CN114774047A - Flexible heat-conducting glue composition and preparation method thereof - Google Patents
Flexible heat-conducting glue composition and preparation method thereof Download PDFInfo
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- CN114774047A CN114774047A CN202210539174.XA CN202210539174A CN114774047A CN 114774047 A CN114774047 A CN 114774047A CN 202210539174 A CN202210539174 A CN 202210539174A CN 114774047 A CN114774047 A CN 114774047A
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000003292 glue Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims description 29
- 230000001070 adhesive effect Effects 0.000 claims description 29
- 239000000539 dimer Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 14
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 14
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- -1 3, 4-epoxy-6-methyl cyclohexyl methyl Chemical group 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- NIDWUZTTXGJFNN-UHFFFAOYSA-N 3-bromopropoxybenzene Chemical compound BrCCCOC1=CC=CC=C1 NIDWUZTTXGJFNN-UHFFFAOYSA-N 0.000 claims description 2
- KPOXQAKDFUYNFA-UHFFFAOYSA-N 3-methyl-7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(O)=O)C(C)CC2OC21 KPOXQAKDFUYNFA-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 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 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 28
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 14
- 235000017491 Bambusa tulda Nutrition 0.000 description 14
- 241001330002 Bambuseae Species 0.000 description 14
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 14
- 239000011425 bamboo Substances 0.000 description 14
- 230000000536 complexating effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001052 transient effect Effects 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- 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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a flexible heat-conducting glue composition and a preparation method thereof, wherein an aluminum nitride filled epoxy resin composite material with good heat-conducting and insulating properties is prepared by the following steps: 18-26 parts of epoxy resin, 8-12 parts of epoxy diluent, 5-7 parts of curing agent, 1.4-1.8 parts of accelerator and 55-65 parts of aluminum nitride heat-conducting filler. The composition has the advantages of good fluidity, high bonding strength, high elongation at break after curing, low tensile modulus and the like, has good heat-conducting property and better flexibility, and has wide application prospect in the field of electronic and electric appliances and thermal interface materials.
Description
Technical Field
The invention relates to a flexible heat-conducting glue composition and a preparation method thereof, belonging to the technical field of composite insulating heat-conducting materials.
Background
In recent years, with the wide application of high-power modules and high-power devices in the electrical and electronic fields and the development of electronic equipment towards high speed, high frequency, high power density and high integration, more and more components are mounted on various types of electronic equipment, the power consumption of the devices per unit volume is larger and larger, and the heat management becomes a key factor influencing the reliability and the service life of the electronic equipment. The insulating adhesive used for packaging the electronic element has a significant influence on the heat dissipation capability of the electronic product. Epoxy resin is widely used for electronic insulating glue because of its excellent adhesive, corrosion resistance and electrical insulation properties, but the thermal conductivity of unmodified epoxy resin is only about 0.2W/(m.K), and it is usually necessary to add a thermal conductive filler to improve the thermal conductivity. Among a plurality of inorganic heat-conducting fillers, the heat conductivity coefficient of the aluminum nitride reaches up to 320W/(m.K), and the aluminum nitride also has excellent thermal stability, electrical insulation property and dielectric property, is an ideal heat-conducting filler, and can greatly improve the heat conductivity of the epoxy resin electronic insulation adhesive after being filled with the aluminum nitride. After excessive aluminum nitride is added into the existing epoxy resin insulating glue, the process performance and the mechanical property of the existing epoxy resin insulating glue are both adversely affected, so that the improvement of the heat conductivity of the existing epoxy resin insulating glue is limited by the requirements of the process performance and the mechanical property.
Besides good heat-conducting property, the electronic insulating adhesive is required to have flexibility in many application scenes because of the difference of thermal expansion coefficients between different electronic components and circuit substrates, internal stress is easy to generate in high-temperature and low-temperature environments, and therefore the stability of electronic products is influenced.
Therefore, the development of the epoxy heat-conducting insulating glue with high flexibility has a high practical value.
Disclosure of Invention
The invention aims to overcome the defects and provide a flexible heat-conducting glue composition with high flexibility, good bonding property and good heat-conducting property and a preparation method thereof.
