CN110010262A - Organic silver complex ultraviolet curing conductive silver paste - Google Patents
Organic silver complex ultraviolet curing conductive silver paste Download PDFInfo
- Publication number
- CN110010262A CN110010262A CN201910236010.8A CN201910236010A CN110010262A CN 110010262 A CN110010262 A CN 110010262A CN 201910236010 A CN201910236010 A CN 201910236010A CN 110010262 A CN110010262 A CN 110010262A
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- China
- Prior art keywords
- silver
- organic silver
- paste
- ultraviolet light
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 30
- 239000004332 silver Substances 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- -1 silver halide Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 25
- 150000003378 silver Chemical class 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000026030 halogenation Effects 0.000 claims description 5
- 238000005658 halogenation reaction Methods 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WWHZZMHPRRFPGP-UHFFFAOYSA-N 2,2,2-triiodoacetic acid Chemical compound OC(=O)C(I)(I)I WWHZZMHPRRFPGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005975 2-phenylethyloxy group Chemical group 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 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
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical group [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical group C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ZYXPMOIHQRKWGT-UHFFFAOYSA-N silver;2,2,2-trifluoroacetic acid Chemical compound [Ag].OC(=O)C(F)(F)F ZYXPMOIHQRKWGT-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses ultraviolet curing conductive silver paste which is composed of organic silver halide, spherical silver powder, hyperbranched polyurethane acrylate, a photoinitiator, a photopolymerization monomer, an organic solvent and an auxiliary agent. The conductive paste added with the organic silver halide can generate a decomposition reaction under the irradiation of ultraviolet light to generate nano-particle simple substance silver which can be filled among micron-sized silver powder, so that the compactness and the uniformity of a film layer are improved, and the content of solid silver powder is reduced due to the introduction of the organic silver, so that the conductive paste is suitable for film printing. The invention also purposefully selects the polyurethane acrylate with a hyperbranched structure, improves the thixotropy of the paste, meets the requirement of high-precision screen printing, simultaneously uses the polyurethane acrylate as the connecting material resin of the silver paste, not only has the characteristics of good solubility, strong adhesive force, good glossiness and the like of polyurethane, but also has the characteristics of high mechanical strength, good water resistance and the like of the polyacrylate, and greatly improves the comprehensive performance of the UV silver paste.
Description
Technical field: the present invention relates to a kind of organic silver complexes ultraviolet light curing conductive slurries and preparation method thereof.
Background technique:
There are many conductive silver paste type, can be divided into room temperature curing conductive paste, intermediate temperature setting conductive paste, height again according to curing system
Temperature sintering conductive paste, ultraviolet light solidification conductive paste etc..Room temperature curing conductive paste is more unstable, and volume resistivity holds when room temperature storage
Easily change；High temperature silver paste sintering temperature is high, to semiconductor, sensing element and the not substrate of resistant against high temperatures such as flexible base board
Deng not applicable, narrow application range, and process cycle is long, and energy consumption is high；What domestic and international application was more at present is intermediate temperature setting conduction
Silver paste, solidification temperature is moderate, matches with the temperature resistant capability of electronic component and using temperature, and mechanical property is also more excellent,
But heat-sensitive element and flexible parent metal are still limited by.
UV photocuring principle refers to that under the irradiation of ultraviolet light photoinitiator absorbs the photon of specific wavelength, is energized into sharp
Hair-like state, forming free radical or cation then by the transmitting of intermolecular energy makes polymerizing prepolymer and photo-sensitive monomer
Etc. becoming excitation state, charge-transfer complexation body is generated, the continuous cross-linked polymeric of these combinations generates solidification in the extremely short time
At the high molecular polymer of tridimensional network.UV-Curing Electric Conductive Adhesives combine UV-curing technology and electrocondution slurry
Come, imparts the new performance of electrocondution slurry and expand application range, but since traditional solid silver powder is commonly available to thickness
Film printing is difficult to reduce printing film thickness, therefore the present invention uses organic halogenation silver and overspends the combination of urethane acrylate, can
To realize ultraviolet rapid curing and effectively improve the electric conductivity of slurry, which can be printed on electricity by way of printing
Sub- wiring board, thin film switch, radio frequency intelligent label (RFID), flexible coil, wearable product, thin film solar electricity
Above the materials such as pond, metal, plastics.Can be widely applied to touch screen, CSP, FPC, FPC/ITO glass, PET/ITOglass,
PET/PET, flip-chip (Flipchip), liquid crystal display (LCD), radio frequency identification (RFID), thin film switch, EL backlight
The quick bonding in the fields such as terminals is conductive.
