CN113845876A - UV (ultraviolet) humidifying dual-curing heat-conducting adhesive and preparation method thereof - Google Patents
UV (ultraviolet) humidifying dual-curing heat-conducting adhesive and preparation method thereof Download PDFInfo
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- CN113845876A CN113845876A CN202110935158.8A CN202110935158A CN113845876A CN 113845876 A CN113845876 A CN 113845876A CN 202110935158 A CN202110935158 A CN 202110935158A CN 113845876 A CN113845876 A CN 113845876A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 37
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 238000009833 condensation Methods 0.000 claims abstract description 15
- 230000005494 condensation Effects 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims description 77
- 238000002156 mixing Methods 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 37
- 229920001400 block copolymer Polymers 0.000 claims description 35
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 238000007259 addition reaction Methods 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 238000007142 ring opening reaction Methods 0.000 claims description 16
- -1 acryloxy groups Chemical group 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000009736 wetting Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 102220275913 rs754497897 Human genes 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- OEKWJQXRCDYSHL-FNOIDJSQSA-N ticagrelor Chemical compound C1([C@@H]2C[C@H]2NC=2N=C(N=C3N([C@H]4[C@@H]([C@H](O)[C@@H](OCCO)C4)O)N=NC3=2)SCCC)=CC=C(F)C(F)=C1 OEKWJQXRCDYSHL-FNOIDJSQSA-N 0.000 claims 1
- 229960002528 ticagrelor Drugs 0.000 claims 1
- 238000003848 UV Light-Curing Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- 235000018185 Betula X alpestris Nutrition 0.000 description 7
- 235000018212 Betula X uliginosa Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000013008 moisture curing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 description 1
- VKSCZTWQDPUHIK-UHFFFAOYSA-N isocyanic acid;trimethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OC)(OC)OC VKSCZTWQDPUHIK-UHFFFAOYSA-N 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a UV (ultraviolet) humidifying dual-curing heat-conducting adhesive and a preparation method thereof, wherein the preparation method comprises the following steps: polyacrylate siloxane, an active diluent, a crosslinking agent, a heat-conducting filler, a photoinitiator, a condensation catalyst, a defoaming agent and hydrophobic fumed silica; the weight percentage of the polyacrylate siloxane is 5-30 percent; the weight percentage of the active diluent is 5 percent to 30 percent; the weight percentage of the cross-linking agent is 1-5%, and the weight percentage of the heat-conducting filler is 50-80%; the weight percentage of the photoinitiator is 0.5 to 5.0 percent; the weight percentage of the condensation catalyst is 0.01 percent to 1.0 percent; the weight percentage of the defoaming agent is 0.2 to 0.5 percent; the weight percentage of the hydrophobic fumed silica is 0.05-1.0%. The UV humidifying dual-curing heat-conducting adhesive provided by the invention takes polyacrylate siloxane as main body resin, can realize complete curing, and avoids the problem that shadow area complete curing cannot be realized by adopting single UV curing heat-conducting adhesive.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to UV (ultraviolet) humidifying dual-curing heat-conducting adhesive and a preparation method thereof.
Background
With the development of the electronic industry technology and the coming of the 5G era, electronic devices tend to be miniaturized and light and thin, meanwhile, the performance and power of electronic components are continuously improved, the heat flux density is rapidly increased, and how to effectively solve the heat dissipation problem becomes the key point of the further development of the electronic technology. The first benefit in the 5G industry chain is the macro base station, the most core material of which is the printed circuit board (PCB for short). The PCB board card is provided with a plurality of heat sources, and the temperature of the whole PCB element can be increased due to the accumulation of heat energy, so that the aging speed of the material is accelerated. In order to ensure that electronic components can work stably and normally, the heat dissipation capability of a system needs to be improved, so that the development of a heat-conducting adhesive with strong heat-conducting property for protecting a PCB is a problem to be solved urgently.
Chinese patent CN107964385A discloses a high heat conduction ultraviolet light curing adhesive, the ultraviolet light curing adhesive can be cured rapidly in several seconds, the production efficiency is high, but the high heat conduction product of additive type needs to add more heat conduction filler, though the filler of chooseing for use has higher luminousness, but also can have certain absorption to the light, influences the curing depth, can't solidify to the unable penetrable shadow region of light simultaneously.
Chinese patent CN112300746A discloses a UV/moisture dual-curing heat-conducting adhesive, which not only solves the curing problem of shadow areas, but also can add heat-conducting fillers with higher proportion into the formula, solves the problem of incomplete photo-curing caused by excessive heat-conducting fillers through moisture curing, and can prepare the UV/moisture dual-curing heat-conducting adhesive with high bonding strength to various base materials and heat conductivity coefficient more than 1.0W/m.k. The adhesive has the defects of strong smell and poor temperature resistance.
