CN114864133A - Ultralow-temperature curing silver paste for flexible transparent metal grid conductive film and preparation method thereof - Google Patents
Ultralow-temperature curing silver paste for flexible transparent metal grid conductive film and preparation method thereof Download PDFInfo
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- CN114864133A CN114864133A CN202210593816.4A CN202210593816A CN114864133A CN 114864133 A CN114864133 A CN 114864133A CN 202210593816 A CN202210593816 A CN 202210593816A CN 114864133 A CN114864133 A CN 114864133A
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention discloses ultralow-temperature curing silver paste for a flexible transparent metal grid conductive film, which is respectively 30-45 parts of submicron spherical silver powder, 8-23 parts of flaky silver powder, 0.5-1.5 parts of alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol ethyl ether acetate and 7-8.5 parts of diethyl carbonate, wherein the average particle size D50 of the submicron spherical silver powder is 0.45 mu m, and the specific surface area is 1.07 m 2 The average grain diameter D50 of the flaky silver powder is 0.95 mu m, and the specific surface area is 1.35 m 2 (ii)/g; also discloses a preparation method thereof; the curing temperature of the cured silver paste is reduced to 80 ℃, the curing time is shortened to 20min, and the cured silver paste has the remarkable characteristics of good printing performance, excellent grid filling performance, weather resistance and electric conductivity, greatly improved yield, reduced energy consumption and the like, and has strong market competitiveness.
Description
Technical Field
The invention belongs to the technical field of novel electronic conductive silver paste materials for microelectronic flexible display touch control, and particularly relates to ultralow-temperature curing silver paste for a flexible transparent metal grid conductive film and a preparation method thereof.
Background
With the continuous development of flexible electronics and wearable electronics, various devices have higher and higher requirements on flexible transparent conductive film electrodes, and meanwhile, the flexible transparent conductive films are more and more widely applied. In the traditional flexible transparent conductive film, a flexible ITO film is taken as a main factor, but the cost of ITO is high, the preparation process is complex, high-vacuum equipment is needed, and the ITO is rigid and fragile, so that the application of the ITO film in flexibility is limited. The newly developed alternative ITO materials mainly comprise high-molecular conductive polymers, carbon materials, metal nanowires and particles. Although these alternative materials achieve good photoelectric properties, there is a bottleneck that conductivity and transmittance are mutually restricted, and when the conductivity is improved, the thickness of the conductive layer needs to be increased, while the carbon material and the metal nanoparticles or nanowires are opaque, so that a part of the transmittance needs to be sacrificed.
The metal grid flexible transparent conductive film can solve the contradiction between low sheet resistance and high light transmittance of a transparent electrode due to good flexibility, excellent electrical property (low sheet resistance) and optical property (high light transmittance), particularly by only changing the line width, period, aspect ratio, shape and arrangement of the grid, can cut and regulate the electrical property and the optical property according to the actual performance requirement, and can realize the required photoelectric property by designing the line width, period and metal thickness of the metal grid while ensuring the low sheet resistance and high light transmittance, and meanwhile, the metal grid flexible transparent conductive film has low cost, can realize flexibility and stretchability and the like, so that the metal grid flexible transparent conductive film becomes the best alternative material of ITO.
At present, conductive film silver paste on the market is micron-sized silver paste, and the conductive film silver paste has large particle size and poor dispersibility and cannot be effectively filled in a 3-micron superfine groove; the conductive film silver paste prepared by adopting the nano-scale silver powder with small particle size has good filling property, but the nano-scale silver powder with small particle size is easy to agglomerate, and the effective contact (conduction) area after solidification is relatively small, so that the conductive film silver paste is difficult to obtain stronger conductive performance.
In addition, the silver paste is generally filled in the micron-sized superfine grooves, and after low-temperature baking, the silver paste is difficult to generate strong mechanical properties, and the silver paste and the substrate are difficult to realize strong binding force.
Disclosure of Invention
One of the purposes of the invention is to provide the ultralow temperature curing silver paste for the flexible transparent metal grid conductive film, which can realize excellent grid filling property, printing property, adhesive force and weather resistance under the conditions of ultralow curing temperature and shorter curing time, aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the ultralow-temperature curing silver paste for the flexible transparent metal grid conductive film comprises 30-45 parts of submicron spherical silver powder, 8-23 parts of flaky silver powder, 0.5-1.5 parts of alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol ethyl ether acetate and 7-8.5 parts of diethyl carbonate; the average particle size D50 of the submicron spherical silver powder is 0.45 mu m, and the specific surface area is 1.07 m 2 (iv) g; the average grain diameter D50 of the flaky silver powder is 0.95 mu m, and the specific surface area is 1.35 m 2 /g。
The ultra-low temperature curing silver paste for the flexible transparent metal grid conductive film is characterized in that polyurethane resin is prepared by fully dissolving 20% of halogen-free thermoplastic polyurethane elastomer rubber in 80% of organic solvent, and the organic solvent is composed of 24% of isophorone and 76% of diethyl carbonate by mass fraction.