The purpose of the invention is realized by the following steps:
the flexible heat-conducting glue composition comprises the following components in parts by weight: 18-26 parts of epoxy resin, 8-12 parts of epoxy diluent, 5-7 parts of dimer acid epoxy curing agent, 1.4-1.8 parts of accelerator and 55-65 parts of aluminum nitride heat-conducting filler.
Further, the epoxy resin includes at least one of electronic grade bisphenol a epoxy resin, bisphenol F epoxy resin, dimer acid-modified epoxy resin, bisphenol S epoxy resin, novolac epoxy resin and hydrogenated bisphenol a epoxy resin, multifunctional glycidyl amine epoxy resin, biphenyl glycidyl ether epoxy resin, naphthol epoxy resin, 3, 4-epoxycyclohexylcarboxylic acid, 3',4' -epoxycyclohexylmethyl ester, 3, 4-epoxy-6-methylcyclohexylcarboxylic acid, 3',4' -epoxy-6 ' -methylcyclohexylmethyl ester and 3, 4-epoxy-6-methylcyclohexylmethyl ester.
Further, the epoxy diluent comprises at least one of benzyl glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, cardanol glycidyl ether, 4-tert-butylphenyl glycidyl ether, vinylcyclohexene dioxide, and diglycidyl aniline.
Further, the dimer acid-based epoxy curing agent is at least one of dimer acid P1025, dimer acid P1027, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride and hydrogenated methyl nadic anhydride.
Further, the accelerator includes at least one of zinc acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, an imidazole adduct, and a tertiary amine adduct.
Further, the aluminum nitride heat-conducting filler is composed of irregular micron-sized aluminum nitride powder with the average particle size of 2-10 um.
A preparation method of the flexible heat-conducting glue composition based on claims 1 to 6, comprising the following steps:
mixing 18-26 parts by weight of epoxy resin, 8-12 parts by weight of epoxy diluent, 5-7 parts by weight of curing agent and 1.4-1.8 parts by weight of accelerator, and then putting the mixture into a dispersing instrument for dispersing;
adding 55-65 parts of aluminum nitride heat-conducting filler into the dispersed mixture, mixing, and then, allowing the mixture to enter a dispersing instrument for dispersing;
and (4) placing the dispersed mixture into a defoaming machine for defoaming treatment to obtain the heat-conducting glue composition.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the carboxylic acid curing agent is combined with the imidazole accelerator to cure the epoxy resin system, so that the formed heat-conducting adhesive has high bonding performance and excellent flexibility, and meanwhile, the addition amount of the aluminum nitride heat-conducting filler is increased on the basis, so that the heat-conducting performance of the heat-conducting adhesive is improved while the bonding performance and the flexibility of the heat-conducting adhesive meet the requirements.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The invention relates to a flexible heat-conducting glue composition which comprises the following components in parts by weight: 18-26 parts of epoxy resin, 8-12 parts of epoxy diluent, 5-7 parts of dimer acid epoxy curing agent, 1.4-1.8 parts of accelerator and 55-65 parts of aluminum nitride heat-conducting filler.
The parts in the examples of the present invention are parts by weight.
Example 1
The present embodiment provides a flexible thermal conductive adhesive composition, including: 25.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 11 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 6.5 parts of curing agent dimer acid P1025 (complexing high-tech), 1.35 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Taitan science), 0.45 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical), and 55 parts of aluminum nitride heat-conducting filler (average particle size of 2um) (bamboo road application material).
The embodiment also provides a preparation method of the flexible heat-conducting glue composition, which specifically comprises the following steps: 25.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 11 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 6.5 parts of curing agent dimer acid P1025 (complexing high-tech), 1.35 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Tantan technology) and 0.45 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annagi chemical) are added into a revolution autorotation disperser for dispersing for 2 min. Adding 55 parts of aluminum nitride heat-conducting filler (with the average particle size of 2um) (bamboo application material) into the obtained liquid mixture, adding the mixture into a revolution and rotation disperser again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the flexible heat-conducting glue composition.
