CN114709005A - Silver paste for flexible transparent conductive film metal grid, preparation method and application thereof - Google Patents
Silver paste for flexible transparent conductive film metal grid, preparation method and application thereof Download PDFInfo
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- CN114709005A CN114709005A CN202210323707.0A CN202210323707A CN114709005A CN 114709005 A CN114709005 A CN 114709005A CN 202210323707 A CN202210323707 A CN 202210323707A CN 114709005 A CN114709005 A CN 114709005A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 76
- 239000004332 silver Substances 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 45
- 238000001723 curing Methods 0.000 claims description 41
- 239000010408 film Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 17
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 150000001253 acrylic acids Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract 2
- 229920002799 BoPET Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 240000004282 Grewia occidentalis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/12—Braided wires or the like
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a silver paste for a flexible transparent conductive film metal grid, a preparation method and application thereof, wherein the silver paste comprises the following components in percentage by weight: 60-80% of silver powder, 5-15% of polyester, 15-25% of organic solvent, 0.5-1% of dispersing agent, 0.5-1% of accelerating agent and 0.5-1% of curing agent. According to the silver paste disclosed by the invention, through a unique formula design, the curing temperature of the silver paste is reduced, the curing time is effectively shortened, the lower resistivity is obtained, the bonding force and the mechanical property of the silver paste on a PET (polyethylene terephthalate) film can be increased, and the silver paste has good fluidity and a good dispersion effect, so that the silver paste has a good filling effect on a 3-micrometer groove, and the finally prepared conductive film has good conductivity and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of conductive materials, and particularly relates to a silver paste for a flexible transparent conductive thin film metal grid, a preparation method and application thereof.
Background
With the development of smart devices, touch panels play a dominant role in smart devices, and transparent conductive films are one of the core materials of touch panels. At present, most of transparent conductive thin film materials used in the market are still traditional Indium Tin Oxide (ITO), but because the deposition temperature of ITO metal Oxide is high, the process is complex, the flexibility is poor, and Indium element is a rare resource, the production cost is expensive. Therefore, a material which has good flexibility and low cost and can replace ITO is urgently needed to be found. The metal mesh conductive film has high conductivity, high light transmittance, good flexibility and simple production process, can replace ITO (indium tin oxide), and provides a direction for the development of flexible transparent conductive materials.
Obtaining a latticed groove on the PET film through the processes of exposure, development, etching and the like, filling silver paste into the groove for 50 ℃ pre-curing, then wiping off the residual silver paste on the surface of the PET film by using alcohol cloth, only leaving the silver paste filled in the groove, and finally curing at low temperature (100 plus 150 ℃) to form a metal conductive grid, thus obtaining the flexible transparent conductive film material. The silver paste is one of the core materials, and the performance of the silver paste directly influences the use performance of the conductive film. The viscosity, thixotropic value, fineness and resistivity of the silver paste directly influence the filling property and conductivity of the PET film, the silver paste needs to be cured at low temperature, and the silver paste has excellent binding force with a substrate.
Chinese patent application CN104332214B discloses a low-temperature cured conductive silver paste and a preparation method thereof, wherein the conductive silver paste is prepared from the following components by mass percent: silver powder: 60-80 parts of; polymer resin carrier: 5-20; epoxy resin oligomer: 5-20; solvent: 5-10; curing agent: 0.1 to 5. A method of making a conductive silver paste, comprising the steps of: preparing a prepolymer, preparing a dispersoid, preparing a precursor, adding silver powder into a stirring box, mixing, grinding and filtering to obtain the conductive silver paste. The low-temperature curing conductive silver paste can achieve a low-temperature curing effect, has excellent adhesive force and hardness performance, but has high resistivity and poor fluidity and dispersibility, and is not suitable for being used as a silver paste for a flexible transparent conductive film metal grid, particularly a silver paste for filling a groove with the thickness of 3 micrometers.