Since UV ultraviolet photo-curing conductive silver paste has photochemical sensitivity, production efficiency can be greatly improved；Construction
Safety: participating in without solvent, be environmentally friendly machine, and product solidification temperature is low, is especially excellent to use thermo-sensitive material, and can solve
Deep cure；Low energy consumption for solidification, saves cost；There are good adherence, solvent resistance after solidification；Adhesive strength height, resistivity
It is low；And it is suitable for automatic assembly line to be mass produced.
Summary of the invention
The present invention provides a kind of organic silver complexes ultraviolet light curing conductive slurry, which can print consistency
Film silver layer high, homogeneity is good, electric conductivity is excellent, is suitable for all kinds of electronic equipment films and prints.
Technical scheme is as follows:
1. a kind of organic silver complexes ultraviolet light solidifies conductive silver paste
It is characterized in that the electrocondution slurry each component mass percent is 20-40% organic silver, 20-40% spherical silver
Powder, 5-10% ultra-branched polyurethane acrylate, the photo polymerization monomer of 3-10%, the Photoepolymerizationinitiater initiater of 0.5-5%, 10-
40% solvent, 1% auxiliary agent.
2. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that hyperbranched propenoic acid resin
The preparation method is as follows:
(1) in N2Protection under, by quality accounting be 30-40% isophorone diisocyanate (IPDI) and 30-
40% n,N-Dimethylformamide (DMF), the dibutyl tin dilaurate (DBTDL) and 5-10% glycerol of 1-2% are placed in
It is 40 ± 5 DEG C of reaction 12-24h in temperature in reactor, the then diethanol amine of addition 20-30%, the reaction was continued 6-10h, so
The colourless transparent liquid of generation is washed afterwards, is separated, it is dry, the super branched polyurethane of white powder is obtained, for use；
(2) in N2Protection under, by quality accounting be 30-40% isophorone diisocyanate (IPDI), 30-40%
N,N-Dimethylformamide (DMF), the dibutyl tin dilaurate (DBTDL) of 1-2%, 20-40% hydroxy-ethyl acrylate
(HEA) it is placed in reactor with 1% metoxyphenol (MEHQ), is 40 ± 5 DEG C of reaction 12-24h in temperature, obtains terminal double bond
IPDI-HEA intermediate, for use；
(3) in N2Under protection, (1) (2) are added in reaction vessel according to mass ratio for 3: 2, gross mass is then added
1% DBTDL is finally blocked with di-n-butylamine in 70 ± 5 DEG C of reaction 6-10h, is obtained weak yellow liquid and separated, purified
And drying, obtain white powder ultra-branched polyurethane acrylate.
3. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that the halogenation organic silver is
Fluorine-containing organic silver complexes, brominated organic silver complexes, organic silver complexes containing iodine, preferably halogenation organic silver are trifluoroacetic acid
Silver, triiodoacetic acid silver is a kind of or combines；
4. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that the ball shape silver powder is grain
0.6-1.2 μm of diameter, tap density 4.6-5.3g/ml；
5. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that photo polymerization monomer is new penta
Omega-diol diacrylate, the third oxidation trimethylolpropane trimethacrylate, pentaerythritol triacrylate, two propylene of tripropylene glycol
Acid esters, double-trimethylolpropane trimethacrylate, 2- phenyl ethoxy acrylate it is one or more；
6. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that photoinitiator is 2- phenyl
Benzyl-2- dimethyl amine-1- (4- morpholine benzyl phenyl) butanone (369), 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- third
Ketone (907), 2,4,6- trimethylbenzoyls-diphenyl phosphine oxide (TPO), 2- hydroxyl -4 '-(2- hydroxy ethoxy) -2- methyl
One of propiophenone, 1- [4- (2- hydroxyl-oxethyl) phenyl] -2 methyl-1s of -2- hydroxyl-propane -1- ketone (2959), reactive amines
Or it is a variety of；
7. a kind of organic silver complexes ultraviolet light described in solidifies conductive silver paste, it is characterised in that solvent is diethylene glycol list
One of butyl ether, alcohol ester 12 and terpinol or a variety of mixtures.