Example 2
The present embodiment provides a flexible thermal conductive adhesive composition, including: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 9.7 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Taitan science), 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical), and 60 parts of aluminum nitride heat-conducting filler (average particle size of 2um) (bamboo road application material).
The embodiment also provides a preparation method of the flexible heat-conducting glue composition, which specifically comprises the following steps: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 9.7 parts of epoxy diluent (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Tantan science) and 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) are added into a revolution autorotation disperser to be dispersed for 2 min. And adding 60 parts of aluminum nitride heat-conducting filler (with the average particle size of 2um) (bamboo application material) into the obtained liquid mixture, adding the mixture into a revolution and rotation dispersing instrument again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the flexible heat-conducting glue composition.
Example 3
The present embodiment provides a flexible thermal conductive adhesive composition, including: 20 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 8.6 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 5 parts of curing agent dimer acid P1025 (complexing high-new), 1.05 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Taitan technology), 0.35 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) and 65 parts of aluminum nitride heat-conducting filler (average particle size is 2 mu m) (bamboo road application material).
The embodiment also provides a preparation method of the flexible heat-conducting glue composition, which specifically comprises the following steps: 20 parts of bisphenol F type epoxy resin 170 (Shanghai Wallace), 8.6 parts of epoxy diluent (lake northern green home), 5 parts of curing agent dimer acid P1025 (complexing high-tech), 1.05 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Tantan technology) and 0.35 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annagi chemical) are added into a revolution and rotation disperser for dispersing for 2 min. Adding 65 parts of aluminum nitride heat-conducting filler (with the average particle size of 2um) (bamboo application material) into the obtained liquid mixture, adding the mixture into a revolution and rotation disperser again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the flexible heat-conducting glue composition.
Example 4
The present embodiment provides a flexible thermal conductive adhesive composition, including: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 9.7 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Taitan science), 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical), and 60 parts of aluminum nitride heat-conducting filler (average particle size of 5um) (bamboo road application material).
The embodiment also provides a preparation method of the flexible heat-conducting glue composition, which specifically comprises the following steps: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 9.7 parts of epoxy diluent (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Tantan science) and 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) are added into a revolution autorotation disperser to be dispersed for 2 min. And adding 60 parts of aluminum nitride heat-conducting filler (with the average particle size of 5 micrometers) (bamboo application materials) into the obtained liquid mixture, adding the mixture into a revolution and rotation dispersing instrument again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the flexible heat-conducting glue composition.
Example 5
The present embodiment provides a flexible thermal conductive adhesive composition, including: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 9.7 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Taitan science), 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) and 60 parts of aluminum nitride heat-conducting filler (average particle size 10 mu m) (bamboo road application material).
The embodiment also provides a preparation method of the flexible heat-conducting glue composition, which specifically comprises the following steps: 22.7 parts of bisphenol F type epoxy resin 170 (Shanghai Wallace), 9.7 parts of epoxy diluent (Hubei green home), 6 parts of curing agent dimer acid P1025 (complexing high-new), 1.2 parts of accelerator 2-ethyl-4-methylimidazole (Shanghai Tantan science) and 0.4 part of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) are added into a revolution and rotation dispersing instrument for dispersing for 2 min. And adding 60 parts of aluminum nitride heat-conducting filler (with the average particle size of 10 mu m) (bamboo application material) into the obtained liquid mixture, adding the mixture into a revolution and rotation dispersing instrument again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the flexible heat-conducting glue composition.
Comparative example 1
The present embodiment provides a thermally conductive adhesive composition, including: 26 parts of bisphenol F type epoxy resin 170 (Shanghai friendship), 12 parts of epoxy diluent 1, 4-butanediol diglycidyl ether (Hubei green home), 2 parts of curing agent 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical), and 60 parts of aluminum nitride heat-conducting filler (average particle size of 5um) (bamboo application material).
