent of monomer
30-80% of conductive powder
0.1 to 10 percent of photoinitiator
1 to 10 percent of high-temperature cured resin
1-10% of bentonite slurry
0.1 to 5 percent of auxiliary agent
0.1-50% of solvent;
wherein, the modified photosensitive resin is prepared by the following method:
adding 80g-120g of epoxy resin with TG of 35-75 ℃ into DBE filled with 30g-50g, heating to 90-100 ℃ to dissolve for 5h-6h until the epoxy resin is completely dissolved, then adding a polymerization inhibitor and a catalyst, stirring for 10-20min until the epoxy resin is completely dissolved, adding 38-45g of acrylic acid, heating to 110-115 ℃ to react, adding 70-90g of DBE and 60-80g of tetrahydrophthalic anhydride when the acid value is less than 5, reducing the temperature to 94-96 ℃ until the acid value reaches 65-70, then adding 20-40g of 2-acrylamido-2-phenyl ethane sulfonic acid, and cooling after heat preservation for 3-4 hours to obtain modified photosensitive resin;
the conductive powder is silver powder, and the silver powder is prepared by the following method:
adding 1-6 micron flake silver powder into a planetary ball mill, adding zirconia beads, increasing the rotating speed to 500 rpm, maintaining for 4-8h, increasing to 800 rpm, and maintaining for 4-8h to obtain the required spheroidal spherical silver powder, wherein the particle size distribution of the spheroidal spherical silver powder is 0.05-15 microns;
the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, methyl benzoate, 2-isopropylthioxanthone or 2, 4-diethylthioxanthone.
2. The conductive ink according to claim 1, wherein the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone; the catalyst is one or more of hydrochloric acid, oxalic acid, phosphoric acid, sulfuric acid and metal salts.
3. The conductive ink of claim 1 wherein the monomer is one or more of a monofunctional and a multifunctional acrylate resin.
4. The conductive ink of claim 3 wherein the monomer is at least one of DPHA, EMPTA, or HEMA.
5. A conductive ink as claimed in claim 3 wherein the monomer is DPHA.
6. The conductive ink of claim 1 wherein the high temperature curable resin is one or more of an epoxy resin, a polyacrylate resin, an isocyanate resin.
7. The conductive ink of claim 6 wherein the high temperature curable resin is an epoxy resin.
8. The conductive ink as claimed in claim 6, wherein the high temperature curing resin is bisphenol a type epoxy resin having TG of 45 to 75 ℃.
9. The conductive ink of claim 1 wherein the bentonite slurry is activated bentonite and is prepared by:
one or more of BYK-APA, BYK-1958, BYK-MP100, BENTONE SD-1 or BENTONE 828 are selected, and dispersed by using a tetramethylbenzene solvent, and bentonite: the mass ratio of the tetramethylbenzene is 4:1.
10. the conductive ink of claim 9 wherein the bentonite is BYK-APA or BENTONE SD-1.
11. The conductive ink of claim 1 wherein the auxiliary agent is at least one of KS-66, KS-538, KS-603, BYK-354, BYK-204, or BYK-405.
12. The conductive ink of claim 11 wherein the auxiliary agent is at least one of KS-66, KS-583 or BYK-354.
13. The conductive ink of claim 11 wherein the auxiliary agent is KS-66.
14. The conductive ink of claim 1, wherein the solvent is at least one of dimethyl nylon, dipropylene glycol methyl ether, diethylene glycol ethyl ether acetate, propylene glycol methyl ether, ethylene glycol butyl ether, or tetramethylene.
15. The conductive ink of claim 14, wherein the solvent is at least one of dimethyl nylon acid, dipropylene glycol methyl ether, or propylene glycol methyl ether.
16. The conductive ink of claim 14 wherein the solvent is at least one of dipropylene glycol methyl ether or propylene glycol methyl ether.
17. A method for preparing the photosensitive spray type conductive ink according to claim 1, wherein the method for preparing the conductive ink comprises the following steps:
s1, uniformly dispersing modified photosensitive resin, a monomer, a photoinitiator, bentonite slurry, a solvent, an auxiliary agent and conductive powder for 15-20 minutes, grinding by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to be between 180PS and 200PS after uniform dispersion to obtain an agent A;
s2, uniformly dispersing the high-temperature cured resin and the solvent for 10-15 minutes, grinding the mixture by a three-roller machine until the fineness is below 8 mu m, and adjusting the viscosity to 180PS-200PS after uniform dispersion to obtain a preparation B;
and S3, mixing and stirring the agent A and the agent B, adding 30-50% PM, and dispersing by using a high-speed dispersing machine to obtain the photosensitive spray type conductive ink.
18. Use of a conductive ink according to any one of claims 1 to 16 for the preparation of a spray-type conductive circuit, wherein the conductive ink is applied in the following manner:
step 1: flatly placing a substrate to be sprayed on a table top, and vacuumizing to fix the substrate;
step 2: placing the printing ink into a closed tank, pressurizing to 0.06-0.15MPa, and then spraying the base material in the step 1 by using a nozzle, wherein the thickness of the printing ink is different according to the requirement;
step 3: directly placing the sprayed base material obtained in the step 2 into a tunnel furnace for pre-baking, wherein the pre-baking parameters are as follows: baking at 70-80 ℃ for 30-50 minutes, naturally cooling after finishing, and then placing a UV or LED lamp source for para-position exposure, wherein the energy of the lamp source is controlled as follows: 100-500mj/cm 2 Based on the energy grid 6-12;
step 4: and (3) placing the base material subjected to illumination obtained in the step (3) into a developing machine filled with sodium carbonate solution with the concentration of 0.8-1.2%, developing, washing with water, drying under the developing pressure of 0.05-0.15MPa, placing into an oven with the temperature of 120-160 ℃ after drying, and curing at high temperature for 30-70 minutes, thus obtaining the conductive circuit.
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