A kind of ultraviolet light of organic silver complexes solidify the preparation method of conductive silver paste the following steps are included:
(1) by certain mass than organic silver, ball shape silver powder, ultra-branched polyurethane acrylate, photo polymerization monomer, photopolymerization
Initiator, solvent and auxiliary agent are mixed in container, are stirred continuously, and premix is configured to thick slurry, for use；
(2) planetary stirring machine is used, by rotation 2000RPM, revolve 800RPM, and a certain amount of (1) slurry is continued to mix
Splitting or integrating dissipates, and paste mixture is made；
(3) it takes step (2) to be ground with three-roller, obtains less than 5 μm light curable conductive silver pastes of fineness；
The present invention has following effect
The present invention is by selection halogenation organic silver and ball shape silver powder, while the hyperbranched propenoic acid resin and suitable molten of arranging in pairs or groups
Agent, the high-performance ultraviolet cured silver paste being prepared, which has the following advantages that, to be: (1) present invention introduces super branched polyurethane
The complementary independent disadvantage of acrylic resin and polyurethane of acrylate, synthesized with high mechanical strength, it is non-aging, be not easy
Jaundice and water-resistance are good and have the high performance resin of better organic solvent solubility, elasticity, glossiness and hardness stabilization；(2)
Electrocondution slurry surface layer is fine and close, and uniformity is good, and electric conductivity is superior；(3) solidifying film layer thinner thickness is suitable for each class of electronic devices
Film printing；(4) rapid curing meets industrial production efficiency, and environmental protection and energy saving.
Specific embodiment:
It to facilitate a better understanding of the present invention, is illustrated by following embodiment, these examples belong to guarantor of the invention
Range is protected, but is not limited the scope of the invention.
Embodiment 1
Hyperbranched propenoic acid resin preparation:
(1) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI) and etc. quality
N,N-Dimethylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL) and 6% glycerol are placed in reactor,
Temperature is 40 DEG C of reaction 12h, then the diethanol amine of addition 20%, the reaction was continued 6-10h, then by the colorless and transparent liquid of generation
Body is washed, and is separated, dry, obtains the super branched polyurethane of white powder, for use；
(2) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI), 36%N, N- bis-
Methylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL), 25% hydroxy-ethyl acrylate (HEA) and 1% methoxy
Base phenol (MEHQ) is placed in reactor, is 40 DEG C of reaction 12h in temperature, is obtained the IPDI-HEA intermediate of terminal double bond, for use；
(3) in N2Under protection, (1) (2) are added in reaction vessel according to mass ratio for 3: 2, gross mass is then added
1% DBTDL is finally blocked with di-n-butylamine in 70 DEG C of reaction 6h, obtains weak yellow liquid through separation, purification and drying,
Obtain white powder ultra-branched polyurethane acrylate.
Slurry preparation, the following are mass percents:
(1) each component mass percent be 40% silver trifluoroacetate, 20% ball shape silver powder (partial size 0.6-1.2um), 10%
Ultra-branched polyurethane acrylate, 6% tripropylene glycol diacrylate, 3% 2- methyl-1-(4- methyl mercapto phenyl)-2-
Morpholine -1- acetone (907), 1% dispersing agent PVP, solvent diethylene glycol monobutyl ether (5%), alcohol ester 12 (5%) and terpinol
(10%) it is placed in a beaker, is stirred continuously, premix, be configured to thick slurry, for use
(2) planetary stirring machine is used, by rotation 2000RPM, revolve 800RPM, and a certain amount of (1) slurry is continued to mix
Splitting or integrating dissipates, and paste mixture is made；
(3) it takes step (2) to be ground with three-roller, obtains less than 5 μm light curable conductive silver pastes of fineness；
Embodiment 2
Hyperbranched propenoic acid resin preparation:
(1) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI) and etc. quality
N,N-Dimethylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL) and 6% glycerol are placed in reactor,
Temperature is 40 DEG C of reaction 12h, then the diethanol amine of addition 20%, the reaction was continued 6h, then by the colourless transparent liquid of generation
It is washed, is separated, it is dry, the super branched polyurethane of white powder is obtained, for use；
(2) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI), 36%N, N- bis-
Methylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL), 25% hydroxy-ethyl acrylate (HEA) and 1% methoxyl group
Phenol (MEHQ) is placed in reactor, is 40 DEG C of reaction 12h in temperature, is obtained the IPDI-HEA intermediate of terminal double bond, for use；
(3) in N2Under protection, (1) (2) are added in reaction vessel according to mass ratio for 3: 2, gross mass is then added
1% DBTDL is finally blocked with di-n-butylamine in 70 DEG C of reaction 6h, obtains weak yellow liquid, through separation, purification and drying,
Obtain white powder ultra-branched polyurethane acrylate.