26 parts of bisphenol F type epoxy resin 170 (Shanghai Wallace), 12 parts of epoxy diluent (lake northern green home) and 2 parts of curing agent 1-cyanoethyl-2-ethyl-4-methylimidazole (Annaiji chemical) are added into a revolution and rotation disperser to be dispersed for 2 min. And adding 60 parts of aluminum nitride heat-conducting filler (with the average particle size of 5um) (bamboo application material) into the obtained liquid mixture, adding the mixture into a revolution and rotation disperser again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the heat-conducting glue composition.
Comparative example 2
The present embodiment provides a thermally conductive adhesive composition, including: 13.4 parts of bisphenol F type epoxy resin 170 (Shanghai Huayi), 5.8 parts of epoxy diluent (Hubei green home), 19.6 parts of curing agent methyl hexahydrophthalic anhydride (complexing high-tech), 1.2 parts of accelerant 2-ethyl-4 methylimidazole (Shanghai Taitan science) and 60 parts of aluminum nitride heat-conducting filler (average particle size is 5 mu m) (bamboo application material). Obtaining the heat-conducting glue composition.
13.4 parts of bisphenol F type epoxy resin 170 (Shanghai Wallace), 5.8 parts of epoxy diluent (Hubei green home), 19.6 parts of curing agent methyl hexahydrophthalic anhydride (complexing high-tech) and 1.2 parts of accelerator 2-ethyl-4 methylimidazole (Shanghai Tantan technology) are added into a revolution and rotation dispersing instrument for dispersing for 2 min. And adding 60 parts of aluminum nitride heat-conducting filler (with the average particle size of 5 micrometers) (bamboo application materials) into the obtained liquid mixture, adding the mixture into a revolution and rotation dispersing instrument again for dispersing for 2min, and defoaming the obtained mixture for 30min under the condition of-0.1 MPa to obtain the heat-conducting glue composition.
The thermally conductive adhesive compositions of examples 1 to 5 and comparative examples 1 to 2 were tested.
1. Viscosity measurement
The viscosity of the above obtained sample at normal temperature was measured using a laminar rotary viscometer.
2. Volume resistivity test
The volume resistivity of the samples obtained above was tested according to ASTM D257-2007 test Standard.
3. Test of thermal conductivity
The samples obtained above were tested for thermal conductivity using a thermal conductivity tester and according to the ASTM D5930 test standard using the transient hot wire method.
4. Shear strength test
The aluminum-aluminum shear strength of the samples obtained above was tested using an electronic universal tester and in accordance with ASTM D1002 test standards.
5. Tensile Property test
The tensile properties of the samples obtained in examples 1-5 above were tested using an electronic universal tester and according to ASTM D638 test standards.
The results of all the above tests are shown in table 1.
TABLE 1
As can be seen from the test results in table 1:
the tensile-shear strength, the elongation at break and the tensile modulus of the epoxy heat-conducting adhesive in the embodiments 1-5 are greatly superior to those of the conventional epoxy heat-conducting adhesive in the comparative examples 1-2, and the high tensile-shear strength and the high elongation at break indicate that the epoxy heat-conducting adhesive has high plastic deformation capability while strong tensile-shear resistance capability, namely good toughness, and is brittle otherwise; high elongation at break and low tensile modulus indicate strong plastic deformation capability and good tensile elasticity, reflecting the flexibility of the heat-conducting glue, otherwise, rigidity. Therefore, the heat-conducting glue composition has the advantages of high toughness and high flexibility.
The content of the aluminum nitride heat-conducting filler in the embodiments 1 to 3 is gradually increased, the viscosity of the heat-conducting adhesive is increased, the heat-conducting coefficient is increased, the tensile-shear strength is not obviously reduced, the elongation at break and the tensile modulus are increased and then reduced, but the amplitude is very small, which indicates that the viscosity performance and the heat-conducting performance of the heat-conducting adhesive are improved along with the increase of the aluminum nitride heat-conducting filler, and the toughness and the flexibility are slightly fluctuated and are not obviously reduced. Therefore, the heat-conducting glue composition can be added with more aluminum nitride heat-conducting fillers on the basis of meeting the requirements of bonding performance and flexibility performance so as to further improve the heat-conducting performance of the heat-conducting glue composition.
