CN109473197A - It is a kind of to contain silver-supramolecular organogel high-resolution conductive silver paste and preparation method thereof - Google Patents
It is a kind of to contain silver-supramolecular organogel high-resolution conductive silver paste and preparation method thereof Download PDFInfo
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- CN109473197A CN109473197A CN201811351475.XA CN201811351475A CN109473197A CN 109473197 A CN109473197 A CN 109473197A CN 201811351475 A CN201811351475 A CN 201811351475A CN 109473197 A CN109473197 A CN 109473197A
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- silver paste
- argentiferous
- organogel
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 38
- 239000004332 silver Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- OEYQBKYISMRWQB-UHFFFAOYSA-N Santal Chemical compound C=1C(OC)=CC(O)=C(C2=O)C=1OC=C2C1=CC=C(O)C(O)=C1 OEYQBKYISMRWQB-UHFFFAOYSA-N 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 235000001014 amino acid Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- -1 alcohol ester Chemical class 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000008729 phenylalanine Nutrition 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000002994 phenylalanines Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 7
- 238000010008 shearing Methods 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000013008 thixotropic agent Substances 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229940100616 topical oil Drugs 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Contain silver-supramolecular organogel high-resolution conductive silver paste and preparation method thereof the present invention provides a kind of, the conductive silver paste, as unit of parts by weight, including following raw material: 55-70 parts of silver powder, 1-3 parts of glass powder with low melting point, silver -30-50 parts of supramolecular organogel.Wherein, conductive silver paste is prepared using argentiferous-supramolecular organogel, on the one hand, argentiferous organogel can be gathered into tiny 1-2nm fiber element in slurry system, then it is self-assembly of the belt fibre bundle of the 10-20nm largely mutually wound, system can be easy to when removing shearing force in this way, quickly form stable gel rubber system, realize high-fineness printing, on the other hand, the nano silver that silver is decomposed to form in argentiferous organogel when silver paste is sintered is dispersed in silver paste system, it solves the problems, such as directly to add the dispersion of nano silver difficulty, therefore, it is bad that the present invention well solves existing conductive silver paste electric conductivity, the problems such as printed resolution is low and stability is inadequate.
Description
The invention belongs to silver paste preparation technical fields for technical field, and in particular to one kind contains silver-supramolecular organogel
High-resolution conductive silver paste and preparation method thereof.Background technique conductive silver paste by silver powder, organic or inorganic binder, solvent,
The paste of additive composition mainly forms conductive film by printing-sintering to conduct electric current.What conductive silver paste needed to have
Characteristic has: electric conductivity is good, adhesive force is strong and printing adaptability superior properties.Electrocondution slurry is the basis for developing electronic component,
Silver-based electric slurry is become with mechanical performances such as its high conductivity, excellent adhesion property and solderabilities produces various electronics member devices
The key function material of part product, has the function of can not be substituted in the electronics industry.The high-speed transfer of electronic information industry and
Miniaturization, intelligentized development trend, it is desirable that element has higher performance and smaller size, therefore used conductive silver
Slurry must have higher electric conductivity, higher printed with fine resolution ratio and uniformity consistency.
Currently, preparing electrocondution slurry to improve the main method of conductivity is addition portion size for nano-silver powder, promotion is burnt
Knot, to form fine and close conductive network, still, common nano-Ag particles (are mainly adopted using physical method or chemical method
With liquid phase reduction) it prepares, these methods reuse after obtaining pure nano-Ag particles.One is directly add it to contain
Have in the formula mixed solutions such as surfactant, adjusts viscosity and obtain silver paste, and in this preparation process, nano-Ag particles do not have
Surfactant package is easy to happen reunion, reduces Argent grain and receive since nano-Ag particles have very high interfacial energy
The advantage of rice sintering, is not achieved the purpose for improving electric conductivity；Another kind is by a large amount of Coated with Organic Matter of nano-silver powder, in this way
The dispersed in silver paste system of nano powder can be improved, but a large amount of organic matter can not decompose completely during the sintering process,
The generation that will lead to residual carbon in this way, causes cavity, influences conductivity.