CN106847369A discloses a low-temperature curing conductive silver paste for a printed capacitive touch screen and a preparation method thereof, wherein the printed conductive silver paste for the printed capacitive touch screen comprises 50-82% of silver powder, 5-15% of a polymer binder, 2-5% of a curing agent, 10-25% of a solvent and 1-5% of an auxiliary agent by weight. The preparation method comprises the following steps: 1) selecting according to the weight percentage of the formula; 2) weighing the macromolecular binder according to the formula; 3) adding a low-temperature deblocking latent curing agent and an auxiliary agent; 4) weighing silver powder according to the formula, and uniformly stirring the silver powder in an organic carrier through a high-speed dispersion machine; 5) grinding for 6-10 times by using a three-roll grinder; 6) and (5) vacuum degassing by a stirring defoaming machine, and detecting to be qualified to obtain the silver paste. The conductive silver paste prepared by the patent has good printability, the printing resolution reaches 50um, the conductivity is good, but the square resistance is large, the printing resolution is large, and the conductive silver paste is not suitable for being used as a silver paste for a flexible transparent conductive film metal grid, especially for filling a silver paste with a groove of 3 mu m.
CN110993149A discloses a metal mesh capacitive flexible touch screen silver paste, which comprises: high molecular weight saturated polyester resin, low molecular weight saturated polyester resin, nano silver powder, an organic solvent, a wetting dispersion auxiliary agent and a curing agent. The preparation method of the silver paste comprises the following steps: mixing, stirring and dispersing low-molecular-weight saturated polyester resin, a curing agent, a wetting dispersant auxiliary agent and an organic solvent to obtain a mixture; adding nano silver powder into the obtained mixture, stirring and dispersing for 5-20 min, then adding high molecular weight saturated polyester resin, stirring and dispersing for 10-30 min to obtain slurry; and finally, centrifuging the obtained slurry until the fineness of the slurry is less than 2 mu m to obtain the metal grid silver paste. The conductive silver paste prepared by the patent needs a baking temperature of 140 ℃ and a baking time of 30 minutes, so that the risk of PET deformation caused by a higher baking temperature is avoided, and the conductive silver paste is not suitable for a high-efficiency tunnel furnace baking process.
Therefore, there is still a need to develop a silver paste suitable for a tunnel furnace baking process, having low resistivity and excellent bonding force and mechanical properties on a PET film, and suitable for a flexible transparent conductive thin film metal grid.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the silver paste for the flexible transparent conductive film metal grid, which has low curing temperature, baking time of less than 10 minutes and good fluidity and conductivity, so that the paste has a good filling effect on a 3-micrometer groove, and the filling density and the saturation of the paste are high, so that the conductive film has good conductivity and mechanical properties.
The invention also aims to provide a preparation method of the silver paste for the flexible transparent conductive film metal grid.
The invention further aims to provide application of the silver paste for the flexible transparent conductive thin film metal grid.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the silver paste for the flexible transparent conductive film metal grid comprises the following components in parts by weight:
60-80 parts of silver powder, preferably 65-75 parts;
5-15 parts of polyester, preferably 8-12 parts;
10-25 parts of organic solvent, preferably 13-20 parts;
0.5-1 part of dispersant, preferably 0.5 part;
0.5-1 part of accelerator, preferably 0.5 part;
0.5-1 part of curing agent, preferably 0.5 part.
In a specific embodiment, the silver powder is a monodisperse, submicron, spheroidal silver powder; preferably, the particle size of the silver powder is 300-500 nm.
In a particular embodiment, the polyester is a linear saturated polyester, preferably a linear saturated polyester having a molecular weight Mn of 10000-50000.
In a specific embodiment, the organic solvent is an ester solvent, preferably selected from any one or a mixture of ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate.
In a specific embodiment, the dispersant is selected from any one or two of modified polyesters, alkylolammonium salts, high molecular weight block copolymers, and the like.
In a specific embodiment, the accelerator is selected from any one of acrylic modified polyesters, acrylic modified chlorinated polyolefins or modified acrylics, preferably acrylic modified polyesters.
In a particular embodiment, the curing agent is selected from lewis acid amine adduct type curing agents, preferably any one selected from boron trifluoride-amine complex, zinc chloride-amine complex, aluminum chloride-amine complex.
