CN111303813B - Room temperature curing pouring sealant for precise electronic components and use method thereof - Google Patents
Room temperature curing pouring sealant for precise electronic components and use method thereof Download PDFInfo
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- 239000000565 sealant Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- 239000003085 diluting agent Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims description 28
- 239000004593 Epoxy Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical group 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- -1 alicyclic amine Chemical class 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 description 14
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- 230000004048 modification Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JNTYLPFZLSURCZ-UHFFFAOYSA-L C(C)(=O)O[Zn]Br Chemical compound C(C)(=O)O[Zn]Br JNTYLPFZLSURCZ-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a room temperature curing pouring sealant for electronic components and a use method thereof, and relates to the technical field of electronic component protection. The pouring sealant comprises a component A, a component B and a component C; the component A is prepared by mixing 100 parts of modified epoxy resin, 1-10 parts of reactive diluent, 1-5 parts of accelerant and 0.5-3 parts of coupling agent in parts by weight; the component B is an amine curing agent; the component C is a solvent-free nanofluid. The pouring sealant disclosed by the invention has the characteristics of low viscosity, high impact strength, high adhesive force, high dynamic mechanical strength, low linear expansion coefficient and the like, and is excellent in comprehensive performance.
Description
Technical Field
The invention relates to the technical field of electronic component protection in the electronic industry, in particular to a room temperature curing pouring sealant for a precise electronic component and a using method thereof.
Background
The epoxy resin condensate is usually applied to the field of encapsulation of electronic components by virtue of excellent comprehensive properties of the epoxy resin condensate, can strengthen the integrity of the electronic components, improves the resistance to external impact and vibration, and improves the insulativity of internal components or circuits. However, the epoxy resin has the problems of brittle quality, poor impact resistance, high internal stress, easy cracking and the like, so that the reliability of the work of the epoxy potting product for the precise electronic component with the complex structure is greatly influenced.
Research on epoxy resin encapsulating materials in domestic and foreign research institutes generally only focuses on static performance, and little relates to dynamic performance related research. In fact, some special precise electronic systems have extremely high requirements on the performance of materials for encapsulating and protecting electronic components thereof, particularly epoxy resin materials, including the raw material viscosity of encapsulating glue, the bonding performance of devices, the impact strength, the dynamic mechanical strength, the linear expansion coefficient and the like of the materials.
For the encapsulation of precise electronic components, the curing temperature of epoxy resin is generally required to be as low as possible, so that the damage of the precise electronic components in the high-temperature curing process is avoided, and the heat release in the curing process and the comprehensive mechanical properties of a cured substance must be considered. However, most of the epoxy pouring sealants researched and developed at present are either high-temperature pouring sealants or general in all comprehensive properties, such as Chinese patent application 201010284290, the prepared low-viscosity epoxy pouring sealant has the viscosity (25 ℃) of less than or equal to 2500mPa ∙ s, and the curing temperature is as high as 70-120 ℃; for example, the highest curing temperature experienced in the preparation process of the epoxy pouring sealant in the Chinese patent application 201210288422.4 is as high as 105 ℃; for example, the viscosity of the room temperature curing epoxy pouring sealant reported by Wanghao et al (preparation and performance research of the room temperature curing epoxy pouring sealant, bonding, 2019, 18-21) is as high as 8000-; and the impact strength of the epoxy pouring sealant reported by Nailongjiang chemical research institute, Kimbean and the like (preparation of the room temperature curing epoxy resin pouring sealant, chemical engineers, 09 year 2012) is only 10-15MPa, and the performance is general.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides the room-temperature curing pouring sealant for the precise electronic components, which is particularly suitable for the protection requirements of the precise electronic components. The invention aims to solve the problem that the pouring sealant in the prior art can not meet the performance requirement of the pouring of precise electronic components. The pouring sealant disclosed by the invention has the characteristics of low viscosity, high impact strength, high adhesive force, high dynamic mechanical strength, low linear expansion coefficient and the like, and is excellent in comprehensive performance.
In order to solve the problems in the prior art, the invention is realized by the following technical scheme:
the utility model provides a room temperature curing casting glue for accurate electronic components which characterized in that: the adhesive comprises a component A, a component B and a component C, wherein the component A is prepared by mixing the following components in parts by weight:
100 parts of modified epoxy resin, 1-10 parts of reactive diluent, 1-5 parts of accelerator and 0.5-3 parts of coupling agent; the component B is an amine curing agent; the component C is a solvent-free nanofluid.
