CN116344098A - Low-rigidity conductive paste and preparation method and application thereof - Google Patents
Low-rigidity conductive paste and preparation method and application thereof Download PDFInfo
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- CN116344098A CN116344098A CN202310247608.3A CN202310247608A CN116344098A CN 116344098 A CN116344098 A CN 116344098A CN 202310247608 A CN202310247608 A CN 202310247608A CN 116344098 A CN116344098 A CN 116344098A
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- 238000002360 preparation method Methods 0.000 title abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 80
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000805 composite resin Substances 0.000 claims abstract description 17
- 239000011231 conductive filler Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 229920000459 Nitrile rubber Polymers 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000007649 pad printing Methods 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims 2
- 235000010650 Hyssopus officinalis Nutrition 0.000 claims 1
- 240000001812 Hyssopus officinalis Species 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 43
- 239000002002 slurry Substances 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012789 electroconductive film Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000009864 tensile test 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
- H01B1/20—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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of new materials, in particular to low-rigidity conductive paste, and a preparation method and application thereof. The conductive paste comprises 50-80wt% of conductive filler; the conductive paste further comprises a composite resin; the mass ratio of the composite resin to the conductive filler is (11.5-60): (50-80); the composite resin comprises the following components in percentage by mass (8-30): (3-20): (0.5-10), modified SIS resins, modified acrylic resins, and TPU resins. The conductive paste provided by the invention further has lower rigidity on the basis of high conductivity; the grid-shaped conductive circuit formed by the conductive paste has the advantages of good surface uniformity, good conductivity and low rigidity; finally, the conductive vibrating diaphragm with low rigidity is provided.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to low-rigidity conductive paste, and a preparation method and application thereof.
Background
In recent years, vibrating diaphragms with conductive functions are widely applied to sound generating devices; in order to make the diaphragm have good conductive function, researchers often adopt a mode of adding a conductive circuit layer on the surface of the diaphragm (i.e. forming a conductive circuit on the surface of the diaphragm by using conductive paste). However, the diaphragm with the conductive circuit layer added has large overall rigidity, and the requirement of a flexible device is difficult to meet.
In view of this, the present invention has been made.
Disclosure of Invention
In order to provide a low-rigidity conductive vibrating diaphragm, the invention researches a method for reducing the rigidity of the conductive vibrating diaphragm so as to solve the problem of overlarge integral rigidity of the conductive vibrating diaphragm.
Specifically, the inventors have studied the cause of this problem, and found that it is mainly due to the increase of the conductive wiring layer, that is, the decrease of the rigidity of the conductive wiring layer is a key to solving the above problem.
Based on the above findings, the present invention provides an electroconductive paste, which reduces the rigidity of the entire electroconductive film by a method of reducing the rigidity of the paste.
Specifically, the conductive paste comprises 50-80wt% of conductive filler;
the conductive paste further comprises a composite resin;
the mass ratio of the composite resin to the conductive filler is (11.5-60): (50-80);
the composite resin comprises the following components in percentage by mass (8-30): (3-20): (0.5-10), modified SIS resins, modified acrylic resins, and TPU resins.
In the prior art, the rigidity of the conductive paste is reduced by reducing the content of the conductive filler, but the slurry resistance is easy to surge due to the reduction of the content of the conductive filler; that is, it is difficult for the electroconductive paste to simultaneously achieve both "high electroconductive filler addition amount" and "low rigidity".
The invention surprisingly discovers that the composite resin formed by mixing the modified SIS resin, the modified acrylic resin and the TPU resin is expected to obviously improve the flexibility of a slurry system and further reduce the rigidity of the slurry on the basis that the conductivity of the slurry is not affected after being compounded with the conductive filler.
Further, the mass ratio of the modified SIS resin, the modified acrylic resin and the TPU resin is controlled to be (8-30): (3-20): (0.5-10), and simultaneously controlling the mass ratio of the composite resin to the conductive filler to be (11.5-60): (50-80), the slurry rigidity can be further reduced (the addition amount of the conductive filler in the conductive slurry is more than 40wt percent) on the basis of ensuring good conductivity of the slurry, and the sheet resistance of a conductive line formed by the conductive slurry is less than 100mΩ/≡m/mil.
Preferably, the modified SIS resin is made by a process comprising the steps of:
(1) Mixing SIS resin (styrene-isoprene-styrene block copolymer) with the first solvent, and stirring at 50-500rpm at 90-150deg.C for 12-48 hr;
(2) Mixing the product obtained in the step (1) with the first modifier, and uniformly stirring at 50-80 ℃ and 100-200 rpm.
