CN114539960A - Bi-component epoxy resin adhesive and preparation method thereof - Google Patents
Bi-component epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN114539960A CN114539960A CN202111471022.2A CN202111471022A CN114539960A CN 114539960 A CN114539960 A CN 114539960A CN 202111471022 A CN202111471022 A CN 202111471022A CN 114539960 A CN114539960 A CN 114539960A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 29
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000003063 flame retardant Substances 0.000 claims abstract description 24
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims abstract description 5
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 3
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-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
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920006332 epoxy adhesive Polymers 0.000 claims 6
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical class [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical class CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 1
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical class CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 206010013642 Drooling Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 208000008630 Sialorrhea Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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
-
- 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
Abstract
The invention discloses a bi-component epoxy resin adhesive, which is prepared from the following components in percentage by volume of 1: (0.6-1.5) mixing the component A and the component B; the component A comprises the following raw materials in parts by weight: 80-100 parts of modified epoxy resin, 3-20 parts of diluent, 2-10 parts of thixotropic agent, 3-10 parts of flame retardant, 3-12 parts of silane coupling agent and 1-10 parts of auxiliary agent; the component B comprises the following raw materials in parts by weight: 80-100 parts of curing agent and 1-5 parts of curing accelerator; wherein the thixotropic agent is a mixture of fumed silica and nano calcium carbonate; the flame retardant is one or a mixture of melamine, melamine urate and melamine phosphate. The product has stable flowing performance, moderate flowing property at room temperature, high thixotropy, excellent bonding performance, flame retardant property and mechanical property.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a bi-component epoxy resin adhesive and a preparation method thereof.
Background
The epoxy resin adhesive has high cohesive strength and high crosslinking density, has excellent bonding performance to most rigid materials, also has excellent electrical insulation performance and chemical resistance, is suitable for the rapid bonding and packaging of glass, rigid plastics, electronic elements and precise devices, is suitable for the operation of high-efficiency production lines, and is widely used for the bonding and sealing of electronic products and the protective reinforcing and sealing protection of important parts.
When the epoxy resin adhesive is used as an adhesive and a sealing material of an electronic product, the epoxy resin adhesive is required to have moderate flowability, if the flowability is low, the adhesive cannot be leveled during use, the appearance is poor, if the flowability is too high, the adhesive flows into an electronic element, the sealing performance is poor, and the connection or the action of the electronic element is poor. The flowability of the existing epoxy resin adhesive changes along with the preservation time in the preservation process, so that the service performance of the adhesive is influenced; secondly, the existing epoxy resin adhesive has poor comprehensive performance, and the mechanical strength of the system is reduced along with the addition of the flame retardant.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a bi-component epoxy resin adhesive which has stable flowing performance, moderate flowing performance at room temperature, high thixotropy, excellent bonding performance, flame retardant performance and mechanical performance. In addition, the invention also provides a preparation method of the bi-component epoxy resin adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, a two-component epoxy resin adhesive is provided, which is prepared from a mixture of 1: (0.6-1.5) mixing the component A and the component B;
the component A comprises the following raw materials in parts by weight: 80-100 parts of modified epoxy resin, 3-20 parts of diluent, 2-10 parts of thixotropic agent, 3-10 parts of flame retardant, 3-12 parts of silane coupling agent and 1-10 parts of auxiliary agent;
the component B comprises the following raw materials in parts by weight: 80-100 parts of curing agent and 1-5 parts of curing accelerator;
wherein the thixotropic agent is a mixture of fumed silica and nano calcium carbonate;
the flame retardant is one or a mixture of more of melamine, melamine urate and melamine phosphate.
Preferably, the particle size of the fumed silica in the thixotropic agent is 2-8 μm, and the weight ratio of the fumed silica to the nano-scale calcium carbonate in the thixotropic agent is 1: (0.4-0.8).