Disclosure of Invention
To achieve the above and other related objects, the present invention provides a UV-wetting dual-curing thermal conductive paste, comprising: polyacrylate siloxane, an active diluent, a crosslinking agent, a heat-conducting filler, a photoinitiator, a condensation catalyst, a defoaming agent and hydrophobic fumed silica; wherein the content of the first and second substances,
the weight percentage of the polyacrylate siloxane is 5-30%; the weight percentage of the active diluent is 5 to 30 percent; the weight percentage of the cross-linking agent is 1-5%, and the weight percentage of the heat-conducting filler is 50-80%; the weight percentage of the photoinitiator is 0.5 to 5.0 percent; the weight percentage of the condensation catalyst is 0.01 percent to 1.0 percent; the weight percentage of the defoaming agent is 0.2-0.5%; the weight percentage of the hydrophobic fumed silica is 0.05-1.0%.
Optionally, the polyacrylate siloxane contains at least two acryloxy groups and at least one alkoxy group in one molecule at the same time.
Alternatively, the polyacrylate siloxane has the structure of the formula:
wherein: r is epoxy-terminated epoxy organosilicon block copolymer, which comprises an organosilicon part and an epoxy part, R2 is-CH 3 or alkoxy of C1-C2, R3 is-CH 3 or alkoxy of C1-C2, k is an integer from 1 to 8, and j is an integer from 1 to 2;
the organosilicon moiety has the general structure:
wherein: r4 is C1-C12 methyl, alkoxy or phenyl, R5 is C1-C12 methyl, alkoxy or phenyl, and x is a natural number from 0 to 1000.
Optionally, the epoxy moiety in the epoxy-terminated epoxy silicone block copolymer comprises one or more of bisphenol a glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol a glycidyl ether, and hydrogenated bisphenol F glycidyl ether; the organosilicon part in the epoxy-terminated epoxy organosilicon block copolymer comprises polysiloxane terminated by hydroxyl groups at two ends or polysiloxane terminated by amino groups at two ends; the epoxy equivalent of the epoxy-terminated epoxy organosilicon copolymer is 400-1500.
Optionally, the reactive diluent comprises a gurley 107 resin having a viscosity of 500cps to 5000 cps.
Optionally, the crosslinking agent comprises at least one of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane; the heat conducting filler comprises at least one of spherical alumina, zinc oxide, boron nitride, aluminum nitride and silicon carbide with different particle sizes; the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexylphenyl ketone, benzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide; the condensation catalyst comprises at least one of dibutyltin dilaurate, tributyltin trilaurate, tin chloride, n-butyl titanate and stannous chloride; the defoaming agent comprises at least one of Pico chemistry BYK-088, BYK-A501, BYK-A506 and BYK-A535; the hydrophobic fumed silica comprises at least one of carbopol TS-720, watt H20, H13L and H15.
The invention also provides a preparation method of the UV-humidifying dual-curing heat-conducting adhesive, which comprises the following steps:
providing 5-30 parts by weight of polyacrylate siloxane, 5-30 parts by weight of reactive diluent, 1-5 parts by weight of cross-linking agent, 0.2-0.5 part by weight of defoaming agent and 0.5-5.0 parts by weight of photoinitiator, and carrying out first mixing and stirring to obtain a first mixture;
adding 0.01-1.0 part of condensation catalyst into the first mixture for second mixing and stirring to obtain a second mixture;
adding 50-80 parts of heat-conducting filler into the second mixture for third mixing and stirring to obtain a third mixture;
adding 0.05-1.0 part of hydrophobic fumed silica into the third mixture, and carrying out fourth mixing and stirring to obtain a fourth mixture;
and placing the fourth mixture in a preset vacuum degree environment for fifth mixing and stirring to obtain the UV humidifying dual-curing heat-conducting glue.
Optionally, the first mixing and stirring speed is 800r/min to 1200r/min, and the first mixing and stirring time is 30 minutes to 40 minutes; the second mixing and stirring speed is 200 r/min-300 r/min, and the second mixing and stirring time is 10 minutes-15 minutes; the third mixing and stirring speed is 200 r/min-300 r/min, and the third mixing and stirring time is 10 minutes-15 minutes; the fourth mixing and stirring speed is 200 r/min-300 r/min, and the fourth mixing and stirring time is 10 minutes-15 minutes; the vacuum degree of the environment with the preset vacuum degree is-0.10 MPa to-0.01 MPa; the fifth mixing and stirring speed is 200 r/min-300 r/min, and the fifth mixing and stirring time is 10 minutes-15 minutes.