On the other hand, for the performance boost of high printed resolution and high stability, conventional method mainly by using
Macromolecule thixotropic agent such as polyamide wax or inorganic thixotropic agent such as bentonite, fumed silica etc. adjust the thixotroping of conductive silver paste
Performance improves printed with fine degree, is mostly silver powder and solvent in slurry, while the macromolecule thixotropic agent external world responds still
Speed and system network structure restore slow, are limited using the thixotropic agent for adding a small amount of to improve printed resolution, can not
Reach market demands, and then will affect electric conductivity using nonconducting inorganic matter thixotropic agent.
In order to expand the application field of silver paste, meet electronics industry to the high performance requirement of silver paste, develop a kind of high lead
The silver paste of electricity, high-resolution and high stable consistency is imperative.
The present invention prepares conductive silver paste using argentiferous-supramolecular organogel, can well solve the above problem.One
Aspect, argentiferous organogel can in slurry system with intermolecular hydrogen bonding, hydrophobic effect etc. be driving force be gathered into it is tiny
Then 1-2nm fiber element is self-assembly of the belt fibre bundle of 10-20nm largely mutually wound or so on this basis,
Viscosity becomes smaller when system being made to apply shearing force in this way, and system can be easy to, quickly be formed surely when removing shearing force
Fixed gel rubber system, can be realized high-fineness, high-resolution printing, at the same can better stabilization of solid particle, keep
The stable and consistent of product；On the other hand, the nano silver that silver is decomposed to form in argentiferous organogel when silver paste is sintered is evenly dispersed
In silver paste system, solves the problems, such as directly to add the dispersion of nano silver difficulty, improve the electric conductivity and uniformity of silver paste, because
This, silver paste of the invention had not only had high electric conductivity but also had had outstanding printing precision, it can satisfy more use occasions,
Application range and market prospects are more wide.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of high-performance conductive silver pastes and preparation method thereof, to solve existing lead
The problem that electric silver paste electric conductivity is bad, printed resolution is low and stability is inadequate.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of to contain silver-supramolecular organogel high-resolution conductive silver paste, which is characterized in that as unit of parts by weight, packet
Include following raw material:
55-70 parts of silver powder；
1-3 parts of glass powder with low melting point；
30-50 parts of argentiferous supramolecular organogel；
The silver powder is the silver powder that oleamide or lauric amide are surface-treated, and silver powder average grain diameter is 200-500nm；
The glass powder with low melting point is Bi2O3-B2O3-SiO2-Al2O3- CuO system, softening point are 460-650 DEG C, partial size 2-4 μ
m；
The argentiferous supramolecular organogel the preparation method is as follows:
(1) under nitrogen protection and 50 DEG C of heating conditions, 1-3 parts of phenylalanines are dissolved in 2-5 parts of tetrahydrofurans, thereto by
Two (trichloromethyl) carbonic ester of 2-5 part gradually is added until solution becomes transparent, reaction 3h, product vacuum is dry and recrystallizes, and obtains
To white crystal；
(2) 15-30 parts of white crystal of gained, 1-5 parts of methylene chloride and 3-5 parts of alkyl amino acid silver in step (1) are placed in appearance
It in device, in 40-60 DEG C of reaction 12-36h, is put into ether and sediment is precipitated, in drying at room temperature 8h, it is neat to obtain argentiferous phenylpropyl alcohol amino
Polymers.
(3) 1 part of phenylpropyl alcohol amino oligomer of gained in step (3) is added in 3-6 parts of organic solvents, is heated to 40 DEG C of stirrings
30min is mixed until dissolution, is cooled to room temperature to get silver-supramolecular organogel.
Further, the structure of the alkyl amino acid silver is as follows:
H2N-R--COOAg
R indicates alkyl (CH2)12-(CH2)18Further, the structure of the argentiferous phenylpropyl alcohol amino oligomer is as follows:
Wherein, n 5-8；R indicates alkyl (CH2)12-(CH2)18；Ph represents phenyl ring
Further, the organic solvent is one of santal 803, alcohol ester 12 and terpinol or a variety of mixtures
Further, the preparation method of the conductive silver paste, it is characterised in that following processing step:
(1) silver powder is uniformly mixed with glass powder with low melting point with airflow milling；
(2) mixture in step (1) is added in silver-supramolecular organogel, is placed in double-planet mixing and blending machine in 50-
80rmp speed stirs 1-2h；
(3) said mixture dispersion mixing is uniformly carried out to three roller grindings afterwards, fineness is rolled less than 10 μm, conductive silver paste is made.