Further, the Shore hardness of the SIS resin is less than 50A, and the elongation at break is more than 100%.
Further, the first solvent is a ketone, ether, ester or alcohol having a boiling point above 150 ℃; preferably ISOP (isophorone) or DEAC (diethylene glycol diethyl ether acetate).
Further, the first modifier is liquid styrene-butadiene rubber.
Still further, SIS resin, in mass ratio: a first solvent: first modifier = 1: (2-5): (0.5-2).
Preferably, the modified acrylic resin is prepared by a process comprising the steps of:
(1) Mixing the acrylic resin and the second solvent, and stirring at 50-500rpm at 90-150deg.C for 12-48 hr;
(2) Mixing the product obtained in the step (1) with a second modifier, and uniformly stirring at 40-60 ℃ and 50-100 rpm.
Further, the second solvent is a ketone, ether, ester or alcohol having a boiling point above 150 ℃; preferably, one or a combination of two of DEAC (diethylene glycol ethyl ether acetate) and ethyl acetate.
Further, the second modifier is carboxyl terminated nitrile rubber or hydroxyl terminated nitrile rubber.
Still further, the acrylic resin: a second solvent: second modifier = 1: (3-6): (0.5-2).
Preferably, the TPU resin is subjected to the following treatment in advance: the TPU resin and the third solvent are mixed according to 1: (4-6) by mass ratio.
Further, the third solvent is DEAC (diethylene glycol diethyl ether acetate) and/or CYC (cyclohexanone).
In the invention, the modified SIS resin, the modified acrylic resin and the TPU resin which are respectively prepared according to the mode are mixed to form the composite resin, and the composite resin has higher elongation at break and lower modulus, and is more beneficial to improving the performances (especially the rigidity) of the slurry in all aspects after being matched with other components.
Preferably, the conductive filler is selected from one or more of gallium, indium, tin, zinc, bismuth, gold, silver, iron, nickel and aluminum; preferably spherical silver powder; more preferably, the spherical silver powder has a particle diameter of < 5. Mu.m.
In the invention, specific conductive fillers (especially spherical silver powder with particle size less than 5 μm) are screened, so that the resistance of the conductive paste can be further reduced.
The person skilled in the art can arrange the other functional components of the formulation according to common general knowledge, which all achieve an effect comparable to the above description of the invention. However, there are also more preferable technical solutions concerning other components, and for this purpose, the present invention has been further studied and the following preferable solutions have been obtained.
Preferably, the conductive paste further comprises 0.1 to 2wt% of a curing agent;
the curing agent is a polyisocyanate-based curing agent; blocked isocyanates are preferred.
In the present invention, screening for a specific curing agent (particularly, blocked isocyanate) can further improve the elongation at break of the composite resin and reduce the modulus of the composite resin.
Preferably, the conductive paste further comprises 0.1 to 0.5wt% of an auxiliary agent;
the auxiliary agent is one or more selected from flatting agent, dispersing agent and defoaming agent.
The above technical solutions can be combined by a person skilled in the art according to common general knowledge to obtain a preferred embodiment of the conductive paste according to the present invention.
As a preferred embodiment of the present invention, the conductive paste comprises the following components in parts by weight: 8-30 parts of modified SIS resin, 3-20 parts of modified acrylic resin, 0.5-10 parts of TPU resin, 0.1-2 parts of blocked isocyanate, 50-80 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.1-0.5 part of auxiliary agent.
As a preferred embodiment of the present invention, the conductive paste comprises the following components in mass percent:
8-30wt% of modified SIS resin, 3-20wt% of modified acrylic resin, 0.5-10wt% of TPU resin, 0.1-2wt% of blocked isocyanate, 50-80wt% of spherical silver powder with particle size smaller than 5 mu m and 0.1-0.5wt% of auxiliary agent.
The invention also provides a preparation method of the conductive paste, which comprises the following steps: and uniformly mixing the conductive filler, the composite resin, the curing agent and the auxiliary agent, and then grinding.
In a specific embodiment, the grinding is performed using a three-roll grinder.
The invention also provides application of the conductive paste in a circuit board; preferably in flexible circuit boards.
The invention also provides an electronic device, which comprises a substrate and a conductive line positioned on the substrate, wherein the conductive line is formed by printing, heating and curing the conductive paste; the conductive circuit is in a grid structure.
The invention also finds that the rigidity of the conductive lines in a grid-like structure is lower; however, the surface uniformity of the grid-like conductive line is poor, and there is a risk of cracking during practical application.