Alternatively, the method of preparing the polyacrylate siloxane comprises:
preparing an epoxy-terminated epoxy silicone block copolymer solution;
preparing a mixed solution of acrylic acid, a polymerization inhibitor and a catalyst I;
adding the mixed solution into the epoxy-terminated epoxy organic silicon block copolymer solution to perform epoxy ring-opening addition reaction to obtain an acrylate polysilane compound;
mixing the acrylate polysilane compound with isocyanate-containing silane and a catalyst II to obtain a composition;
subjecting the composition to a hydroxyl addition reaction to obtain the polyacrylate siloxane.
Optionally, the temperature of the epoxy ring-opening addition reaction is 70 ℃ to 150 ℃, and the time of the epoxy ring-opening addition reaction is 2 hours to 8 hours; the temperature of the hydroxyl addition reaction is 50-70 ℃, and the time of the epoxy ring-opening addition reaction is 3-8 hours.
As mentioned above, the UV-wetting dual-curing heat-conducting adhesive and the preparation method thereof have the following beneficial effects: the UV humidifying dual-curing heat-conducting adhesive takes polyacrylate siloxane as main resin, can realize complete curing, and avoids the problem that shadow area complete curing cannot be realized by adopting single UV curing heat-conducting adhesive; the high-temperature resistant performance is excellent; meanwhile, the heat-conducting filler with a higher proportion is added in the formula, the problem of incomplete photocuring caused by excessive heat-conducting filler is solved through moisture curing by compounding the heat-conducting filler with a large particle size and adding the heat-conducting filler with a high specific surface area and a high heat conductivity, and the combination of UV (ultraviolet) moisture dual curing and high-temperature-resistant high-heat-conducting performance is realized.
Drawings
FIG. 1 is a flow chart of a method for preparing a UV-wetting dual-curing thermal conductive adhesive according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
Example one
The invention provides a UV (ultraviolet) humidification dual-curing heat-conducting adhesive, which comprises: polyacrylate siloxane, an active diluent, a crosslinking agent, a heat-conducting filler, a photoinitiator, a condensation catalyst, a defoaming agent and hydrophobic fumed silica; wherein the content of the first and second substances,
the weight percentage of the polyacrylate siloxane is 5-30%; the weight percentage of the active diluent is 5 to 30 percent; the weight percentage of the cross-linking agent is 1-5%, and the weight percentage of the heat-conducting filler is 50-80%; the weight percentage of the photoinitiator is 0.5 to 5.0 percent; the weight percentage of the condensation catalyst is 0.01 percent to 1.0 percent; the weight percentage of the defoaming agent is 0.2-0.5%; the weight percentage of the hydrophobic fumed silica is 0.05-1.0%.
According to the invention, during the reaction of the UV humidifying dual-curing heat-conducting adhesive, the rapid curing and positioning are realized by using ultraviolet light, the subsequent operation of a production line is not influenced, and the problem that the shadow area can not be completely cured by using a single UV curing heat-conducting adhesive is avoided; the UV humidifying dual-curing heat-conducting adhesive takes the polyacrylate siloxane as main resin, can realize complete curing, and has excellent high-temperature resistance; meanwhile, the heat-conducting filler with a higher proportion is added in the formula, the problem of incomplete photocuring caused by excessive heat-conducting filler is solved through moisture curing by compounding the heat-conducting filler with a large particle size and adding the heat-conducting filler with a high specific surface area and a high heat conductivity, and the combination of UV (ultraviolet) moisture dual curing and high-temperature-resistant high-heat-conducting performance is realized.
Specifically, the polyacrylate siloxane may be present in an amount of 7%, 9%, 15%, 28%, or the like; the weight percentage of the reactive diluent may be 7%, 9%, 15%, or 28%, etc.; the weight percentage of the cross-linking agent may be 2%, 3%, or 4%, etc.; the weight percentage of the thermally conductive filler may be 60%, 65%, 70%, or 75%, etc.; the weight percentage of the photoinitiator may be 1%, 1.5%, 3%, or 4%, etc.; the weight percent of the condensation catalyst may be 0.02%, 0.5%, 0.7%, or 0.9%, etc.; the weight percentage of the defoamer can be 0.3%, 0.35%, 0.4%, or the like; the weight percentage of the hydrophobic fumed silica can be 0.06%, 0.08%, 0.6%, or 0.9%, and so forth.
As an example, the polyacrylate siloxane contains at least two acryloxy groups and at least one alkoxy group in one molecule at the same time.
Specifically, one molecule of the polyacrylate siloxane may simultaneously include two acryloxy groups and two alkoxy groups, which is not limited herein and may be selected according to specific needs.