Examples 4 to 5 take example 2 as an optimal basic formula, and change the particle size of the aluminum nitride filler, the results show that the viscosity of the thermal conductive adhesive shows a tendency of first increasing and then decreasing along with the gradual increase of the particle size of the aluminum nitride filler, the thermal conductive performance is continuously improved, and the flexibility is not greatly changed, further showing that the thermal conductive adhesive composition of the present invention can further improve the thermal conductive performance on the basis of ensuring the requirements of the adhesive performance and the flexibility.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A flexible heat-conducting glue composition is characterized in that: the composition comprises the following components in parts by weight: 18-26 parts of epoxy resin, 8-12 parts of epoxy diluent, 5-7 parts of dimer acid epoxy curing agent, 1.4-1.8 parts of accelerator and 55-65 parts of aluminum nitride heat-conducting filler.
2. A flexible thermally conductive adhesive composition according to claim 1, wherein: the epoxy resin comprises at least one of electronic grade bisphenol A epoxy resin, bisphenol F epoxy resin, dimer acid modified epoxy resin, bisphenol S epoxy resin, novolac epoxy resin and hydrogenated bisphenol A epoxy resin, multifunctional glycidyl amine epoxy resin, biphenyl glycidyl ether epoxy resin, naphthol epoxy resin, 3, 4-epoxy cyclohexyl carboxylic acid, 3',4' -epoxy cyclohexyl methyl ester, 3, 4-epoxy-6-methyl cyclohexyl carboxylic acid, 3',4' -epoxy-6 ' -methyl cyclohexyl methyl ester and 3, 4-epoxy-6-methyl cyclohexyl methyl ester.
3. A flexible thermally conductive adhesive composition according to claim 1, wherein: the epoxy diluent comprises at least one of benzyl glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, cardanol glycidyl ether, 4-tert-butylphenyl glycidyl ether, vinylcyclohexene dioxide and diglycidyl aniline.
4. A flexible thermally conductive adhesive composition according to claim 1, wherein: the dimer acid type epoxy curing agent is at least one of dimer acid P1025, dimer acid P1027, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride and hydrogenated methyl nadic anhydride.
5. A flexible thermally conductive adhesive composition according to claim 1, wherein: the accelerant comprises at least one of zinc acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, an imidazole adduct and a tertiary amine adduct.
6. A flexible thermally conductive adhesive composition according to claim 1, wherein: the aluminum nitride heat-conducting filler is composed of irregular micron-sized aluminum nitride powder with the average particle size of 2-10 um.
7. A method for preparing the flexible thermal conductive adhesive composition according to claims 1 to 6, wherein: comprises the following steps:
mixing 18-26 parts of epoxy resin, 8-12 parts of epoxy diluent, 5-7 parts of curing agent and 1.4-1.8 parts of accelerator according to parts by weight, and then putting the mixture into a dispersing instrument for dispersing treatment;
adding 55-65 parts of aluminum nitride heat-conducting filler into the dispersed mixture, mixing, and then, entering a dispersing instrument for dispersing;
and (4) placing the dispersed mixture into a defoaming machine for defoaming treatment to obtain the heat-conducting glue composition.
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| CN1405261A (en) * | 2001-07-06 | 2003-03-26 | 东丽株式会社 | Resin composition, film with adhesive for semiconductor device and semiconductor device with laminated film of metal foil and using same |
| CN102676105A (en) * | 2011-03-16 | 2012-09-19 | 新日铁化学株式会社 | High thermal conductivity membrane adhesive, adhesive composition and semiconductor package using the adhesive and manufacturing method thereof |
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| US5367006A (en) * | 1992-03-16 | 1994-11-22 | Hughes Aircraft Company | Superior thermal transfer adhesive |
| CN1405261A (en) * | 2001-07-06 | 2003-03-26 | 东丽株式会社 | Resin composition, film with adhesive for semiconductor device and semiconductor device with laminated film of metal foil and using same |
| CN102676105A (en) * | 2011-03-16 | 2012-09-19 | 新日铁化学株式会社 | High thermal conductivity membrane adhesive, adhesive composition and semiconductor package using the adhesive and manufacturing method thereof |
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