The grid-shaped conductive circuit formed by the conductive paste provided by the invention can effectively avoid the risks.
Preferably, the printing mode is roll printing, silk printing or pad printing.
In a specific embodiment, the conductive circuit is printed by pad printing.
Preferably, the substrate is a diaphragm.
Based on the scheme, the beneficial effects of the invention are as follows:
the conductive paste provided by the invention further has lower rigidity on the basis of high conductivity; the grid-shaped conductive circuit formed by the conductive paste has the advantages of good surface uniformity, good conductivity and low rigidity; finally, the conductive vibrating diaphragm with low rigidity is provided.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The embodiment provides a conductive paste, which comprises the following formula:
30 parts of modified SIS resin, 16.5 parts of modified acrylic resin, 2.5 parts of TPU resin, 0.5 part of blocked isocyanate, 50 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:5:2;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:6:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Example 2
The embodiment provides a conductive paste, which comprises the following formula:
25 parts of modified SIS resin, 20 parts of modified acrylic resin, 4 parts of TPU resin, 0.5 part of blocked isocyanate, 50 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 4:15:6, preparing a base material;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:5:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Example 3
The embodiment provides a conductive paste, which comprises the following formula:
30 parts of modified SIS resin, 9 parts of modified acrylic resin, 10 parts of TPU resin, 0.5 part of blocked isocyanate, 50 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:5:1.5;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:6:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Example 4
The embodiment provides a conductive paste, which comprises the following formula:
24 parts of modified SIS resin, 12.5 parts of modified acrylic resin, 2.5 parts of TPU resin, 0.5 part of blocked isocyanate, 60 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:5:2;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:5:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Example 5
The embodiment provides a conductive paste, which comprises the following formula:
17.5 parts of modified SIS resin, 11 parts of modified acrylic resin, 0.5 part of TPU resin, 0.5 part of blocked isocyanate, 70 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:4.75:2;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:6:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Example 6
The embodiment provides a conductive paste, which comprises the following formula:
11.5 parts of modified SIS resin, 5 parts of modified acrylic resin, 2.5 parts of TPU resin, 0.5 part of blocked isocyanate, 80 parts of spherical silver powder with the particle size smaller than 5 mu m and 0.5 part of auxiliary agent;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:4.6:2;
the preparation method of the modified acrylic resin comprises the following steps:
(1) Mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
(2) Mixing the product obtained in the step (1) with carboxyl-terminated nitrile rubber, and uniformly stirring at 40 ℃ and 50 rpm;
wherein, according to mass ratio, acrylic resin: a second solvent: carboxyl terminated nitrile rubber = 1:4:2;
the TPU resin is subjected to the following treatment in advance: TPU resin and third solvent (DEAC: cyc=1:1) were combined according to 1:4 mass ratio.
The embodiment further provides a preparation method of the conductive paste, which specifically comprises the following steps: after the components are uniformly mixed, grinding is carried out by adopting a three-roller grinder.
Comparative example 1
This comparative example provides a conductive paste which differs from example 1 in that in the formulation, the preparation method of the modified SIS resin is different, specifically as follows:
mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
wherein, according to mass ratio, SIS resin: deac=1: 5.
comparative example 2
This comparative example provides a conductive paste which is different from example 1 in that in the formulation, the preparation method of the modified acrylic resin is different, specifically as follows:
mixing the acrylic resin and the second solvent (DEAC: ethyl acetate=2:1) and stirring at 90 ℃ for 48h at 500 rpm;
wherein, according to mass ratio, acrylic resin: second solvent = 1:5.6.
comparative example 3
This comparative example provides a conductive paste which is different from example 1 in that the addition amount of the modified SIS resin in the formulation is 32.5 parts by weight and the preparation method of the modified SIS resin is different; the addition amount of the TPU resin is 0.5 part by weight, and the TPU resin is not pretreated; the addition amount of the blocked isocyanate is 0 weight part;
the preparation method of the modified SIS resin comprises the following steps:
(1) Mixing SIS resin (Shore hardness less than 50A, elongation at break > 100%) with DEAC, and stirring at 90deg.C and 500rpm for 48 hr;
(2) Mixing the product obtained in the step (1) with liquid styrene-butadiene rubber, and uniformly stirring at 50 ℃ and 150 rpm;
wherein, according to mass ratio, SIS resin: DEAC: liquid styrene butadiene rubber = 1:5:3.