The invention has the following advantages:
A. for the performance boost of high printed resolution and high stability, conventional method is mainly by using macromolecule thixotropic agent
Such as polyamide wax or inorganic thixotropic agent such as bentonite, fumed silica adjust the thixotropic property of conductive silver paste, improve print
Brush fineness, still, macromolecule thixotropic agent restore slow to extraneous response speed and system network structure, a small amount of using addition
Thixotropic agent is limited to improve printed resolution, can not reach market demands, and uses nonconducting inorganic matter thixotropic agent
It then will affect electric conductivity.Conductive silver paste prepared by the present invention uses argentiferous-supramolecular organogel, can be in slurry system
In with intermolecular hydrogen bonding, hydrophobic effect etc. be driving force be gathered into tiny 1-2nm fiber element, then on this basis from group
Dress forms the belt fibre bundle of 10-20nm largely mutually wound or so, so that and viscosity becomes smaller when system applies shearing force,
System can be easy to, quickly form stable gel rubber system when removing shearing force, so that slurry filament printing performance
Excellent, moulding ability is good, can be realized high-fineness, high-resolution printing, at the same can better stabilization of solid particle, protect
Hold the stable and consistent of product；
B. it is direct addition nano-silver powder in silver paste that tradition, which improves silver paste electric conductivity, and nano-silver powder specific surface area is small, easily
The characteristic of reunion reduces the clinkering-aid advantage of nano-Ag particles, and argentiferous-supermolecule that silver paste prepared by the present invention uses has
In homogeneously in system, resolving into nano silver in sintering can be dispersed in silver paste system machine gel, solve
The problem of directly addition nano silver difficulty is dispersed, the uniformity consistency and stability of silver paste are improved, while improving the burning of silver powder
Knot activity, the densification of acceleration of sintering silver layer improve conductivity.
Detailed description of the invention
Fig. 1 is that supermolecular gel forms schematic diagram
Fig. 2 is the fibre bundle SEM figure mutually wound in argentiferous supermolecular gel system
Fig. 3 is the fast quick-recovery schematic diagram of argentiferous supramolecular organogel conductive silver paste stress.
Specific embodiment is to facilitate a better understanding of the present invention, is illustrated by following embodiment, these example categories
It is limited the scope of the invention in protection scope of the present invention, but not.
Embodiment 1
The preparation of argentiferous supramolecular organogel, following ratio are by weight:
(1) under nitrogen protection and 50 DEG C of heating conditions, 1 part of phenylalanine is dissolved in 3 parts of tetrahydrofurans, is gradually added thereto
Enter 3 part of two (trichloromethyl) carbonic ester until solution becomes transparent, reaction 3h, product vacuum is dry and recrystallizes, and obtains white
Crystal；
(2) by 15 parts of white crystals of gained, 1 part of methylene chloride and 3 parts of alkyl amino acid silver H in step (1)2N--(CH2)12-
COOAg is placed in container, for 24 hours in 40 DEG C of reactions, is put into ether and sediment is precipitated, and in the dry 8h of room temperature in vacuo, obtains argentiferous
Phenylpropyl alcohol amino oligomer 。
(3) 1 part of phenylpropyl alcohol amino oligomer of gained in step (3) is added in 3 portions of santals 803, it is mixed is heated to 40 DEG C of stirrings
30min is closed until dissolution, clear gel can be obtained by being cooled to room temperature, as silver-supramolecular organogel.
The preparation of conductive silver paste, following ratio are by weight:
(1) by 55 parts of silver powder and 1 part of Bi2O3-B2O3-SiO2-Al2O3- CuO system glass powder with low melting point airflow milling mixes equal
It is even.Wherein, glass powder softening point is 500 DEG C, and average grain diameter is 1.5 μm；Silver powder average grain diameter is 200 nanometers, topical oil acid
Amide modifications processing.
(2) mixture in step (1) is added in 44 parts of silver-supramolecular organogels, merging planet gravity is mixed
Machine stirs 3min in 100rmp speed；
(3) said mixture dispersion mixing is uniformly carried out to three roller grindings afterwards, fineness is rolled less than 10 μm, conductive silver paste is made.