By way of example, the polyacrylate siloxane has the structure of the formula:
wherein: r is epoxy-terminated epoxy organosilicon block copolymer, which comprises an organosilicon part and an epoxy part, R2 is-CH 3 or alkoxy of C1-C2, R3 is-CH 3 or alkoxy of C1-C2, k is an integer from 1 to 8, and j is an integer from 1 to 2;
the organosilicon moiety has the general structure:
wherein: r4 is C1-C12 methyl, alkoxy or phenyl, R5 is C1-C12 methyl, alkoxy or phenyl, and x is a natural number from 0 to 1000.
Specifically, the epoxy-terminated epoxy silicone block copolymer can include at least one of ALBIFLEX 246, ALBIFLEX 296, and ALBIFLEX 348.
By way of example, the epoxy moiety in the epoxy-terminated epoxy silicone block copolymer comprises one or more of bisphenol a glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol a glycidyl ether, and hydrogenated bisphenol F glycidyl ether; the organosilicon part in the epoxy-terminated epoxy organosilicon block copolymer comprises polysiloxane terminated by hydroxyl groups at two ends or polysiloxane terminated by amino groups at two ends; the epoxy equivalent of the epoxy-terminated epoxy organosilicon copolymer is 400-1500.
Further, the epoxy moiety in the epoxy-terminated epoxy silicone block copolymer in this example is preferably a bisphenol a epoxy resin. The epoxy-terminated epoxy silicone block copolymer silicone moiety is preferably a polydimethylsiloxane end-capped with amino groups at both ends.
Specifically, the epoxy equivalent of the epoxy-terminated epoxy silicone copolymer in the embodiment is preferably 600 to 1400; still further, the epoxy-terminated epoxy silicone copolymer can have an epoxy equivalent weight of 700, 800, 1000, 1200, or 1300, and so forth.
As an example, the reactive diluent includes a gurley 107 resin having a viscosity of 500cps to 5000 cps.
Specifically, the reactive diluent may include at least one of a birch 107 resin having a viscosity of 500cps, a birch 107 resin having a viscosity of 1000cps, a birch 107 resin having a viscosity of 1500cps, a birch 107 resin having a viscosity of 2000cps, a birch 107 resin having a viscosity of 3000cps, a birch 107 resin having a viscosity of 4000cps, and a birch 107 resin having a viscosity of 5000 cps. The reactive diluent is preferably a resin of Tripter 107 with a viscosity of 500cps, a resin of Tripter 107 with a viscosity of 1000cps, a resin of Tripter 107 with a viscosity of 1500cps, preferably O-FT05, O-F750, O-F1550 from New materials of orange, F-01A, J-15 of New materials of Jiangsu family.
Illustratively, the crosslinking agent includes at least one of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane; the heat conducting filler comprises at least one of spherical alumina, zinc oxide, boron nitride, aluminum nitride and silicon carbide with different particle sizes; the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexylphenyl ketone, benzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide; the condensation catalyst comprises at least one of dibutyltin dilaurate, tributyltin trilaurate, tin chloride, n-butyl titanate and stannous chloride; the defoaming agent comprises at least one of Pico chemistry BYK-088, BYK-A501, BYK-A506 and BYK-A535; the hydrophobic fumed silica comprises at least one of carbopol TS-720, watt H20, H13L and H15.
Referring to fig. 1, the present invention further provides a method for preparing a UV-wetting dual-curing thermal conductive adhesive, including:
s1: providing 5-30 parts by weight of polyacrylate siloxane, 5-30 parts by weight of reactive diluent, 1-5 parts by weight of cross-linking agent, 0.2-0.5 part by weight of defoaming agent and 0.5-5.0 parts by weight of photoinitiator, and carrying out first mixing and stirring to obtain a first mixture;
s2: adding 0.01-1.0 part of condensation catalyst into the first mixture for second mixing and stirring to obtain a second mixture;
s3: adding 50-80 parts of heat-conducting filler into the second mixture for third mixing and stirring to obtain a third mixture;
s4: adding 0.05-1.0 part of hydrophobic fumed silica into the third mixture, and carrying out fourth mixing and stirring to obtain a fourth mixture;
s5: and placing the fourth mixture in a preset vacuum degree environment for fifth mixing and stirring to obtain the UV humidifying dual-curing heat-conducting glue.