test examples
In this test example, the conductive pastes of examples and comparative examples were respectively pad-printed on a TPEE diaphragm having a thickness of 20 μm, the paste thickness was 10 μm, and cured at 100 ℃ for 0.5h to form conductive line bars having a width of 10mm and a length of 50mm, and then performance tests were performed on each bar and the TPEE diaphragm, respectively, as follows:
1. sheet resistance: testing the resistance of each spline and the resistance of the TPEE vibrating diaphragm by using a resistance meter, and then calculating the sheet resistance;
2. tensile stress (i.e., stiffness): stretching each spline and the TPEE vibrating diaphragm by 10%, and testing the stretched tensile stress by using a universal tensile testing machine;
3. the test results are shown in Table 1;
TABLE 1
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A conductive paste, characterized in that it comprises 50-80wt% of a conductive filler;
the conductive paste further comprises a composite resin;
the mass ratio of the composite resin to the conductive filler is (11.5-60): (50-80);
the composite resin comprises the following components in percentage by mass (8-30): (3-20): (0.5-10), modified SIS resins, modified acrylic resins, and TPU resins.
2. The conductive paste of claim 1 wherein the modified SIS resin is made by a process comprising the steps of:
(1) Mixing SIS resin and the first solvent, and stirring at 90-150deg.C and 50-500rpm for 12-48 hr;
(2) Mixing the product obtained in the step (1) with a first modifier, and uniformly stirring at 50-80 ℃ and 100-200 rpm;
preferably, the method comprises the steps of,
the Shore hardness of the SIS resin is less than 50A, and the elongation at break is more than 100%; and/or the number of the groups of groups,
the first solvent is ketone, ether, fat or alcohol with the boiling point higher than 150 ℃; preferably ISOP or DEAC; and/or the number of the groups of groups,
the first modifier is liquid styrene-butadiene rubber;
more preferably, the process is carried out,
SIS resin: a first solvent: first modifier = 1: (2-5): (0.5-2).
3. The electroconductive paste according to claim 1, wherein the modified acrylic resin is prepared by a process comprising the steps of:
(1) Mixing the acrylic resin and the second solvent, and stirring at 50-500rpm at 90-150deg.C for 12-48 hr;
(2) Mixing the product obtained in the step (1) with a second modifier, and uniformly stirring at 40-60 ℃ and 50-100 rpm;
preferably, the method comprises the steps of,
the second solvent is ketone, ether, fat or alcohol with the boiling point higher than 150 ℃; preferably one or a combination of two of DEAC and ethyl acetate; and/or the number of the groups of groups,
the second modifier is carboxyl-terminated nitrile rubber or hydroxyl-terminated nitrile rubber;
more preferably, the process is carried out,
acrylic resin: a second solvent: second modifier = 1: (3-6): (0.5-2).
4. The electroconductive paste according to claim 1, wherein the TPU resin is previously subjected to the following treatment: the TPU resin and the third solvent are mixed according to 1: mixing the components (4-6) in a mass ratio;
preferably, the third solvent is DEAC and/or CYC.
5. The conductive paste according to any one of claims 1 to 4, wherein the conductive filler is one or more selected from the group consisting of gallium, indium, tin, zinc, bismuth, gold, silver, iron, nickel, and aluminum; preferably spherical silver powder; more preferably, the spherical silver powder has a particle diameter of < 5. Mu.m.
6. The electroconductive paste according to any one of claims 1-5, further comprising 0.1-2wt% of a curing agent;
the curing agent is a polyisocyanate-based curing agent; blocked isocyanates are preferred.
7. The electroconductive paste according to any one of claims 1-6, further comprising 0.1-0.5wt% of an auxiliary agent;
the auxiliary agent is one or more selected from flatting agent, dispersing agent and defoaming agent.
8. The method for producing a conductive paste according to any one of claims 1 to 7, comprising: and uniformly mixing the conductive filler, the composite resin, the curing agent and the auxiliary agent, and then grinding.
9. Use of the electroconductive paste according to any one of claims 1-7 in a circuit board; preferably in flexible circuit boards.
10. An electronic device comprising a substrate and a conductive trace on the substrate, wherein the conductive trace is printed from the conductive paste of any one of claims 1-7 and is formed after heat curing; the conductive circuit is in a grid structure;
preferably, the printing mode is roll printing, silk printing or pad printing;
more preferably, the substrate is a diaphragm.
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| CN110776847A (en) * | 2018-07-27 | 2020-02-11 | 杭州蓉阳电子科技有限公司 | Conductive adhesive, raw material composition, electronic element, preparation method and application |
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