On the other hand, the preparation method of the silver paste for the flexible transparent conductive thin film metal grid comprises the following steps:
A. uniformly mixing polyester and an organic solvent in proportion, and heating until the polyester and the organic solvent are completely dissolved to prepare a mixture a;
B. mixing the mixture a with a dispersant, an accelerator and a curing agent in proportion, and putting the mixture into a centrifugal defoaming machine to be uniformly stirred to prepare a mixture b;
C. and mixing the mixture b and the silver powder in proportion, putting the mixture into a centrifugal defoaming machine, uniformly stirring, grinding the mixture by using a ball mill until the fineness is less than 2 mu m, and uniformly stirring the mixture by using centrifugal defoaming to obtain the finished product silver paste.
In a specific embodiment, the mixing mass ratio of the polyester and the organic solvent in the step a is 60: and 40, heating to 60-80 ℃ to completely dissolve.
On the other hand, the silver paste for the metal mesh of the flexible transparent conductive film is applied to the metal mesh conductive film.
Compared with the prior art, the invention has the following beneficial effects:
the silver paste for the flexible transparent conductive film metal grid is designed by a unique formula, particularly the Lewis acid complex is added, so that the curing time of the silver paste is shortened, the curing temperature of the silver paste is reduced, and the volume resistivity can reach 1 multiplied by 10 at least-5Omega cm, the binding force and the mechanical property of the silver paste on the PET film can be increased, and the adhesive force can reach 5B; in addition, the silver paste formula disclosed by the invention has the advantages that the solvents with different boiling points are added, so that the paste can be quickly surface-dried at about 50 ℃, and the cleaning is avoidedWhen residual silver paste on the surface of the PET film is left, the silver paste in the groove is wiped off; the silver paste prepared by using the linear saturated polyester and adding the dispersing agent and the accelerant has good fluidity and dispersing effect, and the fineness of the paste can reach 1 mu m, so that the paste has good filling effect on the grooves with the size of 3 mu m, and the filling density and the saturation of the paste are high, so that the conductive film has good conductivity and mechanical property.
Drawings
FIG. 1 is an SEM spectrum of a silver paste obtained in example 1 of the present invention after mold filling and curing.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting.
In one scheme of the invention, the silver paste for the flexible transparent conductive film metal grid comprises the following components in parts by weight: 60-80 parts of silver powder, 5-15 parts of polyester, 10-25 parts of organic solvent, 0.5-1 part of dispersant, 0.5-1 part of accelerator and 0.5-1 part of curing agent.
In a preferred scheme, the silver paste for the flexible transparent conductive film metal grid comprises the following components in parts by weight: 65-75 parts of silver powder; 8-12 parts of polyester; 13-20 parts of an organic solvent; 0.5 part of a dispersant; 0.5 part of an accelerator; 0.5 part of curing agent.
In a more preferable scheme, the silver paste for the flexible transparent conductive film metal grid comprises the following components in parts by weight: 75 parts of silver powder; 10 parts of polyester; 13.5 parts of an organic solvent; 0.5 part of a dispersant; 0.5 part of an accelerator; 0.5 part of curing agent.
In the present invention, the silver powder is a monodisperse, submicron, spherical-like silver powder, the method for preparing the silver powder is not particularly limited, the purity of the silver is, for example, 99.95% or more, and the particle size of the silver powder is preferably 300-500nm, including, but not limited to, 300nm, 325nm, 350nm, 380nm, 400nm, 425nm, 450nm, 475nm, 500 nm.
In the present invention, the polyester is a linear saturated polyester, preferably a linear saturated polyester having a molecular weight Mn of 10000-50000, more preferably a linear saturated polyester having a molecular weight Mn of 20000-30000, and examples thereof include, but are not limited to, Dynapol L912, Dynapol L411, Dynapol L952, and Desmophen1652, all of the Cordsura.