Embodiment 2
The preparation of argentiferous supramolecular organogel, following ratio are by weight:
(1) under nitrogen protection and 50 DEG C of heating conditions, 3 parts of phenylalanines are dissolved in 5 parts of tetrahydrofurans, are gradually added thereto
Enter 5 part of two (trichloromethyl) carbonic ester until solution becomes transparent, reaction 3h, product vacuum is dry and recrystallizes, and obtains white
Crystal；
(2) by 30 parts of white crystals of gained, 5 parts of methylene chloride and 5 parts of alkyl amino acid silver H in step (1)2N--(CH2)18-
COOAg is placed in container, in 60 DEG C of reaction 30h, is put into ether and sediment is precipitated, and in the dry 8h of room temperature in vacuo, obtains argentiferous
Phenylpropyl alcohol amino oligomer 。
(3) santal 803 of 5 parts of 1:3 and mixing for alcohol ester 12 is added in 1 part of phenylpropyl alcohol amino oligomer of gained in step (3)
It closes in liquid, is heated to 40 DEG C and is stirred 30min until dissolution, clear gel can be obtained by being cooled to room temperature, and as silver-supermolecule has
Machine gel.
The preparation of conductive silver paste, following ratio are by weight:
(1) by 70 parts of silver powder and 3 parts of Bi2O3-B2O3-SiO2-Al2O3- CuO system glass powder with low melting point airflow milling mixes equal
It is even.Wherein, glass powder softening point is 600 DEG C, and average grain diameter is 3 μm；Silver powder average grain diameter is 500 nanometers, surface lauric acid
Amide modifications processing.
(2) mixture in step (1) is added in 27 parts of silver-supramolecular organogels, merging planet gravity is mixed
Machine stirs 1min in 2000rmp speed；
(3) said mixture dispersion mixing is uniformly carried out to three roller grindings afterwards, fineness is rolled less than 10 μm, conductive silver paste is made.
Embodiment 3
The preparation of argentiferous supramolecular organogel, following ratio are by weight:
(1) under nitrogen protection and 50 DEG C of heating conditions, 2 parts of phenylalanines are dissolved in 4 parts of tetrahydrofurans, are gradually added thereto
Enter 4 part of two (trichloromethyl) carbonic ester until solution becomes transparent, reaction 3h, product vacuum is dry and recrystallizes, and obtains white
Crystal；
(2) by 21 parts of white crystals of gained, 3 parts of methylene chloride and 4 parts of alkyl amino acid silver H in step (1)2N--(CH2)16-
COOAg is placed in container, for 24 hours in 50 DEG C of reactions, is put into ether and sediment is precipitated, and in the dry 8h of room temperature in vacuo, obtains argentiferous
Phenylpropyl alcohol amino oligomer 。
(3) 4 parts of ratios are added in 1 part of phenylpropyl alcohol amino oligomer of gained in step (3) is 1:2;2 santal 803, alcohol ester ten
Two and terpinol mixed liquor in, be heated to 40 DEG C be stirred 30min until dissolution, clear gel can be obtained by being cooled to room temperature,
As silver-supramolecular organogel.
The preparation of conductive silver paste, following ratio are by weight:
(1) by 62 parts of silver powder and 2 parts of Bi2O3-B2O3-SiO2-Al2O3- CuO system glass powder with low melting point airflow milling mixes equal
It is even.Wherein, glass powder softening point is 650 DEG C, and average grain diameter is 2 μm；Silver powder average grain diameter is 300 nanometers, topical oil acid acyl
Amine modification.
(2) mixture in step (1) is added in 36 parts of silver-supramolecular organogels, merging planet gravity is mixed
Machine stirs 2min in 1000rmp speed；
(3) said mixture dispersion mixing is uniformly carried out to three roller grindings afterwards, fineness is rolled less than 10 μm, conductive silver paste is made.
Comparative example 1
Supermolecular gel in embodiment 1 is changed into the conventional organic carrier of ethyl cellulose preparation；0.7% is added in conductive silver paste
Polyamide wax is as thixotropic agent；The silver powder that 1% 30nm is added simultaneously replaces silver in argentiferous supermolecular gel to decompose the nanometer generated
In addition to this particle prepares conductive silver paste in the same manner as example 1.