The ultralow temperature curing silver paste for the flexible transparent metal grid conductive film is characterized in that the alkyl (aryl) ketoxime is one of benzophenone oxime group, acetophenone oxime group and butanone oxime group.
The invention also aims to provide a preparation method of the ultralow temperature curing silver paste for the flexible transparent metal grid conductive film, which has excellent grid filling property, printing property, adhesive force and weather resistance under the conditions of ultralow curing temperature and shorter curing time.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of ultralow temperature curing silver paste for a flexible transparent metal grid conductive film comprises the following steps:
premixing slurry components: firstly, polyurethane resin and alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate are fully dissolved and uniformly mixed in a container, and then submicron spherical silver powder and flake silver powder are poured in and fully and uniformly stirred;
adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-shaped slurry, and continuously stirring the mixture fully and uniformly in a short time;
step three, uniformly mixing and finely rolling: fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to eliminate residues and bubbles in the silver paste;
step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the ultralow temperature curing silver paste for the metal grid conductive film.
Compared with the prior art, the invention has the beneficial effects that:
the submicron spherical silver powder is prepared by a hydrothermal chemical reaction reduction method, the flaky silver powder is prepared by a mechanical ball milling method, the two silver powders have the characteristics of high dispersibility, narrow particle size distribution and the like, the two types of superfine silver powders are mixed according to different proportions, the mixing condition of the superfine silver powder is optimized, the self-made benzophenone oxime group-sealed hexamethylene diisocyanate, acetophenone oxime group-sealed hexamethylene diisocyanate and butanone oxime group-sealed hexamethylene diisocyanate are used as curing agents, the crosslinking reaction rate of the self-made benzophenone oxime group-sealed hexamethylene diisocyanate and polyurethane resin is promoted, the curing temperature of the self-made benzophenone oxime group-sealed hexamethylene diisocyanate and polyurethane resin is reduced, the ultralow-temperature curing silver paste for the flexible transparent metal grid conductive film is obtained, and the ultralow-temperature curing silver paste can realize the characteristics of excellent grid filling property, printing property, adhesive force, weather resistance and the like under the conditions of the curing temperature and shorter curing time.
Drawings
FIG. 1 is a scanning electron microscope image of a submicron spherical silver powder according to the present invention;
FIG. 2 is a scanning electron micrograph of the silver flake of the present invention;
FIG. 3 is a scanning electron microscope image of the flexible transparent metal grid conductive film of the present invention after curing.
Detailed Description
The technical scheme of the invention is clearly and completely described below by combining the drawings and the specific embodiment.
The invention discloses ultralow temperature curing silver paste for a flexible transparent metal grid conductive film, which comprises 30-45 parts of submicron spherical silver powder, 8-23 parts of flaky silver powder, 0.5-1.5 parts of alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol ethyl ether acetate and 7-8.5 parts of diethyl carbonate.
The parameters of the submicron spherical silver powder and the flaky silver powder are different, wherein the average particle size D50 of the submicron spherical silver powder is 0.45 mu m, and the specific surface area is 1.07 m 2 (g), shown in a scanning electron micrograph of FIG. 1, the average particle diameter D50 of the silver flakes is 0.95 mu m, and the specific surface area is 1.35 m 2 The scanning electron micrograph is shown in FIG. 2.
The polyurethane resin is prepared by fully dissolving 20% of halogen-free thermoplastic polyurethane elastomer rubber in 80% of organic solvent, wherein the organic solvent is composed of 24% of isophorone and 76% of diethyl carbonate by mass fraction. The polyurethane resin is selected from halogen-free thermoplastic polyurethane elastomer rubber (TPU), has the characteristics of good hardness, tensile strength, adhesion, rebound resilience, wear resistance, bending resistance and the like, is easy to disperse and dissolve in a composite solvent of isophorone and diethyl carbonate, is prepared into environment-friendly halogen-free low-temperature curing thermoplastic polyurethane resin with good fluidity, is used as a matrix framework of a conductive film layer, can ensure that conductive silver powder is stably suspended and bonded on the matrix framework, and can realize the adhesion and bonding of the conductive film layer and a base material. The adhesive force and the conductive performance of the conductive film layer are directly influenced by the wrapping degree of the polyester carrier and the silver powder and the shrinkage capacity of the molecular chain in the curing process.
