CN117487496B - Conductive silver adhesive based on modified silver powder and preparation method thereof - Google Patents
Conductive silver adhesive based on modified silver powder and preparation method thereof Download PDFInfo
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- CN117487496B CN117487496B CN202311781075.3A CN202311781075A CN117487496B CN 117487496 B CN117487496 B CN 117487496B CN 202311781075 A CN202311781075 A CN 202311781075A CN 117487496 B CN117487496 B CN 117487496B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical class C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims abstract 2
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- IFDFMWBBLAUYIW-UHFFFAOYSA-N ethane-1,2-diol;ethyl acetate Chemical compound OCCO.CCOC(C)=O IFDFMWBBLAUYIW-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 229910007116 SnPb Inorganic materials 0.000 description 1
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a conductive silver adhesive based on modified silver powder and a preparation method thereof, wherein the conductive silver adhesive comprises the following raw materials: 50-70 parts of bisphenol A type epoxy resin, 0.5-5 parts of curing agent, 10-20 parts of diluent, 0.1-5 parts of accelerator, 0.1-2 parts of coupling agent and 20-30 parts of modified silver powder, wherein the raw materials used by the modified silver powder comprise, by weight: 5-10 parts of silver powder, 1-2 parts of p-mercaptobenzoic acid and 10-30 parts of bisimidazole salt ionic liquid. The conductive silver adhesive prepared by the invention has the advantages of good conductivity, high temperature resistance, high bonding strength and the like, and the performance is obviously superior to the prior art, thus having good industrial production value.
Description
Technical Field
The invention relates to the technical field of conductive adhesives, in particular to a conductive silver adhesive based on modified silver powder and a preparation method thereof.
Background
Conductive adhesives have a lower curing temperature and a simpler curing process than conventional tin-lead solders, and have received much attention in recent years. Conductive adhesives are widely used in the electronic packaging field such as die attach, multilayer printed circuit and surface mount technology, and are considered as substitutes for conventional eutectic SnPb solder alloys.
Silver powder also has good conductivity due to the oxide thereof, so that the silver powder becomes the first choice of conductive filler of conductive adhesive, and epoxy resin has the advantages of excellent mechanical property and thermal property, low shrinkage, good adhesion capability, mechanical impact resistance and thermal shock resistance, strong resistance to humidity, solvents and chemical reagents, and the like. Silver powder filled epoxy composites are therefore currently the more commonly used conductive adhesives. However, at present, certain defects still exist, such as higher volume resistivity, insufficient bonding strength, poor storage and transportation performances and the like. In order to improve the conductivity of the conductive adhesive, the content of the metal filler (65% -90%) is often increased, and although the conductivity of the conductive adhesive can be increased to a certain extent, part of the mechanical properties can be lost due to the reduction of the content of the resin, the viscosity of the conductive adhesive is increased, the bonding strength and the operation performance are reduced, and the cost of the conductive adhesive is greatly increased. As CN106753133B discloses a conductive silver paste and a preparation method thereof, which introduces an ionic liquid with catalytic activity into a conductive paste formulation, so as to promote further curing of epoxy resin, improve volume shrinkage, greatly improve conductive performance of the conductive silver paste, however, the silver powder used in the method is still excessive, and volume resistivity is still to be improved.
Therefore, development of a conductive silver paste with good conductivity, high temperature resistance and excellent mechanical properties of a film is needed.
Disclosure of Invention
The invention aims to provide a conductive silver adhesive based on modified silver powder and a preparation method thereof, which are used for solving the technical problems of poor conductive performance, poor heat resistance and poor film mechanical property in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the conductive silver adhesive based on the modified silver powder is characterized by comprising the following raw materials in parts by weight:
50-70 parts of bisphenol A type epoxy resin
0.5 To 5 parts of curing agent
10-20 Parts of diluent
0.1 To 5 parts of promoter
0.1 To 2 parts of coupling agent
20 To 30 parts of modified silver powder
The modified silver powder comprises the following raw materials in parts by weight: 5-10 parts of silver powder, 1-2 parts of p-mercaptobenzoic acid and 10-30 parts of biimidazole salt ionic liquid;
the preparation method of the modified silver powder comprises the following steps:
Reacting silver powder, p-mercaptobenzoic acid and biimidazole salt ionic liquid at 60-100 ℃ for 3-10h to obtain modified silver powder;
the structural general formula of the bisimidazolium ionic liquid is as follows:
；
wherein R is C 1-3 straight-chain or branched-chain alkyl, and X is BF 4 or F, cl, br, I.