As an example, the speed of the first mixing and stirring is 800r/min to 1200r/min, and the time of the first mixing and stirring is 30 minutes to 40 minutes; the second mixing and stirring speed is 200 r/min-300 r/min, and the second mixing and stirring time is 10 minutes-15 minutes; the third mixing and stirring speed is 200 r/min-300 r/min, and the third mixing and stirring time is 10 minutes-15 minutes; the fourth mixing and stirring speed is 200 r/min-300 r/min, and the fourth mixing and stirring time is 10 minutes-15 minutes; the vacuum degree of the environment with the preset vacuum degree is-0.10 to-0.01 MPa; the fifth mixing and stirring speed is 200 r/min-300 r/min, and the fifth mixing and stirring time is 10 minutes-15 minutes.
Specifically, the speed of the first mixing and stirring can be 900r/min, 1000r/min or 1100r/min, etc., and the time of the first mixing and stirring can be 32 minutes, 35 minutes or 39 minutes, etc.; the speed of the second mixing stirring can be 230r/min, 260r/min or 280r/min and the like, and the time of the second mixing stirring can be 12 minutes, 13 minutes or 14 minutes and the like; the speed of the third mixing and stirring can be 230r/min, 260r/min or 280r/min and the like, and the time of the third mixing and stirring can be 12 minutes, 13 minutes or 14 minutes and the like; the speed of the fourth mixing and stirring can be 230r/min, 260r/min or 280r/min and the like, and the time of the fourth mixing and stirring can be 12 minutes, 13 minutes or 14 minutes and the like; the vacuum degree of the preset vacuum degree environment is-0.08 MPa, -0.06MPa, -0.05MPa, -0.03MPa and the like; the speed of the fifth mixing and stirring can be 230r/min, 260r/min or 280r/min, etc., and the time of the fifth mixing and stirring can be 12 minutes, 13 minutes or 14 minutes, etc.
Further, the vacuum degree of the preset vacuum degree environment in the step S5 is preferably-0.08 MPa.
As an example, the method of preparing the polyacrylate siloxane includes:
s1-1: preparing an epoxy-terminated epoxy silicone block copolymer solution;
s1-2: preparing a mixed solution of acrylic acid, a polymerization inhibitor and a catalyst I;
s1-3: adding the mixed solution into the epoxy-terminated epoxy organic silicon block copolymer solution to perform epoxy ring-opening addition reaction to obtain an acrylate polysilane compound;
s1-4: mixing the acrylate polysilane compound with isocyanate-containing silane and a catalyst II to obtain a composition;
s1-5: subjecting the composition to a hydroxyl addition reaction to obtain the polyacrylate siloxane.
As an example, the temperature of the epoxy ring-opening addition reaction is 70 ℃ to 150 ℃, and the time of the epoxy ring-opening addition reaction is 2 hours to 8 hours; the temperature of the hydroxyl addition reaction is 50-70 ℃, and the time of the epoxy ring-opening addition reaction is 3-8 hours.
Specifically, the temperature of the epoxy ring-opening addition reaction may be 80 ℃, 100 ℃, 120 ℃ or 140 ℃ or the like, and the time of the epoxy ring-opening addition reaction may be 3 hours, 5 hours or 7 hours or the like; the temperature of the hydroxyl group addition reaction may be 55 ℃, 60 ℃, or 65 ℃ or the like, and the time of the epoxy ring-opening addition reaction may be 4 hours, 5 hours, 6 hours, or 7 hours or the like.
Specifically, step S1-1 includes: under nitrogen, a quantity of the epoxy polysiloxane and solvent a (e.g., solvent a is a low polar or non-polar solvent, preferably carbon tetrachloride, toluene, xylene, or cyclohexane, most preferably toluene and xylene) are added to a dry Erlenmeyer flask equipped with magnetons and a serpentine condenser to provide the epoxy terminated epoxy silicone block copolymer solution.
Specifically, in step S2-2, the polymerization inhibitor includes at least one of hydroquinone, p-hydroxyanisole, benzoic acid, p-benzoquinone, and 2, 6-di-tert-butylphenol, and the polymerization inhibitor is preferably 2, 6-di-tert-butylphenol or p-hydroxyanisole. The polymerization inhibitor can prevent the ring-opening polymerization of the epoxy silane copolymer containing epoxy groups from forming gel.
The catalyst I comprises at least one of tetraethylammonium bromide, N-dimethylbenzylamine and triethylamine; the catalyst I is most preferably tetraethylammonium bromide.
In the mixed solution, the mass of the catalyst I is 0.02-1.1% of that of the epoxy terminated epoxy organosilicon block copolymer; the molar ratio of the acrylic acid to the epoxy terminated epoxy organosilicon block copolymer is 1: 1-1.4: 1, wherein the epoxy terminated epoxy organosilicon block copolymer is measured by the molar weight of epoxy groups contained in the epoxy terminated epoxy organosilicon block copolymer. The acrylic acid and the epoxy silicone block copolymer of the epoxy terminated epoxy are introduced to perform epoxy ring-opening addition to form ester, so that the acryloyl group is introduced, has photosensitivity and has the characteristic of rapid curing under ultraviolet irradiation.