The alkyl (aryl) ketoxime is one of benzophenone oxime group, acetophenone oxime group and butanone oxime group. The curing agent is selected from alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate which has obvious effects of improving the adhesion of halogen-free slurry, weather resistance and curing conditions.
The organic solvent is selected from middle-low boiling point organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate, has good compatibility with polyurethane resin and curing agent, and is an excellent environment-friendly low-toxicity solvent. The organic solvent has no chemical action with polyurethane resin, only plays a role in dissolution, does not generate similar swelling and other conditions, does not have the phenomena of solvent precipitation and the like at low temperature, and in addition, the compound of the organic solvent and the organic solvent has higher volatilization rate, thereby being capable of meeting the requirements of the production process of frictioning and drying.
The performance indexes of the submicron spherical silver powder and the flake silver powder are shown in the following table.
The scanning electron microscope image of the cured flexible transparent metal grid conductive film of the invention is shown in figure 3.
Example 1
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 35 parts of submicron spherical silver powder, 18 parts of flake silver powder, 1 part of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 8 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group sealed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 2
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 40 parts of submicron spherical silver powder, 13 parts of flake silver powder, 1 part of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 8 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group sealed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 3
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 45 parts of submicron spherical silver powder, 8 parts of flake silver powder, 1 part of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 8 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group-enclosed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 4
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 30 parts of submicron spherical silver powder, 23 parts of flake silver powder, 1 part of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 8 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group sealed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 5
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 35 parts of submicron spherical silver powder, 18 parts of flake silver powder, 0.5 part of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 8.5 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group sealed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 6
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 35 parts of submicron spherical silver powder, 18 parts of flake silver powder, 1.5 parts of butanone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 7.5 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, butanone oxime group sealed hexamethylene diisocyanate is fully dissolved and mixed evenly in a container, and then submicron spherical silver powder and flake silver powder are poured into the container and fully and evenly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 7
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 35 parts of submicron spherical silver powder, 18 parts of flaky silver powder, 1 part of acetophenone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 7.5 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, the acetophenone oxime group-closed hexamethylene diisocyanate is fully dissolved and uniformly mixed in a container, and then the submicron spherical silver powder and the flake silver powder are poured in and fully and uniformly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
Example 8
The flexible transparent metal grid conductive silver paste comprises the following substances in parts by mass: 35 parts of submicron spherical silver powder, 18 parts of flake silver powder, 1 part of benzophenone oxime group-blocked hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol monoethyl ether acetate and 7.5 parts of diethyl carbonate.
The preparation method of the conductive silver paste comprises the following steps:
premixing slurry components: firstly, benzophenone oxime group closed hexamethylene diisocyanate is fully dissolved and uniformly mixed in a container, and then submicron spherical silver powder and flake silver powder are poured in and fully and uniformly stirred.
Adding and premixing an organic solvent: adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time.
Step three, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding the mixture by using a three-roller grinder to obtain conductive silver paste, and filtering and vacuumizing the conductive silver paste by using a paste impurity removal system to remove residues and air bubbles in the silver paste to obtain the metal grid silver paste.
Step four, testing and packaging: and (3) wiping the container of the slurry completely when the fineness of the slurry measured by a scraper blade fineness meter is less than 5 mu m, covering a cover, and labeling to obtain the metal grid silver paste.
The performance index results of the conductive silver pastes of examples 1-8 are shown in the following table:
note: high temperature and high humidity test (weather resistance): and (3) placing the metal grid in a constant temperature and humidity tester with 85% RH at 85 ℃, taking out the metal grid after 480h, cooling to room temperature, and then testing the current resistance to be compared with the initial resistance.
The ultralow temperature curing silver paste for the flexible transparent metal grid conductive film with excellent grid filling property, printing property, adhesive force and weather resistance is prepared under the conditions of ultralow curing temperature and shorter curing time, and the difficulty of product preparation lies in the selection and proportion of the superfine silver powder and the curing agent.