Preferably, R is methyl, ethyl, propyl, isopropyl.
In some embodiments, the bisimidazolium ionic liquid structure isOr (b)。
In some embodiments, the bisphenol a epoxy resin is E44 epoxy resin, E51 epoxy resin, or 828EL epoxy resin.
In some embodiments, the curative is m-xylylenediamine, diethyltoluenediamine, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, PN23, methyl hexahydrophthalic anhydride, PN50, or C11Z.
In some embodiments, the diluent is xylene, ethyl glycol acetate, acetone, n-butyl glycidyl ether, diglycidyl ether, l, 4-butanediol diglycidyl ether, or polyglycidyl ether.
In some embodiments, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol, N-dimethylbenzylamine, dibenzoyl peroxide, p-toluenesulfonyl isocyanate, or N, N-dimethylcyclohexylamine.
In some embodiments, the coupling agent is a KH560 coupling agent, a KH570 coupling agent, or a KH550 coupling agent.
In some embodiments, the silver powder is selected from one or more of plate-like silver powder, spherical silver powder, and rod-like silver powder.
On the other hand, the invention also provides a preparation method of the conductive silver adhesive, which is characterized by comprising the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the silver powder preparation method, the mercaptobenzoic acid and the diimidazole salt ionic liquid are adopted to modify silver powder so as to eliminate an oxide layer on the surface of silver, and the silver powder is further reacted with silver atoms to form Ag composite nanoparticles, so that the structure plays an important role in regulating and controlling the surface properties of silver. The silver nano particles are attached to the surface of the silver powder, so that contact sites between the silver powder and the silver powder are increased, and the conductivity of the conductive silver adhesive is further improved. The diimidazole salt ionic liquid can be used as a reaction solvent and a catalyst, plays a very important role in adsorption reaction between-COOH or-SH and Ag, and influences the modification degree and surface structure of silver powder.
2) The conductive silver adhesive prepared by the invention has the advantages of good conductivity, high temperature resistance, high bonding strength and the like, and the performance is obviously superior to the prior art, thus having good industrial production value.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1: preparation of modified silver powder (silver powder A1):
spherical silver powder (100.0 g) and p-mercaptobenzoic acid (10.0 G) was slowly added to the bisimidazolium ionic liquid(300.0 G) was reacted at 80℃with stirring for 5 hours. After the reaction, the mixture was filtered, dried in vacuo at 100℃and ground to obtain a modified silver powder (silver powder A1).
Preparation example 2: preparation of modified silver powder (silver powder A2):
Silver flake powder (100.0 g) and p-mercaptobenzoic acid (20.0 G) was slowly added to the bisimidazolium ionic liquid(300.0 G) was stirred at 100℃for 3 hours. After the reaction, the mixture was filtered, dried in vacuo at 100℃and ground to obtain a modified silver powder (silver powder A2).
Preparation example 3: preparation of modified silver powder (silver powder B1):
spherical silver powder (100.0 g) and p-mercaptobenzoic acid (10.0 G) was slowly added to absolute ethanol (300.0 g), and the mixture was stirred at 80℃under reflux for 5 hours. After the reaction, the mixture was filtered, dried in vacuo at 100℃and ground to obtain a modified silver powder (silver powder B1).
Preparation example 4: preparation of modified silver powder (silver powder B2):
spherical silver powder (100.0 g) and p-mercaptobenzoic acid (10.0 G) was slowly added to an ionic liquid [ BMIM ] [ BF 4 ] (300.0 g), and the mixture was stirred at 80℃under reflux for 5 hours. After the reaction, the mixture was filtered, dried in vacuo at 100℃and ground to obtain a modified silver powder (silver powder B2).