Specifically, in the mixed solution, the mass of the catalyst I may be 0.02%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1.0%, or the like of the mass of the epoxy-terminated epoxy silicone block copolymer; the molar ratio of the acrylic acid to the epoxy silicone block copolymer of the epoxy terminated epoxy may be 1.1: 1, 1.2: 1, or 1.3: 1, and so forth.
In the mixed solution, the total amount of the solvent A is 10-50% of the mass of the epoxy-terminated epoxy organosilicon block copolymer, preferably 10-20%; the using amount of the polymerization inhibitor is 0.01-1.0% of the mass of the epoxy-terminated epoxy organosilicon block copolymer, and preferably 0.4-0.8%; the dosage of the catalyst is 0.02-1.4 percent of the mass of the epoxy-terminated epoxy organosilicon block copolymer, preferably 0.06-1.0 percent; the amount of the acrylic acid is related to the epoxy group content in the epoxy-terminated epoxy silicone block copolymer, the molecular weight and the viscosity of the epoxy-terminated epoxy silicone block copolymer are unrelated, and the addition amount molar ratio of the acrylic acid to the epoxy group in the epoxy-terminated epoxy silicone block copolymer is 1-1.4.
Specifically, in step S1-3, the epoxy-terminated epoxysilicone block copolymer solution is stirred at a constant speed within a temperature range of 80 ℃ to 120 ℃, the mixed solution (i.e., the mixed solution of the acrylic acid, the polymerization inhibitor and the catalyst I) is added dropwise into the epoxy-terminated epoxysilicone block copolymer solution by using a micro-injection pump, the epoxy-terminated epoxysilicone block copolymer solution and the mixed solution react for 2 to 8 hours within a temperature range of 80 ℃ to 120 ℃, then the solvent a and the low-boiling-point substances are distilled out, washed with absolute ethyl alcohol, and dried to obtain the acrylate polysilane compound.
Specifically, in step S1-4, the acrylate polysilane compound, the substance g (for example, the substance g contains one molecule of isocyanate and at least one molecule of alkoxy group, and at most 3 molecules of alkoxy group, and the alkoxy group is a common short-chain alkoxy group, such as methoxy, ethoxy, propoxy, etc.), the solvent a and the catalyst II are mixed uniformly to obtain the composition (i.e., the acrylate polysilane compound, the isocyanato-containing silane, the solvent a, the mixed solution of the catalyst II are ready to react); the mass ratio of the using amount of the catalyst II to the using amount of the acrylate polysilane compound is 0.02-1.0%, and preferably 0.04-0.8%; the amount of the substance g and the acrylate polysilane compound is 1.0-1.4, preferably 0.95-1.1, the molar ratio of the isocyanate (NC0) in the substance g to the reactive hydroxyl (OH) in the acrylate polysilane compound is n (NC0)/n (0H);
the catalyst II comprises at least one of dibutyltin dilaurate, tributyltin trilaurate, tin chloride, n-butyl titanate and stannous chloride, and the catalyst II is preferably dibutyltin dilaurate.
The isocyanate-containing silane comprises 1-3 alkoxy groups and an isocyanate group, specifically comprises isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane and the like, wherein the isocyanate group is mainly used as a group bonded with residual hydroxyl of an acrylate polysilane compound, and the alkoxy silicon group is introduced as a moisture-curing active group, so that the moisture-curing has the characteristic of deep curing.
Specifically, in step S-5, the composition (a mixed solution of the acrylate polysilane compound, the isocyanatosilane-containing silane, the solvent a, and the catalyst II) is reacted at 50 to 70 ℃ for 3 to 8 hours, the solvent is distilled off, washed with absolute ethanol, and dried under vacuum at 100 ℃ for 2 to 4 hours to obtain the polyacrylate siloxane.
Example two
The technical solution of the present invention will be clearly and completely described by the following detailed description.