In the present invention, the organic solvent is an ester solvent, preferably a mixed ester solvent of one or more selected from ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, and ethylene glycol ethyl ether acetate, preferably a mixed ester solvent of two kinds, for example, a mixed ester solvent composed of ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate. The mixing ratio of the two kinds of the esters is not particularly limited, and for example, the mass ratio is 1: 1-3; for the mixed solvent of the three esters, the mixing mass ratio is, for example, 1: 2: 2.
in the present invention, the dispersant is selected from any one or two of fatty acid-modified polyester, alkylhydroxylammonium salt, and high molecular weight block copolymer, and preferably alkylhydroxylammonium salt. The fatty acid-modified polyester may be, for example, Effka 6220, the alkylhydroxylammonium salt-based silicone oil may be, for example, BYK180, and the high molecular weight-containing block copolymer may be, for example, Effka 4310.
In the present invention, the accelerator is selected from any one of acrylic-modified polyesters, acrylic-modified chlorinated polyolefins, or modified acrylic acids, and preferably acrylic-modified polyesters. The acrylic modified polyester may be Tech-7205 or TextileLTH, and the modified chlorinated polyolefin may be DX-530P, HM-21P or F-2P.
In the present invention, the curing agent is selected from lewis acid amine complexes, preferably any one of boron trifluoride-amine complexes, zinc chloride-amine complexes, and aluminum chloride-amine complexes.
On the other hand, the preparation method of the silver paste for the flexible transparent conductive thin film metal grid comprises the following steps:
A. polyester and an organic solvent are mixed according to the mass ratio of 60:40, uniformly mixing, and heating to 60-80 ℃ to completely dissolve to prepare a mixture a;
B. mixing the mixture a with a dispersant, an accelerator and a curing agent in proportion, and putting the mixture into a centrifugal defoaming machine to be uniformly stirred to prepare a mixture b;
C. and (4) mixing the mixture b and the silver powder in proportion, putting the mixture into a centrifugal defoaming machine, uniformly stirring, and dispersing by using a ball mill until the fineness is less than 2 mu m to obtain the finished product of silver paste.
The invention is further illustrated, but not limited, by the following more specific examples.
Example 1
The silver paste for the flexible transparent conductive film metal grid comprises metal filler and base material, wherein the weight ratio of the metal filler to the base material is 75: 25.
the base material is prepared from the following raw materials in parts by weight: 10 parts of carrier resin, 13.5 parts of mixed esters, 0.5 part of accelerator, 0.5 part of dispersant and 0.5 part of curing agent.
The metal filler is submicron silver powder, and the particle size and the appearance of the metal filler are monodisperse 300nm spherical silver powder.
The carrier resin is Dynapol L411, and is prepared by mixing with an organic solvent according to the mass ratio of 60:40 and heating and dissolving at 70 ℃.
The mixed ester is formed by mixing ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate according to the mass ratio of 5: 8.5.
The accelerator is degussel LTH.
The dispersant is Effa 6220.
The curing agent is boron trifluoride-amine complex curing agent.
The preparation method of the silver paste for the flexible transparent conductive film metal grid comprises the following steps:
A. mixing polyester and organic solvent according to the proportion of 60:40, uniformly mixing, and heating to 70 ℃ to completely dissolve to prepare a mixture a;
B. mixing the mixture a with a dispersant, an accelerator and a curing agent according to the proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, and stirring for 3min to prepare a mixture b;
C. and mixing the mixture b and silver powder in proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, stirring for 3min, and dispersing by using a ball mill until the fineness is less than 2 mu m to obtain the finished product of silver paste.
Fig. 1 shows an SEM spectrogram of the silver paste obtained in example 1 after mold filling and curing, and it can be found that the paste of the present invention has a good filling effect on a 3 μm groove, and the filling density and the saturation of the paste are high.
Example 2
The silver paste for the flexible transparent conductive film metal grid comprises metal filler and base material, wherein the weight ratio of the metal filler to the base material is 65: 35;
the base material is prepared from the following raw materials in parts by weight: 15 parts of carrier resin, 17 parts of mixed esters, 1 part of accelerator, 1 part of dispersant and 1 part of curing agent.
The metal filler is submicron silver powder, and the particle size and the appearance of the metal filler are monodisperse 400mm sphere-like silver powder.