The modified epoxy resin is one or a combination of polyurethane modified CYD-128 epoxy resin, liquid carboxyl-terminated butyronitrile modified CYD-128 epoxy resin and hyperbranched epoxy modified CYD-128 epoxy resin.
The diluent is a reactive diluent with an epoxy group, and specifically is one or a combination of more of 662# epoxy diluent, 669# epoxy diluent, 632# epoxy diluent and 636# epoxy diluent.
The accelerator is an epoxy room temperature curing accelerator, and specifically is one or a combination of 2-ethyl-4-methylimidazole accelerator and 2,4, 6-tris [ (dimethylamino) methyl ] phenol.
The coupling agent is a silane coupling agent, and specifically is one or a combination of more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropoxy-trimethoxysilane and gamma-methylpropanoyloxypropyltrimethoxysilane.
The amine curing agent is one or a combination of alicyclic amine curing agent, aliphatic amine curing agent and polyether amine curing agent.
The solvent-free nano fluid is solvent-free TiO2Nanofluid, solventless CaCO3Nanofluid, solventless SiO2A nanofluid, a solvent-free ZnO nanofluid, a solvent-free carbon black nanofluid, a solvent-free graphene nanofluid, and a solvent-free carbon nanotube nanofluid.
The invention also provides a use method of the room temperature curing pouring sealant for the precise electronic components, the pouring sealant can be cured at room temperature, the viscosity, the bonding property, the impact strength, the dynamic compression yield strength and the linear expansion coefficient of the pouring sealant can meet the high-performance pouring protection requirement of the electronic components, and the comprehensive performance is excellent.
A use method of a room temperature curing pouring sealant for precise electronic components is characterized by comprising the following steps: mixing 100 parts of the component A, 15-35 parts of the component B and 0.5-10 parts of the component C, stirring uniformly, vacuumizing, defoaming, and curing at room temperature for 12-96 hours.
Furthermore, the preferred technical scheme of the invention is as follows: mixing 100 parts of component A, 20-30 parts of component B and 0.5-5 parts of component C, stirring uniformly, vacuumizing, defoaming, and curing at room temperature for 36-72 h.
Compared with the prior art, the beneficial technical effects brought by the invention are as follows:
1. the pouring sealant can achieve the following performance indexes: (1) viscosity: at 25 ℃,1500 mPa ∙ s-2400 mPa ∙ s, which can be adjusted by the type and amount of diluent added, (2) gel time: 6-8h, can be adjusted by the type and the addition amount of the accelerator, and (3) the shear strength: not less than 12MPa (aluminum and aluminum), not less than 12MPa (epoxy resin plate and epoxy resin plate), (4) tensile strength: the dynamic compressive yield strength is more than or equal to 60MPa (5) and more than or equal to 190MPa (the strain rate is more than or equal to 1000 s)-1) (6) the impact strength is more than or equal to 70 MPa; (7) linear expansion coefficient less than or equal to 6.0 x 10-5 ℃-1。
2. The invention discloses a room temperature curing pouring sealant with room temperature curability for electronic components, wherein a component A formula in raw materials is epoxy resin consisting of polyurethane with a obdurability unit, a liquid carboxyl-terminated butyronitrile, a hyperbranched epoxy oxygen unit and the like, a curing agent also considers the alicyclic amine/aliphatic amine/polyether amine curing agent with the obdurability unit, a solvent-free nano fluid filler with low viscosity, high dispersibility and functionality is introduced on the basis, the excellent obdurability and good adhesion of the epoxy resin pouring sealant are shown under the organic coordination of the three through the optimization design of the components, and the linear expansion coefficient of an epoxy resin material can be reduced to a certain degree by introducing the solvent-free nano fluid. On the basis of the key three components, an active diluent with an epoxy group, an epoxy room temperature curing accelerator, a silane coupling agent and the like are introduced, so that the viscosity of a resin raw material system can be further reduced, and the effects of improving the curing efficiency and the bonding performance are achieved.