Slurry preparation method, the following are mass percents:
(1) each component mass percent be 30% silver trifluoroacetate, 30% ball shape silver powder (partial size 0.6-1.2um), 10%
Ultra-branched polyurethane acrylate, 6% tripropylene glycol diacrylate, 3% 2- methyl-1-(4- methyl mercapto phenyl)-2-
Morpholine -1- acetone (907), 1% dispersing agent PVP, solvent diethylene glycol monobutyl ether (5%), alcohol ester 12 (5%) and terpinol
(10%) it is placed in a beaker, is stirred continuously, premix, be configured to thick slurry, for use
(2) planetary stirring machine is used, by rotation 2000RPM, revolve 800RPM, and a certain amount of (1) slurry is continued to mix
Splitting or integrating dissipates, and paste mixture is made；
(3) it takes step (2) to be ground with three-roller, obtains less than 5 μm light curable conductive silver pastes of fineness.
Embodiment 3
Hyperbranched propenoic acid resin preparation:
(1) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI) and etc. quality
N,N-Dimethylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL) and 6% glycerol are placed in reactor,
Temperature is 40 DEG C of reaction 12h, then the diethanol amine of addition 20%, the reaction was continued 6h, then by the colourless transparent liquid of generation
It is washed, is separated, it is dry, the super branched polyurethane of white powder is obtained, for use；
(2) in N2Protection under, by quality accounting be 36% isophorone diisocyanate (IPDI), 36%N, N- bis-
Methylformamide (DMF), 2% dibutyl tin dilaurate (DBTDL), 25% hydroxy-ethyl acrylate (HEA) and 1% methoxy
Base phenol (MEHQ) is placed in reactor, is 40 DEG C of reaction 12h in temperature, is obtained the IPDI-HEA intermediate of terminal double bond, for use；
(3) in N2Under protection, (1) (2) are added in reaction vessel according to mass ratio for 3: 2, gross mass is then added
1% DBTDL is finally blocked with di-n-butylamine in 70 DEG C of reaction 6h, obtains weak yellow liquid, through separation, purification and drying,
Obtain white powder ultra-branched polyurethane acrylate.
Slurry preparation method, the following are mass percents:
(1) each component mass percent be 20% silver trifluoroacetate, 40% ball shape silver powder (partial size 0.6-1.2um), 10%
Ultra-branched polyurethane acrylate, 6% tripropylene glycol diacrylate, 3% 2- methyl-1-(4- methyl mercapto phenyl)-2-
Morpholine -1- acetone (907), 1% dispersing agent PVP, solvent diethylene glycol monobutyl ether (5%), alcohol ester 12 (5%) and terpinol
(10%) it is placed in a beaker, is stirred continuously, premix, be configured to thick slurry, for use；
(2) planetary stirring machine is used, by rotation 2000RPM, revolve 800RPM, and a certain amount of (1) slurry is continued to mix
Splitting or integrating dissipates, and paste mixture is made；
(3) it takes step (2) to be ground with three-roller, obtains less than 5 μm light curable conductive silver pastes of fineness.
Comparative example 1
Change ultra-branched polyurethane acrylate in embodiment 1 into epoxy acrylate；In addition to this, with embodiment 1
Identical mode prepares conductive silver paste.
Comparative example 2
Slurry preparation in embodiment 2 is replaced into all silver trifluoroacetates with spherical silver powder (0.6-1.2um), in addition to this,
Conductive silver paste is prepared in the same way as in example 2.
Performance test:
1. ultraviolet light solidifies the test of conductive silver paste printability: on manual silk-screen platform, the polyester halftone of 400 mesh is thick
10um is spent, 30um lines are printed on the ITO film of shrink.Then the UV machine that dominant wavelength is 365nm is crossed, is seen with high-power microscope
Examine linear resolution；
2. ultraviolet light solidifies conductive silver paste viscosity test: fly (DV2THB) rotational viscometer with rich power, it is small in 25 DEG C of constant temperature 1
The viscosity of Shi Hou, 10RPM measurement silver paste sample；
3. the adhesive force test that ultraviolet light solidifies silver paste: marking hundred lattice of test in square pattern with cross-cut tester, then
With the adhesive tape of 3M810 to test, area≤5% that falls off is qualification, otherwise unqualified；
4. ultraviolet light solidifies conductive silver paste resistance test: testing sheet resistance with four probe machines；
5. thickness is tested: using sweep electron microscopic measure thicknesses of layers.