Example 1
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: e44 epoxy 60 parts
Curing agent: PN 23.5 parts
A diluent: diglycidyl ether 20 parts
And (3) an accelerator: 2.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol
Silane coupling agent: KH560 (1 part)
Modified silver powder: silver powder A1 (prepared in preparation example 1) 25 parts
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Example 2
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: e51 epoxy resin 70 parts
Curing agent: methyl hexahydrophthalic anhydride 1.5 parts
A diluent: xylene 15 parts
And (3) an accelerator: 1.0 part of dibenzoyl peroxide
Silane coupling agent: KH 570.5 parts
Modified silver powder: 20 parts of silver powder A2 (prepared in preparation example 2)
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Example 3
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: 828EL epoxy resin 50 parts
Curing agent: C11Z 1.0 part
A diluent: 10 parts of n-butyl glycidyl ether
And (3) an accelerator: 1.5 parts of p-toluenesulfonyl isocyanate
Coupling agent: KH 550.5 parts
Modified silver powder: 30 parts of silver powder A1 (prepared in preparation example 1)
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Comparative example 1: the modified silver powder was replaced with silver powder on the basis of example 1.
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: e44 epoxy 60 parts
Curing agent: PN 23.5 parts
A diluent: diglycidyl ether 20 parts
And (3) an accelerator: 2.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol
Silane coupling agent: KH560 (1 part)
Silver powder 25 parts
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Comparative example 2: replacement of modified silver powder A1 with modified silver powder B1 based on example 1
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: e44 epoxy 60 parts
Curing agent: PN 23.5 parts
A diluent: diglycidyl ether 20 parts
And (3) an accelerator: 2.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol
Silane coupling agent: KH560 (1 part)
Modified silver powder: silver powder B1 (prepared in preparation example 3) 25 parts
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Comparative example 3: replacement of modified silver powder A1 with modified silver powder B2 based on example 1
The conductive silver adhesive comprises the following raw materials in parts by weight:
bisphenol a epoxy resin: e44 epoxy 60 parts
Curing agent: PN 23.5 parts
A diluent: diglycidyl ether 20 parts
And (3) an accelerator: 2.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol
Silane coupling agent: KH560 (1 part)
Modified silver powder: 25 parts of silver powder B2 (prepared in preparation example 4)
The preparation method of the conductive silver adhesive comprises the following steps:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
Performance testing
In order to better embody the performance of the conductive silver paste of the present application, the conductive silver pastes prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to related tests, and the results are shown in table 1.
1) Viscosity measurement
The conductive silver paste was measured using an NDJ28S (Shanghai instrumentation) digital display viscometer.
2) Determination of volume resistivity
Washing the carrier with absolute ethyl alcohol, sticking a insulating adhesive tape, cutting the middle part into standard rectangles, smearing conductive adhesive, and putting into an oven for curing. After solidification, the thickness of the conductive film and the width of the conductive film are measured, and the resistance is directly measured by adopting a direct current digital resistance tester.
The volume resistivity was calculated using the following formula:
ρ=R(w*t)/L
ρ - - -resistivity, Ω/cm;
R- - -measured resistance, Ω;
w- -the width of the glue layer, cm;
t-the thickness of the glue layer, cm;
l- -the length of the glue layer, cm.
Measuring the thickness of five places on each slide, and taking an average value; each formulation produced 5 test samples and an average of 5 resistivities.
3) High temperature resistance: the sample was observed at an elevated temperature of 300 ℃.
4) Bond strength test
And (3) sticking conductive silver adhesive as an adhesive, an aluminum sheet as a substrate, and a sample adopting a single-sided lap joint test piece. The bond strength test was performed on a microcomputer controlled electronic universal tester.
TABLE 1
| Sequence number | Viscosity (mpa.s) | Volume resistivity (10 -4 ohm/cm) | Bond Strength (Mpa) | High temperature resistance test |
| Example 1 | 1900 | 0.7 | 46 | No change |
| Example 2 | 2200 | 1.0 | 48 | No change |
| Example 3 | 2100 | 0.9 | 44 | No change |
| Comparative example 1 | 3600 | 8.5 | 34 | The sample part is destroyed |
| Comparative example 2 | 3400 | 5.4 | 37 | The sample part is destroyed |
| Comparative example 3 | 3050 | 2.9 | 40 | The sample part is destroyed |
As can be seen from the data in Table 1, the conductive silver paste prepared by the invention has the advantages of excellent conductivity, high temperature resistance, high bonding strength and the like.