Experiments show that the adhesive with higher flowing stability can be obtained by compounding fumed silica and nano calcium carbonate as a thixotropic agent, wherein the fumed silica with the particle size of 2-8 mu m has larger particle size and smaller specific surface area, the fumed silica has smaller influence on the viscosity of the adhesive system when added into the adhesive system, and the nano calcium carbonate has smaller particle size, larger specific surface area and larger influence on the viscosity of the adhesive system, so the weight ratio of the fumed silica to the nano calcium carbonate is defined as 1: (0.4-0.8), so that the prepared adhesive system has higher flow stability, moderate fluidity at normal temperature, small viscosity and high thixotropy, does not generate a flow phenomenon when in use, and can be suitable for packaging electronic product elements with smaller sizes.
Preferably, the modified epoxy resin is prepared by the following steps: mixing the components in a weight ratio of 1: (0.3-0.5) adding the epoxy resin and hydroxyl-terminated polybutadiene into a reaction vessel in sequence, and stirring and reacting for 20-40min at the temperature of 65-75 ℃ to obtain the modified epoxy resin.
Hydroxyl groups in the hydroxyl-terminated polybutadiene and partial epoxy groups of the epoxy resin are subjected to ring-opening polymerization, so that the epoxy resin is modified, and the modified epoxy resin introduces a tough structural segment of the hydroxyl-terminated polybutadiene, so that the toughness of the adhesive is greatly improved.
Preferably, the epoxy resin is hydrogenated bisphenol A epoxy resin, and the number average molecular weight of the hydroxyl-terminated polybutadiene is 1800-2500.
The molecular chain of the hydrogenated bisphenol A epoxy resin does not contain double bonds, has excellent light radiation resistance, weather resistance and aging resistance, excellent electric arc resistance, breakdown resistance and other properties, and can react with a curing agent to generate a three-dimensional network structure, so that the mechanical property of the adhesive is effectively improved.
Preferably, the silane coupling agent is one or a mixture of methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.
Preferably, the diluent is one or a mixture of more of trimethylolpropane triglycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, ethylene glycol glycidyl ether and phenyl glycidyl ether.
When in use, the diluent can be selectively added according to the viscosity degree of the system.
Preferably, the curing agent is an organic acid anhydride curing agent.
The organic acid anhydride curing agent is one or a mixture of more of methylhexahydrophthalic anhydride, phthalic anhydride and maleic anhydride.
Preferably, the curing accelerator is one or a mixture of triethanolamine, triphenylphosphine, 2-ethyl-4-methylimidazole, nonylphenol or benzyl alcohol.
The auxiliary agent is one or a combination of a plurality of dispersing agents, defoaming agents and antioxidants. The dispersant, the defoamer and the antioxidant can be selected from common products sold in the market.
Specifically, the dispersant can be selected from triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol or cellulose derivatives. The defoaming agent is a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether or polyoxyethylene polyoxypropylene amine ether. The UV light absorber is titanium dioxide with a particle size of 10 nm. The antioxidant is 2, 6-di-tert-butyl-p-cresol, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
The second aspect of the present invention provides a preparation method of the above two-component epoxy resin adhesive, comprising the following steps:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 60-70 ℃, uniformly stirring and mixing for 1-2h, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding a curing agent and a curing accelerator into a second reaction container, stirring and mixing for 1-2 hours at normal temperature until the components are uniformly mixed, filtering by using a filter screen, discharging after vacuumizing, and standing and storing in a closed and dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: (0.6-1.5) to obtain the bi-component epoxy resin adhesive.
Compared with the prior art, the invention has the following beneficial effects:
the bi-component epoxy resin adhesive has stable flowing performance, moderate flowing performance at room temperature, high thixotropy, excellent bonding performance, flame retardant performance and mechanical performance;
the fumed silica and the nano calcium carbonate are compounded to be used as the thixotropic agent, and the proportion of the fumed silica and the nano calcium carbonate is regulated and controlled, so that the prepared adhesive system has higher flowing stability, moderate fluidity at normal temperature, small viscosity and high thixotropy, does not generate a flowing phenomenon when in use, and can be suitable for packaging electronic product elements with smaller sizes;
a uniform composite network system is formed between the amino group in the selected flame retardant and the epoxy group in the epoxy resin through intermolecular hydrogen bond acting force, so that the adhesive has an excellent flame retardant effect, and the mechanical property of the system is not affected.