As can be found from the above table 2, in the embodiments 1 to 4, the submicron silver powder and the flake silver powder are compounded according to different parts by weight, and when the curing temperature exceeds 130 ℃, the long-time curing may generate denaturation influence on the flexible film layer of the PET substrate, and the yield is reduced, so that at the curing temperature of 125 ℃, the compound parts by weight of the submicron silver powder and the flake silver powder is selected at a curing time of 60min, and when the submicron spherical silver powder is 35 parts and the flake silver powder is 18 parts, the prepared silver paste has higher conductivity and filling property, which is because the submicron silver powder and the flake silver powder are highly dispersed and have narrow particle size distribution, and the filling property is good, so that a compact conductive network is formed, the contact resistance is effectively reduced, and the conductivity is more excellent.
In examples 5 to 6, in addition to example 1, it was found that when the amount of the butanone oxime group-blocked hexamethylene diisocyanate curing agent was too large, the crosslinking reaction was too severe during curing, and the adhesion, conductivity, and weather resistance were deteriorated. When the curing agent is 0.5, the curing temperature is unchanged, the crosslinking reaction is slow, and the curing time is prolonged to 95min, but the adhesive force, the conductivity and the weather resistance are not greatly influenced.
Examples 7 to 8 are based on the optimization of examples 1 to 6, compared with different types of alkyl (aryl) ketoxime blocked and modified hexamethylene diisocyanate curing agents, the mass fraction of which is 1, all show excellent conductivity, weather resistance, filling property and good adhesion, wherein it is found that the butanone oxime group blocked hexamethylene diisocyanate curing temperature is 125 ℃, the curing time is 60min, the benzophenone oxime group blocked hexamethylene diisocyanate curing temperature is 95 ℃, the curing time is 45min, the acetophenone oxime group blocked hexamethylene diisocyanate curing temperature is 80 ℃, the curing time is shortened to 20min, which shows that the aryl functional group introduced hexamethylene diisocyanate curing agent can lower the curing temperature and the curing time than the alkyl functional group hexamethylene diisocyanate curing agent, because the benzene ring steric hindrance effect is large, the reaction active space is reduced, and the crosslinking reaction rate is increased, but the electrophilic effect of the biphenyl ring makes the reaction inactive, but is superior to butanone oxime-based ketoxime blocked and modified hexamethylene diisocyanate curing agent.
It is to be understood that the above-described embodiments are only a few, and not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (4)
1. Ultra-low temperature solidification silver thick liquid is used to flexible transparent metal grid conducting film, its characterized in that: the components comprise, by weight, 30-45 parts of submicron spherical silver powder, 8-23 parts of flaky silver powder, 0.5-1.5 parts of alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate, 28 parts of polyurethane resin, 10 parts of ethylene glycol ethyl ether acetate and 7-8.5 parts of diethyl carbonate; the average particle size D50 of the submicron spherical silver powder is 0.45 mu m, and the specific surface area is 1.07 m 2 (ii)/g; the average grain diameter D50 of the flaky silver powder is 0.95 mu m, and the specific surface area is 1.35 m 2 /g。
2. The ultra-low temperature curing silver paste for the flexible transparent metal grid conductive film according to claim 1, wherein the polyurethane resin is prepared by fully dissolving 20% of halogen-free thermoplastic polyurethane elastomer rubber in 80% of organic solvent, and the organic solvent is composed of 24% of isophorone and 76% of diethyl carbonate.
3. The ultra-low temperature curing silver paste for the flexible transparent metal grid conductive film according to claim 1, wherein the alkyl (aryl) ketoxime is one of benzophenone oxime, acetophenone oxime and butanone oxime.
4. The preparation method of the ultralow temperature curing silver paste for the flexible transparent metal grid conductive film according to claim 1, is characterized by comprising the following steps:
step one, fully dissolving and uniformly mixing polyurethane resin and alkyl (aryl) ketoxime closed modified hexamethylene diisocyanate in a container, and pouring submicron spherical silver powder and flake silver powder into the container to be fully and uniformly stirred;
adding organic solvents of ethylene glycol ethyl ether acetate and diethyl carbonate into the continuously flowing fluid-like slurry, and continuously stirring the mixture fully and uniformly in a short time;
step three, fully mixing, rolling and finely grinding by using a three-roller grinder to obtain conductive silver paste, filtering and vacuumizing to eliminate residues and bubbles in the silver paste;
and step four, the fineness of the slurry measured by a scraper blade fineness gauge is less than 5 mu m, and the ultralow temperature curing silver slurry for the metal grid conductive film is obtained.
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