From examples 1 and 1,2 and 3, it is known that the addition of the modified silver powder plays a critical role in improving the performance of the conductive silver paste. Firstly, -COOH and-SH have strong adsorption effect with Ag, and the p-mercaptobenzoic acid is adoptedAnd the diimidazole salt ionic liquid is modified to eliminate an oxide layer on the surface of silver and further reacts with silver atoms to form Ag composite nanoparticles, and the structure plays an important role in regulating and controlling the surface properties of silver. The silver nano particles are attached to the surface of the silver powder, so that contact sites between the silver powder and the silver powder are increased, and the conductivity of the conductive silver paste can be further improved. The diimidazole salt ionic liquid can be used as a reaction solvent and a catalyst, plays a very important role in adsorption reaction between-COOH or-SH and Ag, and influences the modification degree and surface structure of silver powder.
In addition, the modified silver powder has good dispersibility and physical properties, so that the viscosity of the conductive silver adhesive is reduced, and the bonding strength and heat resistance are improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The conductive silver adhesive based on the modified silver powder is characterized by comprising the following raw materials in parts by weight:
50-70 parts of bisphenol A type epoxy resin
0.5 To 5 parts of curing agent
10-20 Parts of diluent
0.1 To 5 parts of promoter
0.1 To 2 parts of coupling agent
20 To 30 parts of modified silver powder
The modified silver powder comprises the following raw materials in parts by weight: 5-10 parts of silver powder, 1-2 parts of p-mercaptobenzoic acid and 10-30 parts of biimidazole salt ionic liquid;
the preparation method of the modified silver powder comprises the following steps:
Reacting silver powder, p-mercaptobenzoic acid and biimidazole salt ionic liquid at 60-100 ℃ for 3-10h to obtain modified silver powder;
the structural general formula of the bisimidazolium ionic liquid is as follows:
wherein R is C 1-3 straight-chain or branched-chain alkyl, and X is BF 4 or F, cl, br, I.
2. The conductive silver paste of claim 1, wherein:
the bisphenol A type epoxy resin is E44 epoxy resin, E51 epoxy resin or 828EL epoxy resin.
3. The conductive silver paste of claim 1, wherein:
the curing agent is m-xylylenediamine, diethyl toluenediamine, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1, 2-dimethylimidazole, PN23, methyl hexahydrophthalic anhydride, PN50 or C11Z.
4. The conductive silver paste of claim 1, wherein:
The diluent is xylene, ethylene glycol ethyl acetate, acetone, n-butyl glycidyl ether, diglycidyl ether, l, 4-butanediol diglycidyl ether or polyglycidyl ether.
5. The conductive silver paste of claim 1, wherein:
The accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol, N-dimethylbenzylamine, dibenzoyl peroxide, p-toluenesulfonyl isocyanate or N, N-dimethylcyclohexylamine.
6. The conductive silver paste of claim 1, wherein:
the coupling agent is KH560 coupling agent, KH570 coupling agent or KH550 coupling agent.
7. The conductive silver paste of claim 1, wherein:
the silver powder is selected from one or more of flake silver powder, spherical silver powder and rod-shaped silver powder.
8. The conductive silver paste of claim 1, wherein:
The structure of the bisimidazole salt ionic liquid is that Or (b)。
9. A method for preparing the conductive silver paste according to any one of claims 1 to 8, comprising the steps of:
Uniformly mixing bisphenol A epoxy resin, a curing agent, a diluent, an accelerator and a coupling agent in a high-speed mixer according to the weight ratio to obtain matrix resin, adding modified silver powder into the matrix resin, fully stirring, then putting into a three-roller grinder for grinding and dispersing, and finally filtering, vacuum defoaming and packaging to obtain the conductive silver adhesive.
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| CN106753133A (en) * | 2016-12-30 | 2017-05-31 | 中国科学院深圳先进技术研究院 | A kind of conductive silver glue and its production and use |
| CN114806476A (en) * | 2022-06-01 | 2022-07-29 | 罗卫中 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
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| KR101148019B1 (en) * | 2010-08-05 | 2012-05-24 | (주) 알케머 | Conductive water dispersable composition and conductive coating composition comprising ionic liquid and silver nano particles |
| JP2016110726A (en) * | 2014-12-03 | 2016-06-20 | 三菱製紙株式会社 | Optically transparent conductive material laminate |
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| CN106753133A (en) * | 2016-12-30 | 2017-05-31 | 中国科学院深圳先进技术研究院 | A kind of conductive silver glue and its production and use |
| CN114806476A (en) * | 2022-06-01 | 2022-07-29 | 罗卫中 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
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