The carrier resin is Dynapol L952, and is prepared by mixing with an organic solvent according to the mass ratio of 60:40, and heating and dissolving at 80 ℃.
The mixed ester is formed by mixing ethylene glycol butyl ether acetate and propylene glycol methyl ether acetate according to the mass ratio of 5: 12.
The promoter is Tech-7205.
The dispersant is Effa 6220.
The curing agent is a zinc chloride-amine complex curing agent.
A preparation method of silver paste for a flexible transparent conductive film metal grid comprises the following steps:
A. mixing polyester and organic solvent according to the proportion of 60:40, uniformly mixing, and heating to 80 ℃ to completely dissolve to prepare a mixture a;
B. mixing the mixture a with a dispersant, an accelerator and a curing agent in proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, and stirring for 3min to prepare a mixture b;
C. and mixing the mixture b and silver powder in proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, stirring for 3min, and dispersing by using a ball mill until the fineness is less than 2 mu m to obtain the finished product silver paste.
Example 3
The silver paste for the flexible transparent conductive film metal grid comprises a metal filler and a base material, wherein the weight ratio of the metal filler to the base material is 80: 20;
the base material is prepared from the following raw materials in parts by weight: 5 parts of carrier resin, 13.5 parts of mixed esters, 0.5 part of accelerator, 0.5 part of dispersant and 0.5 part of curing agent.
The metal filler is submicron silver powder, and the particle size and the appearance of the submicron silver powder are 500nm quasi-spherical silver powder.
The carrier resin is Dynapol L952, and is prepared by mixing the Dynapol L952 with an organic solvent according to a mass ratio of 60:40 and heating and dissolving at 60 ℃.
The organic solvent is ethylene glycol butyl ether acetate.
The mixed ester is formed by mixing ethylene glycol butyl ether acetate and ethylene glycol ethyl ether acetate according to the mass ratio of 5: 8.5.
The promoter is Tech-7205.
The dispersant is Effa 6220.
The curing agent is an aluminum chloride-amine complex.
A preparation method of silver paste for a flexible transparent conductive film metal grid comprises the following steps:
A. mixing polyester and organic solvent according to the proportion of 60:40, uniformly mixing, heating to 60 ℃, and completely dissolving to prepare a mixture a;
B. mixing the mixture a with an organic solvent, a dispersant, an accelerator and a curing agent in proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, and stirring for 3min to prepare a mixture b;
C. and mixing the mixture b and silver powder in proportion, putting the mixture into a centrifugal defoaming machine 1800r/min, stirring for 3min, and dispersing by using a ball mill until the fineness is less than 2 mu m to obtain the finished product of silver paste.
Comparative example 1
Compared with example 1, no curing agent was added, and other conditions were completely the same.
Comparative example 2
Compared with example 1, the curing agent is replaced by isocyanate, and other conditions are completely consistent.
Comparative example 3
Compared with example 1, the curing agent is halved, and other conditions are completely consistent.
Comparative example 4
Compared with the silver powder in the embodiment 1, the silver powder is replaced by the submicron silver powder mixed by the spherical silver powder and the massive silver powder, and other conditions are completely consistent.
Comparative example 5
Compared with the organic solvent in the embodiment 1, the organic solvent is replaced by single butyl ether acetate oxalate, and other conditions are completely consistent.
Comparative example 6
Compared with example 1, no accelerator was added, and other conditions were completely the same.
The silver pastes of the examples and the comparative examples are characterized, and the performance characterization step comprises the following steps:
volume resistivity test flow: vacuum defoaming the prepared slurry for 5-10min → introducing the slurry into a mold (length and width 100mm x 5mm x 0.03mm) taking glass as a base material → placing the slurry into an oven to bake at 120 ℃ for 10min → measuring the resistance values at two ends of the slurry by a four-corner probe instrument, measuring for 3 times and taking an average value.
And (3) PET film adhesion: screen printing to PET film using 20mm by 20mm open mesh plate → placing in oven for baking at 120 ℃ for 10min → testing using the checkers method, test 3 times.