Comparative example 2
Supermolecular gel in embodiment 2 is changed into the conventional organic carrier of ethyl cellulose preparation；1% gas is added in conductive silver paste
Aerosil is as thixotropic agent；The silver powder that 3% 50nm is added simultaneously is received instead of what silver decomposition in argentiferous supermolecular gel generated
In addition to this rice grain prepares conductive silver paste in the same way as in example 2.
Performance test:
Evaluating characteristics are carried out to conductive silver paste prepared in embodiment 1,2,3 and comparative example 1,2 in following operating condition.
I) it is printed in the alumina substrate of 20cmX 20cm using method for printing screen；
Ii) 15 minutes dry in 120 DEG C of drying oven；
Iii 15 minutes) are kept the temperature at 850 DEG C using sintering furnace；
Iv) sheet resistance is tested with four probe machines；
V) ultramicroscopic observation printed resolution is used；
Vi sweep electron microscopic measure thicknesses of layers) is used.
Resistivity=sheet resistance * thicknesses of layers
From the above results: under square one, therefore high resolution of the embodiment than comparative example, good conductivity uses silver-
The silver paste of supramolecular organogel production has excellent resolution ratio and electric conductivity.
Silver paste prepared by the present invention expands the application field of silver paste, meets the high performance to silver paste of electronics industry and wants
It asks, has a vast market application prospect.Technical indicator is from printing precision, electric conductivity and the performance indicator that can complete silver electrode
On reach the level of batch production.
Claims (5)
1. a kind of contain silver-supramolecular organogel high-resolution conductive silver paste, which is characterized in that as unit of parts by weight,
Including following raw material:
55-70 parts of silver powder；
1-3 parts of glass powder with low melting point；
30-50 parts of argentiferous supramolecular organogel
The silver powder is the silver powder that oleamide or lauric amide are surface-treated, and silver powder average grain diameter is 200-500nm；
The glass powder with low melting point is Bi2O3-B2O3-SiO2-Al2O3- CuO system, softening point are 460-650 DEG C, 2-4 μm of partial size；
The argentiferous supramolecular organogel the preparation method is as follows:
Under nitrogen protection and 50 DEG C of heating conditions, 1-3 parts of phenylalanines are dissolved in 2-5 parts of tetrahydrofurans, thereto gradually
Two (trichloromethyl) carbonic ester of 2-5 part is added until solution becomes transparent, reaction 3h, product vacuum is dry and recrystallizes, and obtains
White crystal；
15-30 parts of white crystal of gained, 1-5 parts of methylene chloride and 3-5 parts of alkyl amino acid silver in step (1) are placed in container
It is interior, it in 40-60 DEG C of reaction 12-36h, is put into ether and sediment is precipitated, in the dry 8h of room temperature in vacuo, obtain argentiferous phenylpropyl alcohol amino
Oligomer.
2. 1 part of phenylpropyl alcohol amino oligomer of gained in step (3) is added in 3-6 parts of organic solvents, it is heated to 40 DEG C and is stirred
30min is until dissolution, and clear gel can be obtained by being cooled to room temperature, as silver-supramolecular organogel.
3. the structure of alkyl amino acid silver according to claim 1 is as follows:
H2N-R--COOAg
R indicates alkyl (CH2)12-(CH2)18The structure of argentiferous phenylpropyl alcohol amino oligomer according to claim 1 is as follows:
Wherein, n 5-8；R indicates alkyl (CH2)12-(CH2)18；Ph represents phenyl ring.
4. organic solvent according to claim 1 is one of santal 803, alcohol ester 12 and terpinol or a variety of mixing
Object.
5. the preparation method of conductive silver paste according to claim 1, it is characterised in that following processing step:
Silver powder is uniformly mixed with glass powder with low melting point with airflow milling；
Mixture in step (1) is added in silver-supramolecular organogel, is placed in planet gravity mixing and blending machine in 1000-
2000rmp speed stirs 1-3min；
Said mixture dispersion mixing is uniformly carried out to three roller grindings afterwards, fineness is rolled less than 10 μm, conductive silver paste is made.
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