3. In the invention, the excessive amine groups are remained on part of the solvent-free nanofluid, so that the amine groups can participate in the curing process of the epoxy resin as the function similar to that of the curing agent, and the curing reaction can be promoted. The nano fluid has the characteristics of single dispersion and fluidity at a state close to room temperature, so that the resin viscosity cannot be increased when the nano fluid is introduced into an epoxy resin system, on the contrary, the introduction of the solvent-free nano fluid with lower viscosity has a certain effect of reducing the viscosity of the resin system (the nano particles can increase the viscosity of the system after being introduced), the nano fluid can be dispersed in the epoxy resin material uniformly due to the good dispersibility, and a large modification effect can be exerted when a small amount of the solvent-free nano fluid is added (although the introduction of the nano particles can bring a certain modification effect, the nano particles are easy to agglomerate, so that the mechanical property of part of the resin material can be obviously reduced or the modification effect is not obvious when the addition amount of the nano particles is increased due to stress concentration in the material). In addition, in the preparation process of partial solvent-free nano fluid, because-OH which is not completely grafted exists on the surface of the nano particle or an outer organic matter which is grafted on the surface of the solvent-free nano fluid contains some active terminal amino groups, the nano fluid can participate in the curing reaction of the epoxy resin, so that the epoxy resin composite material shows better performance, such as solvent-free SiO2The incomplete surface grafted-OH during nanofluid preparation increases the chemical reaction cross-linking points and lowers the reaction temperature. At the same timeThe fluid outer layer polyetheramine also contains a large number of reactive terminal amine groups, which can also provide crosslinking sites for the epoxy resin.
Detailed Description
The technical solution of the present invention is further elaborated below with reference to the embodiments.
In this embodiment, the room temperature curing pouring sealant for the precision electronic component comprises a component A, a component B and a component C, wherein the component A is formed by mixing the following components in the following table 1 in parts by weight.
Table 1 shows the composition and amount of component A.
The component B in the room temperature curing pouring sealant for the precise electronic components is an amine curing agent; the component C is a solvent-free nanofluid. The modified epoxy resin is one or a combination of polyurethane modified CYD-128 epoxy resin, liquid carboxyl-terminated butyronitrile modified CYD-128 epoxy resin and hyperbranched epoxy modified CYD-128 epoxy resin; the diluent is a reactive diluent with an epoxy group, and specifically is one or a combination of more of 662# epoxy diluent, 669# epoxy diluent, 632# epoxy diluent and 636# epoxy diluent.
The accelerator is an epoxy room temperature curing accelerator, and specifically is one or a combination of 2-ethyl-4-methylimidazole accelerator and 2,4, 6-tris [ (dimethylamino) methyl ] phenol.
The coupling agent is a silane coupling agent, and specifically is one or a combination of more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropoxy-trimethoxysilane and gamma-methylpropanoyloxypropyltrimethoxysilane.
The amine curing agent is one or a combination of alicyclic amine curing agent, aliphatic amine curing agent and polyether amine curing agent.
The solvent-free nano fluid is solvent-free TiO2Nanofluid, solventless CaCO3Nanofluid, solventless SiO2A nanofluid, a solvent-free ZnO nanofluid, a solvent-free carbon black nanofluid, a solvent-free graphene nanofluid, and a solvent-free carbon nanotube nanofluid.
Wherein the solvent-free nano TiO2The fluid preparation method comprises the following steps: hydroxylating surface of nano TiO2Grafted with quaternized silane coupling agent, and then ion-exchanged with polyoxyethylene functionalized organic long chain.
Solvent-free CaCO3The preparation method of the nano-fluid comprises the following steps of (Li Q and other J Am Chem Soc, 2009, 131 (26): 9148-9149): under specific chemical conditions, the number of hydroxyl groups on the surface of the nano fluid is increased, and then the nano fluid is treated by adopting a silane coupling agent grafting technology, so that the solvent-free calcium carbonate nano fluid can be prepared.
Solventless SiO2The preparation method of the nanofluid comprises the following steps: preparing solid SiO with different grain diameters by using absolute ethyl alcohol, ammonia water, deionized water, methanol and tetraethoxysilane at room temperature by adopting a Stober method2Nanometer microsphere, wherein KH560 is used to graft polyether amine (monoamine, diamine or triamine) on SiO2Surface, preparing to obtain solvent-free SiO2A nanofluid. Or, first, in SiO2The surface of the particles is treated by an acidic silane coupling agent, then is neutralized by NaOH to form salt, after the reaction is carried out for 24 hours at 70 ℃, sodium ions are removed by a particle exchange column and are fully protonated, the obtained product and alkaline PEG functionalized tertiary amine are subjected to acid-base reaction to prepare the solvent-free SiO2A nanofluid.
The preparation method of the solvent-free ZnO nanofluid comprises the following steps: firstly, NaOH and ZnCl are used2Reaction to prepare Zn (OH)2Then reacting with bromoacetic acid to obtain bromozinc acetate, then reacting with N, N-dimethyl octadecyl amine to obtain corresponding quaternary ammonium salt, then carrying out anion exchange with quinine sulfate to obtain zinc ionic liquid, and finally reacting with LiOH to obtain ZnO ionic liquid, namely the solvent-free ZnO nanofluid.