Test result:
Resistivity=sheet resistance * thicknesses of layers
From the above results: comparative example 1 demonstrates, and is had using the silver paste of ultra-branched polyurethane acrylate excellent
Lines resolution ratio and adhesive force；Comparative example 2,3 is also demonstrated by the use of organic silver convenient for the regulation of printing thicknesses of layers, in fact simultaneously
Existing film printing, and densification is filled, uniformly, the electric conductivity of slurry is good, meets modern electronic equipment high-performance conductive and wants
It asks.
Claims (7)
1. a kind of organic silver complexes ultraviolet light solidifies conductive silver paste
It is characterized in that the electrocondution slurry each component mass percent is 20-40% organic silver, 20-40% ball shape silver powder, 5-
10% ultra-branched polyurethane acrylate, the photo polymerization monomer of 3-10%, the Photoepolymerizationinitiater initiater of 0.5-5%, 10-40% are molten
Agent, 1% auxiliary agent.
2. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that hyperbranched
Acrylic resin the preparation method is as follows:
(1) in N2Protection under, by quality accounting be 30-40% isophorone diisocyanate (IPDI) and 30-40% N,
Dinethylformamide (DMF), the dibutyl tin dilaurate (DBTDL) and 5-10% glycerol of 1-2% are placed in reactor,
It is 40 ± 5 DEG C of reaction 12-24h in temperature, the diethanol amine of 20-30% is then added, the reaction was continued 6-10h then will generation
Colourless transparent liquid washed, separate, it is dry, obtain the super branched polyurethane of white powder, for use；
(2) in N2Protection under, by quality accounting be 30-40% isophorone diisocyanate (IPDI), 30-40%N, N-
Dimethylformamide (DMF), the dibutyl tin dilaurate (DBTDL) of 1-2%, 20-40% hydroxy-ethyl acrylate (HEA) and
1% metoxyphenol (MEHQ) is placed in reactor, is 40 ± 5 DEG C of reaction 12-24h in temperature, is obtained the IPDI- of terminal double bond
HEA intermediate, for use；
(3) in N2Under protection, (1) (2) are added in reaction vessel according to mass ratio for 3: 2, gross mass 1% is then added
DBTDL is finally blocked with di-n-butylamine in 70 ± 5 DEG C of reaction 6-10h, obtains weak yellow liquid through separation, purification and drying,
Obtain white powder ultra-branched polyurethane acrylate.
3. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that the halogen
Change organic silver is fluorine-containing organic silver complexes, and brominated organic silver complexes, organic silver complexes containing iodine, preferably halogenation organic silver is
Silver trifluoroacetate, triiodoacetic acid silver is a kind of or combines.
4. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that the ball
Shape silver powder is 0.6-1.2 μm of partial size, tap density 4.6-5.3g/ml.
5. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that photopolymerization
Monomer is neopentylglycol diacrylate, the third oxidation trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 3 third
Omega-diol diacrylate, double-trimethylolpropane trimethacrylate, 2- phenyl ethoxy acrylate it is one or more.
6. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that light-initiated
Agent is 2- phenyl benzyl-2- dimethyl amine-1- (4- morpholine benzyl phenyl) butanone (369), 2- methyl-1-(4- methyl mercapto phenyl)-2-
Morpholine -1- acetone (907), 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO), 2- hydroxyl -4 '-(2- hydroxyl ethoxy
Base) -2- methyl phenyl ketone, 1- [4- (2- hydroxyl-oxethyl) phenyl] -2 methyl-1s of -2- hydroxyl-propane -1- ketone (2959), activity
One of amine is a variety of.
7. a kind of organic silver complexes ultraviolet light according to claim 1 solidifies conductive silver paste, it is characterised in that solvent is
One of diethylene glycol monobutyl ether, alcohol ester 12 and terpinol or a variety of mixtures.
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| CN1699492A (en) * | 2005-07-11 | 2005-11-23 | 大连轻工业学院 | Photo-curable conductive adhesive and method for making same |
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|---|---|---|---|---|
| CN1699492A (en) * | 2005-07-11 | 2005-11-23 | 大连轻工业学院 | Photo-curable conductive adhesive and method for making same |
| US20100140564A1 (en) * | 2006-03-07 | 2010-06-10 | Gerardus Cornelis Overbreek | Conductive ink |
| CN105021589A (en) * | 2015-06-18 | 2015-11-04 | 北京航空航天大学 | Method for preparing hydrophobic SERS substrate by using silk-screen printing technology |
| CN105542573A (en) * | 2016-01-29 | 2016-05-04 | 华南理工大学 | Preparation method of conductive ink vehicle |
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