Example 1
table-UV moisture dual-curing heat-conducting adhesive composition table
Example 2
Composition table of surface-II UV (ultraviolet) moisture dual-curing heat-conducting adhesive
Example 3
Composition table of surface three UV moisture dual-curing heat-conducting adhesive
Comparative example 4
Composition table of UV (ultraviolet) light-cured heat-conducting adhesive
Comparative example 5
| Raw materials | Dosage of |
| Aliphatic urethane acrylate | 30g |
| Acrylic acid isobornyl ester | 30g |
| Silane coupling agent KH560 | 3g |
| BYK-088 | 2g |
| Photoinitiator 1-hydroxy-cyclohexyl phenyl ketone | 6g |
| Spherical alumina with average particle diameter of 7.5um | 30g |
| Spherical alumina with average particle size of 20.36um | 110g |
| Hydrophobic fumed silica | 1.05g |
Table five UV light-curing adhesive composition table
Performance testing
Performance testing was performed on examples 1-3, comparative example 4, and comparative example 5, respectively
(1) Tensile shear strength test: the test was carried out according to GB/T7124-2008, the test substrates were 304 stainless steel and light-transmitting polycarbonate plastic, the curing conditions were a 365nm UV LED light source, an energy irradiation of 250mw/cm2 for 20s, and moisture curing was carried out at room temperature for three days
(2) And (3) testing the heat conductivity coefficient: testing according to ISO22007-2
(3) Curing for 3 days under the condition of avoiding light and pure moisture, and testing the tensile shear property
(4) And (3) testing high-temperature resistance: the dumbbell shape of the specified standard is manufactured according to GB/T13022-1991, the curing condition is a UV LED light source with the wavelength of 365nm, the energy irradiation is carried out for 20s at 250mw/cm2, and the dumbbell shape is moisture-cured for three days under the condition of room temperature. After the curing is completed, at least 5 standard samples are placed in a 150-DEG oven for 48H, and after the samples are taken out and cooled to room temperature, the elongation at break before and after aging is tested according to the GB/T13022-1991 plastic film tensile property test method.
Table six examples 1-3, comparative examples 4-5 specific test results
Examples 1-3 all had higher elongation at break, essentially maintained elongation at break after 150 degrees aging for 48H, and higher tensile shear strength for the stainless steel substrate. Example 2 is compared with example 1, with the same addition amount of heat conductive filler, but since spherical alumina phases with different particle sizes are arranged and distributed in an embedded manner with each other to form a denser heat conductive channel and boron nitride with higher heat conductivity and a lamellar structure with a large specific surface area is added, example 2 is significantly higher than example 1, and the monomolecular reaction functionality of example 2 is further improved compared with example 1, so that example 2 has higher crosslinking density, stronger tensile shear strength, but slightly lower elongation at break. Example 3 the addition amount of the heat conductive filler was further increased to a final thermal conductivity of 2.5W/m · k, the monomolecular reactive functional group of example 3 was further increased, the tensile shear strength was further increased, and the elongation at break was decreased to 170%. Comparative example 5 because spherical alumina addition is great, influences the absorption of glue to the ultraviolet light, and the curing degree reduces, and tensile shear strength is lower, moreover because can not moisture solidification lead to the curing depth not enough, can't make heat conduction test sample piece, coefficient of heat conductivity and elongation at break can't test. Comparative example 4 has higher tensile shear strength and higher elongation at break, but after aging at 150 ℃ for 48 hours, the colloid becomes hard, brittle and breaks, the elongation at break is zero, and the high temperature resistance is poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A UV-wetting dual-curing heat-conducting adhesive is characterized by comprising: polyacrylate siloxane, an active diluent, a crosslinking agent, a heat-conducting filler, a photoinitiator, a condensation catalyst, a defoaming agent and hydrophobic fumed silica; wherein the content of the first and second substances,
the weight percentage of the polyacrylate siloxane is 5-30%; the weight percentage of the active diluent is 5 to 30 percent; the weight percentage of the cross-linking agent is 1-5%, and the weight percentage of the heat-conducting filler is 50-80%; the weight percentage of the photoinitiator is 0.5 to 5.0 percent; the weight percentage of the condensation catalyst is 0.01 percent to 1.0 percent; the weight percentage of the defoaming agent is 0.2-0.5%; the weight percentage of the hydrophobic fumed silica is 0.05-1.0%.
2. The UV-wetting dual-curing heat-conducting adhesive according to claim 1, wherein: the polyacrylate siloxane contains at least two acryloxy groups and at least one alkoxy group in one molecule at the same time.
3. The UV-wetting dual-curing heat-conducting adhesive according to claim 1, wherein: the polyacrylate siloxane has the structure of the following general formula:
wherein: r is an epoxy terminated epoxy silicone block copolymer comprising a silicone moiety and an epoxy moiety, R2is-CH 3 or alkoxy of C1-C2, R3is-CH 3 or alkoxy of C1-C2, k is an integer from 1 to 8, j is an integer from 1 to 2;
the organosilicon moiety has the general structure:
wherein: r4Is a methyl, alkoxy or phenyl radical of C1-C12, R5Is a methyl, alkoxy or phenyl group of C1-C12, and x is a natural number from 0 to 1000.