The preparation method of the solvent-free carbon black nanofluid comprises the following steps: firstly, carrying out strong acid oxidation treatment on original carbon black, then grafting by using a silane coupling agent DC5700 to obtain carbon black organic ionic salt, and finally carrying out ion exchange with PEG functionalized nitrate to prepare the solvent-free carbon black nano fluid with liquid-like behavior.
The preparation method of the solvent-free graphene nanofluid comprises the following steps: grafting diazonium salt to the surface of graphene by utilizing a spontaneous transfer mechanism from graphene surface electrons to the diazonium salt to obtain sulfonated graphene, exchanging flexible long-chain ions with graphene ions to obtain diazo compound graft, and finally obtaining solvent-free graphene fluid.
The preparation method of the solvent-free carbon nanotube nanofluid comprises the following steps: the solvent-free carbon nano tube nano fluid is prepared by carrying out acid-base reaction on octadecylamine polyoxyethylene ether and the carbon nano tube subjected to acid oxidation. Or, grafting polyether amine (mono-, di-or tri-amine) on the surface of the carbon nanotube by using a KH560 coupling agent to prepare the corresponding solvent-free carbon nanotube nanofluid.
The invention also provides a use method of the room temperature curing pouring sealant for the precise electronic components, the pouring sealant is cured at room temperature, the viscosity, the bonding property, the impact strength, the dynamic compressive yield strength and the linear expansion coefficient of the pouring sealant can meet the requirements of special electronic components, and the comprehensive performance is excellent.
A method for using the room temperature curing pouring sealant for precise electronic components comprises the steps of mixing and stirring 100 parts of component A, 15-35 parts of component B and 0.5-10 parts of component C uniformly, vacuumizing and defoaming, and curing at room temperature for 12-96 hours.
Furthermore, the preferred technical scheme of the invention is as follows: mixing 100 parts of component A, 20-30 parts of component B and 0.5-5 parts of component C, stirring uniformly, vacuumizing, defoaming, and curing at room temperature for 36-72 h. Wherein the component A is selected from any mixture ratio of the above examples 1-7, and the specific mixture ratio is shown in the following table 2:
table 2 shows the proportions and performance parameters of components A, B and C.
After the component A, the component B and the component C are mixed at room temperature, a rotational viscometer is adopted for measuring the viscosity, and GB/T22314-; after the component A and the component B were mixed in the proportions of the above examples 1 to 7, they were cured at room temperature, and the shear strengths thereof were measured by adhesion between aluminum plates and adhesion between resin plates, respectively, to obtain the test results shown in the above table (shear strength: measured by a universal tester according to the GB/T7124-86 adhesive tensile shear strength test standard). The linear expansion coefficient test is obtained according to the GB/T1036-89 plastic linear expansion coefficient measuring method; the dynamic compressive yield strength test mainly adopts a Hopkinson pressure bar experiment test system, enables the interior of a sample to generate compression waves, tensile shear waves or compressive shear waves by changing the shapes of the ends of an incident bar and a projection bar which are in contact with the test, and is obtained according to the stress-strain relationship of materials under different strain rates on the basis of a one-dimensional elastic wave theory. The specific test results are shown in table 2 above.
As can be seen from the above table, the potting adhesive provided by the present invention can achieve the following properties: (1) viscosity: at 25 ℃,1500 mPa ∙ s-2400 mPa ∙ s, which can be adjusted by the type and amount of diluent added, (2) gel time: 6-8h, can be adjusted by the type and the addition amount of the accelerator, and (3) the shear strength: not less than 12MPa (aluminum and aluminum), not less than 12MPa (epoxy resin plate and epoxy resin plate), (4) tensile strength: the dynamic compressive yield strength is more than or equal to 60MPa (5) and more than or equal to 190MPa (the strain rate is more than or equal to 1000 s)-1) (6) the impact strength is more than or equal to 70 MPa; (7) linear expansion coefficient less than or equal to 6.0 x 10-5 ℃-1。
In the application, a set of comparison experiments are also provided, namely, the component C is replaced by the nano particles, and the performance of the pouring sealant formed by mixing the component A, the component B and the nano particles is tested, wherein the test method is consistent with the test method. The experimental results obtained are shown in table 3 below.
Table 3 is the performance parameters after replacing the solvent-free nanofluid of component C with nanoparticles.