Drawings
The invention is described in further detail below with reference to specific embodiments and with reference to the following drawings.
FIG. 1 is a flow chart of a process for preparing a two-component epoxy resin adhesive according to the present invention;
FIG. 2 is a graph showing viscosity tests of adhesives in examples 1 to 4 and comparative examples 1 to 2;
FIG. 3 is a thixotropic index test chart of the adhesives of examples 1-4 and comparative examples 1-2;
FIG. 4 is a graph showing tensile strength tests of the adhesives of examples 1 to 4 and comparative examples 1 to 2;
FIG. 5 is a graph showing the elongation at break of the adhesives of examples 1 to 4 and comparative examples 1 to 2;
FIG. 6 is a graph showing the change in the flow of the adhesives of examples 1 to 4 and comparative examples 1 to 2.
Detailed Description
Example 1
A bi-component epoxy resin adhesive is prepared from the following components in a volume ratio of 1: 1.2, mixing the component A and the component B;
the component A comprises the following raw materials in parts by weight: 92 parts of modified epoxy resin, 3 parts of diluent (trimethylolpropane triglycidyl ether), 6 parts of thixotropic agent (fumed silica with the particle size of 2-8 mu m and nano calcium carbonate in the weight ratio of 1: 0.5), 3 parts of flame retardant (melamine), 5 parts of silane coupling agent (methyltrimethoxysilane), 1 part of dispersing agent (sodium dodecyl sulfate), 1 part of defoaming agent (polyoxyethylene polyoxypropylene amine ether) and 1 part of UV light absorber (10nm titanium dioxide);
the component B comprises the following raw materials in parts by weight: 86 parts of curing agent (phthalic anhydride) and 3 parts of curing accelerator (triethanolamine);
the preparation process of the modified epoxy resin comprises the following steps: mixing the components in a weight ratio of 1: 0.5 hydrogenated bisphenol A epoxy resin and hydroxyl-terminated polybutadiene (number average molecular weight 1800-.
The preparation method of the bi-component epoxy resin adhesive comprises the following steps:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 60 ℃, stirring and mixing uniformly for 1.5h, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding a curing agent and a curing accelerator into a second reaction container, stirring and mixing for 1h at normal temperature until the curing agent and the curing accelerator are uniformly mixed, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: 1.2, and obtaining the bi-component epoxy resin adhesive.
Example 2
A bi-component epoxy resin adhesive is prepared from the following components in a volume ratio of 1: 0.6 of component A and component B;
the component A comprises the following raw materials in parts by weight: 80 parts of modified epoxy resin, 9 parts of diluent (dodecyl glycidyl ether), 8 parts of thixotropic agent (fumed silica with the particle size of 2-8 mu m and nano calcium carbonate in the weight ratio of 1: 0.4), 5 parts of flame retardant (melamine), 3 parts of silane coupling agent (methyltrimethoxysilane), 0.2 part of dispersing agent (sodium dodecyl sulfate), 0.3 part of defoaming agent (polyoxyethylene polyoxypropylene amine ether) and 0.5 part of UV light absorber (titanium dioxide with the particle size of 10 nm);
the component B comprises the following raw materials in parts by weight: 80 parts of curing agent (maleic anhydride) and 1 part of curing accelerator (triethanolamine);
the preparation process of the modified epoxy resin comprises the following steps: mixing the components in a weight ratio of 1: 0.3 hydrogenated bisphenol A epoxy resin and hydroxyl-terminated polybutadiene (number average molecular weight 1800-.
The preparation method of the bi-component epoxy resin adhesive comprises the following steps:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 70 ℃, stirring and mixing uniformly for 1h, filtering by a filter screen, vacuumizing, discharging, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding the curing agent and the curing accelerator into a second reaction container, stirring and mixing for 2 hours at normal temperature until the curing agent and the curing accelerator are uniformly mixed, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: 0.6 to obtain the bi-component epoxy resin adhesive.