4. The UV-wetting dual-curing heat-conducting adhesive according to claim 3, wherein: the epoxy part in the epoxy-terminated epoxy organosilicon block copolymer comprises one or more of bisphenol A glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol A glycidyl ether and hydrogenated bisphenol F glycidyl ether; the organosilicon part in the epoxy-terminated epoxy organosilicon block copolymer comprises polysiloxane terminated by hydroxyl groups at two ends or polysiloxane terminated by amino groups at two ends; the epoxy equivalent of the epoxy-terminated epoxy organosilicon copolymer is 400-1500.
5. The UV-wetting dual-curing heat-conducting adhesive according to claim 1, wherein: the reactive diluent comprises a Ticagrelor 107 resin having a viscosity of 500cps to 5000 cps.
6. The UV-wetting dual-curing heat-conducting adhesive according to claim 1, wherein: the cross-linking agent comprises at least one of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane and mercaptopropyltrimethoxysilane; the heat conducting filler comprises at least one of spherical alumina, zinc oxide, boron nitride, aluminum nitride and silicon carbide with different particle sizes; the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexylphenyl ketone, benzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide; the condensation catalyst comprises at least one of dibutyltin dilaurate, tributyltin trilaurate, tin chloride, n-butyl titanate and stannous chloride; the defoaming agent comprises at least one of Pico chemistry BYK-088, BYK-A501, BYK-A506 and BYK-A535; the hydrophobic fumed silica comprises at least one of carbopol TS-720, watt H20, H13L and H15.
7. A preparation method of a UV-humidified dual-curing heat-conducting adhesive is characterized by comprising the following steps:
providing 5-30 parts by weight of polyacrylate siloxane, 5-30 parts by weight of reactive diluent, 1-5 parts by weight of cross-linking agent, 0.2-0.5 part by weight of defoaming agent and 0.5-5.0 parts by weight of photoinitiator, and carrying out first mixing and stirring to obtain a first mixture;
adding 0.01-1.0 part of condensation catalyst into the first mixture for second mixing and stirring to obtain a second mixture;
adding 50-80 parts of heat-conducting filler into the second mixture for third mixing and stirring to obtain a third mixture;
adding 0.05-1.0 part of hydrophobic fumed silica into the third mixture, and carrying out fourth mixing and stirring to obtain a fourth mixture;
and placing the fourth mixture in a preset vacuum degree environment for fifth mixing and stirring to obtain the UV humidifying dual-curing heat-conducting glue.
8. The method for preparing the UV-wetting dual-curing heat-conducting adhesive according to claim 7, wherein: the first mixing and stirring speed is 800 r/min-1200 r/min, and the first mixing and stirring time is 30 minutes-40 minutes; the second mixing and stirring speed is 200 r/min-300 r/min, and the second mixing and stirring time is 10 minutes-15 minutes; the third mixing and stirring speed is 200 r/min-300 r/min, and the third mixing and stirring time is 10 minutes-15 minutes; the fourth mixing and stirring speed is 200 r/min-300 r/min, and the fourth mixing and stirring time is 10 minutes-15 minutes; the vacuum degree of the environment with the preset vacuum degree is-0.10 MPa to-0.01 MPa; the fifth mixing and stirring speed is 200 r/min-300 r/min, and the fifth mixing and stirring time is 10 minutes-15 minutes.
9. The method for preparing the UV-wetting dual-curing heat-conducting adhesive according to claim 7, wherein: the preparation method of the polyacrylate siloxane comprises the following steps:
preparing an epoxy-terminated epoxy silicone block copolymer solution;
preparing a mixed solution of acrylic acid, a polymerization inhibitor and a catalyst I;
adding the mixed solution into the epoxy-terminated epoxy organic silicon block copolymer solution to perform epoxy ring-opening addition reaction to obtain an acrylate polysilane compound;
mixing the acrylate polysilane compound with isocyanate-containing silane and a catalyst II to obtain a composition;
subjecting the composition to a hydroxyl addition reaction to obtain the polyacrylate siloxane.
10. The method for preparing the UV-wetting dual-curing heat-conducting adhesive according to claim 9, wherein: the temperature of the epoxy ring-opening addition reaction is 70-150 ℃, and the time of the epoxy ring-opening addition reaction is 2-8 hours; the temperature of the hydroxyl addition reaction is 50-70 ℃, and the time of the epoxy ring-opening addition reaction is 3-8 hours.
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| CN115505264A (en) * | 2022-08-12 | 2022-12-23 | 超聚变数字技术有限公司 | Paste-like thermal interface material, preparation method thereof and electronic equipment |
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