Testing the joint filling performance: scraping the slurry on the PET film by using a soft printing knife for 5 times up and down, then scraping for 5 times left and right, placing the PET film in an oven with the temperature of 50 ℃ for baking for 1min, wiping the surface of the PET film clean by using alcohol cloth, placing the PET film in the oven for baking at the temperature of 120 ℃ for 10min, and observing the joint filling effect of the slurry by using a scanning electron microscope.
The corresponding evaluation items and evaluation criteria are shown in Table 1, and the test results are shown in Table 2.
Table 1 silver paste performance test method
Table 2 silver paste performance test data table
According to the volume resistivity test flow, the curing time of the silver paste prepared by the embodiment of the invention is lower than 10 minutes, the curing temperature is 120 ℃, the silver paste is suitable for the tunnel furnace baking process, PET deformation cannot be caused, and as shown in the table, the silver paste prepared by the embodiment of the invention has the advantages of low volume resistivity, small viscosity and good gap filling performance, and the adhesive force on a PET film can reach 5B.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The silver paste for the flexible transparent conductive film metal grid is characterized by comprising the following components in parts by weight: 60-80 parts of silver powder, preferably 65-75 parts;
5-15 parts of polyester, preferably 8-12 parts;
10-25 parts of organic solvent, preferably 13-20 parts;
0.5-1 part of dispersant, preferably 0.5 part;
0.5-1 part of accelerator, preferably 0.5 part;
0.5-1 part of curing agent, preferably 0.5 part.
2. The silver paste for the flexible transparent conductive film metal grid according to claim 1, wherein the silver powder is a monodisperse, submicron, spheroidal silver powder; preferably, the particle size of the silver powder is 300-500 nm.
3. The silver paste for the metal grid of the flexible transparent conductive film as claimed in claim 1, wherein the polyester is linear saturated polyester, preferably linear saturated polyester with a molecular weight Mn of 10000-50000.
4. The silver paste for the flexible transparent conductive film metal grid according to claim 1, wherein the organic solvent is an ester solvent, preferably one or a mixture of ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate.
5. The silver paste for the metal grid of the flexible transparent conductive film according to claim 1 or 4, wherein the dispersing agent is selected from any one or two of modified polyesters, alkylol ammonium salts, and block copolymers containing high molecular weight.
6. The silver paste for the flexible transparent conductive film metal grid according to claim 1, wherein the accelerant is selected from any one of acrylic modified polyesters, acrylic modified chlorinated polyolefins or modified acrylic acids, and is preferably acrylic modified polyester.
7. The silver paste for the metal grid of the flexible transparent conductive film according to claim 1, wherein the curing agent is selected from lewis acid amine adduct type curing agents, preferably any one selected from boron trifluoride-amine complex, zinc chloride-amine complex, and aluminum chloride-amine complex.
8. The preparation method of the silver paste for the flexible transparent conductive thin film metal grid according to any one of claims 1 to 7, characterized by comprising the following steps:
A. uniformly mixing polyester and an organic solvent in proportion, and heating until the polyester and the organic solvent are completely dissolved to prepare a mixture a;
B. mixing the mixture a with a dispersant, an accelerator and a curing agent in proportion, and putting the mixture into a centrifugal defoaming machine to be uniformly stirred to prepare a mixture b;
C. and mixing the mixture b and the silver powder in proportion, putting the mixture into a centrifugal defoaming machine, uniformly stirring, grinding the mixture by using a ball mill until the fineness of the mixture is less than 2 mu m, and uniformly stirring the mixture by using centrifugal defoaming to obtain the finished product of the silver paste.
9. The method for preparing silver paste for the metal grid of the flexible transparent conductive film according to claim 8, wherein the mixing mass ratio of the polyester to the organic solvent in the step A is 60: and 40, heating to 60-80 ℃ to completely dissolve.
10. Use of the silver paste for the metal grid of the flexible transparent conductive film according to any one of claims 1 to 7 in a metal mesh conductive film.
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Cited By (1)
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| CN115497663A (en) * | 2022-09-01 | 2022-12-20 | 天津宝兴威科技股份有限公司 | Flexible nano conductive silver paste and preparation method thereof |
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