Example 3
A bi-component epoxy resin adhesive is prepared from the following components in a volume ratio of 1: 1.5, mixing the component A and the component B;
the component A comprises the following raw materials in parts by weight: 96 parts of modified epoxy resin, 20 parts of diluent (tetradecyl glycidyl ether), 10 parts of thixotropic agent (fumed silica and nano calcium carbonate with the particle size of 2-8 mu m and the weight ratio of 1: 0.8), 10 parts of flame retardant (melamine urate), 12 parts of silane coupling agent (methyltrimethoxysilane), 1 part of dispersant (sodium dodecyl sulfate), 3 parts of defoamer (polyoxyethylene polyoxypropylene amine ether) and 6 parts of UV light absorber (titanium dioxide with the particle size of 10 nm);
the component B comprises the following raw materials in parts by weight: 93 parts of curing agent (maleic anhydride) and 5 parts of curing accelerator (benzyl alcohol);
the preparation process of the modified epoxy resin comprises the following steps: mixing the components in a weight ratio of 1: 0.4 hydrogenated bisphenol A epoxy resin and hydroxyl-terminated polybutadiene (number average molecular weight 1800-.
The preparation method of the bi-component epoxy resin adhesive comprises the following steps:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 60 ℃, stirring and mixing uniformly for 2 hours, filtering by a filter screen, vacuumizing, discharging, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding the curing agent and the curing accelerator into a second reaction container, stirring and mixing for 2 hours at normal temperature until the curing agent and the curing accelerator are uniformly mixed, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: 1.5, and obtaining the bi-component epoxy resin adhesive.
Example 4
A bi-component epoxy resin adhesive is prepared from the following components in a volume ratio of 1: 0.9 of component A and component B;
the component A comprises the following raw materials in parts by weight: 100 parts of modified epoxy resin, 16 parts of diluent (trimethylolpropane triglycidyl ether), 2 parts of thixotropic agent (fumed silica and nano calcium carbonate with the particle size of 2-8 mu m and the weight ratio of 1: 0.6), 6 parts of flame retardant (melamine urate), 9 parts of silane coupling agent (methyltrimethoxysilane), 2 parts of dispersing agent (sodium dodecyl sulfate), 2 parts of defoaming agent (polyoxyethylene polyoxypropylene ether) and 2 parts of UV light absorber (10nm titanium dioxide);
the component B comprises the following raw materials in parts by weight: 100 parts of curing agent (methylhexahydrophthalic anhydride) and 3 parts of curing accelerator (triethanolamine);
the preparation process of the modified epoxy resin comprises the following steps: mixing the components in a weight ratio of 1: 0.5 hydrogenated bisphenol A epoxy resin and hydroxyl-terminated polybutadiene (number average molecular weight 1800-.
The preparation method of the bi-component epoxy resin adhesive comprises the following steps:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 70 ℃, stirring and mixing uniformly for 1h, filtering by a filter screen, vacuumizing, discharging, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding a curing agent and a curing accelerator into a second reaction container, stirring and mixing for 2 hours at normal temperature until the curing agent and the curing accelerator are uniformly mixed, filtering through a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: 0.9 to obtain the bi-component epoxy resin adhesive.
Comparative example 1
Comparative example 1 is a comparative example to example 1, and comparative example 1 differs from example 1 in that: the thixotropic agent in comparative example 1 was fumed silica having a particle size of 2 to 8 μm.
Comparative example 2
Comparative example 2 is a comparative example to example 1, and comparative example 2 differs from example 1 in that: the thixotropic agent in comparative example 1 was nano-sized calcium carbonate.
The adhesives prepared in examples 1-4, comparative example 1 and comparative example 2 were tested for flowability, viscosity, thixotropic index, tensile strength, elongation at break, and flame retardant rating, and the results are shown in table 1.
The flowing property test process comprises the following steps: dripping 0.1g of product on a glass plate, flatly placing for 10 minutes, inclining for 45 degrees, placing in a hot air drying box, heating for 30 minutes at 120 degrees, measuring the distance from the upper end to the lower end, testing each group of products for 5 times, and calculating the average value; smaller measured distance values indicate more difficulty in drooling.