As can be seen from tables 2 and 3, the solvent-free nanofluid can effectively reduce the viscosity of the potting adhesive, and the shear strength, the tensile strength, the dynamic compressive yield strength and the impact strength are all improved, and the linear expansion coefficient is reduced.
In the invention, redundant amine groups are remained on part of the solvent-free nanofluid, so that the amine groups can participate in the curing process of the epoxy resin as a function similar to that of a curing agent, and the curing reaction can be promoted. The nano fluid has the characteristics of single dispersion and fluidity at a state close to room temperature, so that the resin viscosity cannot be increased when the nano fluid is introduced into an epoxy resin system, on the contrary, the introduction of the solvent-free nano fluid with lower viscosity has a certain effect of reducing the viscosity of the resin system (the viscosity of the system can be increased after the nano particles are introduced), the nano fluid can be dispersed in the epoxy resin material uniformly due to the good dispersibility, and a large modification effect can be exerted when a small amount of the solvent-free nano fluid is added (although the introduction of the nano particles can bring a good modification effect, the introduction of the nano particles can easily cause stress concentration in the material, so that the mechanical property of part of the resin material can be obviously reduced or the modification effect is not obvious when the addition amount of the nano particles is increased). In the preparation process of partial solvent-free nanofluid, the incomplete grafted-OH exists on the surface of the nano particles or the outer organic matter grafted on the surface of the solvent-free nano particles contains some active terminal amino groups, and the active terminal amino groups can participate in the curing reaction of the epoxy resin, so that the epoxy resin composite material shows better performance, such as solvent-free SiO2the-OH incompletely grafted on the surface in the preparation process of the nanofluid can increase the crosslinking point of chemical reaction, reduce the reaction temperature, and simultaneously contain a large amount of active terminal amino in the polyether amine on the outer layer of the fluid, thereby providing the crosslinking point for the epoxy resin.
Claims (8)
1. The utility model provides a room temperature curing casting glue for accurate electronic components which characterized in that: the adhesive comprises a component A, a component B and a component C, wherein the component A is prepared by mixing the following components in parts by weight:
100 parts of modified epoxy resin, 1-10 parts of reactive diluent, 1-5 parts of accelerator and 0.5-3 parts of coupling agent; the component B is an amine curing agent; the component C is a solvent-free nanofluid; the modified epoxy resin is one or a combination of more of polyurethane modified CYD-128 epoxy resin, liquid carboxyl-terminated butyronitrile modified CYD-128 epoxy resin and hyperbranched epoxy modified CYD-128 epoxy resin; the diluent is a reactive diluent with epoxy groups; the accelerant is an epoxy room temperature curing accelerant; the coupling agent is a silane coupling agent.
2. The room temperature curing pouring sealant for the precise electronic component as claimed in claim 1, wherein: the diluent is specifically one or a combination of more of 662# epoxy diluent, 669# epoxy diluent, 632# epoxy diluent and 636# epoxy diluent.
3. The room temperature curing pouring sealant for the precise electronic component as claimed in claim 1, wherein: the promoter is one or more of 2-ethyl-4-methylimidazole promoter and 2,4, 6-tri [ (dimethylamino) methyl ] phenol.
4. The room temperature curing pouring sealant for the precise electronic component as claimed in claim 1, wherein: the coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropoxy trimethoxysilane and gamma-methylpropanoyloxypropyltrimethoxysilane.
5. The room temperature curing pouring sealant for the precise electronic component as claimed in claim 1, wherein: the amine curing agent is one or a combination of alicyclic amine curing agent, aliphatic amine curing agent and polyether amine curing agent.
6. The room temperature curing pouring sealant for the precise electronic component as claimed in claim 1, wherein: the solvent-free nano fluid is solvent-free TiO2Nanofluid, solventless CaCO3Nanofluid, solventless SiO2A nanofluid, a solvent-free ZnO nanofluid, a solvent-free carbon black nanofluid, a solvent-free graphene nanofluid, and a solvent-free carbon nanotube nanofluid.
7. The use method of the room temperature curing pouring sealant for the precise electronic component as claimed in any one of claims 1 to 6, characterized in that: mixing 100 parts of the component A, 15-35 parts of the component B and 0.5-10 parts of the component C, stirring uniformly, vacuumizing, defoaming, and curing at room temperature for 12-96 hours.
8. The use method of the room temperature curing pouring sealant for the precise electronic component as claimed in claim 7, characterized in that: mixing 100 parts of component A, 20-30 parts of component B and 0.5-5 parts of component C, stirring uniformly, vacuumizing, defoaming, and curing at room temperature for 36-72 h.
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