And (3) viscosity testing: the test was carried out at 25 ℃ using a viscometer of type DV-E from BROOKFIELD.
Thixotropic index: according to GB/T2794-.
Tensile strength, elongation at break: the test was carried out according to GB/T1040-2006 test for tensile Properties of plastics.
TABLE 1
As can be seen from Table 1 and FIGS. 2 to 6, the two-component epoxy resin adhesive of the present invention has stable flow performance, moderate flow at room temperature, high thixotropy, excellent adhesive property, flame retardant property and mechanical property.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (9)
1. The two-component epoxy resin adhesive is characterized by comprising the following components in percentage by volume of 1: (0.6-1.5) mixing the component A and the component B;
the component A comprises the following raw materials in parts by weight: 80-100 parts of modified epoxy resin, 3-20 parts of diluent, 2-10 parts of thixotropic agent, 3-10 parts of flame retardant, 3-12 parts of silane coupling agent and 1-10 parts of auxiliary agent;
the component B comprises the following raw materials in parts by weight: 80-100 parts of curing agent and 1-5 parts of curing accelerator;
wherein the thixotropic agent is a mixture of fumed silica and nano calcium carbonate;
the flame retardant is one or a mixture of more of melamine, melamine urate and melamine phosphate.
2. The two-part epoxy adhesive according to claim 1, wherein the particle size of fumed silica in the thixotropic agent is 2-8 μm, and the weight ratio of fumed silica to nano-sized calcium carbonate in the thixotropic agent is 1: (0.4-0.8).
3. The two-part epoxy adhesive of claim 1, wherein the modified epoxy resin is prepared by the following steps: mixing the components in a weight ratio of 1: (0.3-0.5) adding the epoxy resin and hydroxyl-terminated polybutadiene into a reaction vessel in sequence, and stirring and reacting for 20-40min at the temperature of 65-75 ℃ to obtain the modified epoxy resin.
4. The two-component epoxy adhesive according to claim 3, wherein the epoxy resin is hydrogenated bisphenol A epoxy resin, and the hydroxyl-terminated polybutadiene has a number average molecular weight of 1800-2500.
5. The two-component epoxy resin adhesive according to claim 1, wherein the silane coupling agent is one or a mixture of methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.
6. The two-component epoxy resin adhesive of claim 1, wherein the diluent is one or more of trimethylolpropane triglycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, ethylene glycol glycidyl ether, and phenyl glycidyl ether.
7. The two-part epoxy adhesive of claim 1, wherein the curing agent is an organic anhydride curing agent.
8. The two-part epoxy adhesive of claim 1, wherein the curing accelerator is one or a mixture of triethanolamine, triphenylphosphine, 2-ethyl-4-methylimidazole, nonylphenol, or benzyl alcohol.
9. A method of preparing the two-part epoxy adhesive of claim 1, comprising the steps of:
s1, sequentially adding the modified epoxy resin, the diluent, the thixotropic agent, the flame retardant, the silane coupling agent and the auxiliary agent into a first reaction container, heating to 60-70 ℃, uniformly stirring and mixing for 1-2h, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component A for later use;
s2, sequentially adding a curing agent and a curing accelerator into a second reaction container, stirring and mixing at normal temperature for 1-2 hours until the curing agent and the curing accelerator are uniformly mixed, filtering by a filter screen, discharging after vacuumizing, and standing and storing in a closed dry environment to obtain a component B for later use;
s3, when in use, mixing the component A prepared in the step S1 and the component B prepared in the step S2 in a volume ratio of 1: (0.6-1.5) to obtain the bi-component epoxy resin adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114921210A (en) * | 2022-06-17 | 2022-08-19 | 宜春宇泽新能源有限公司 | Adhesive for solar-grade silicon wafer suitable for large-size flaking and preparation process and use method thereof |
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Cited By (1)
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| CN114921210A (en) * | 2022-06-17 | 2022-08-19 | 宜春宇泽新能源有限公司 | Adhesive for solar-grade silicon wafer suitable for large-size flaking and preparation process and use method thereof |
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