CN116875244B - 一种耐高温快固环氧胶粘剂及其制备方法 - Google Patents
一种耐高温快固环氧胶粘剂及其制备方法 Download PDFInfo
- Publication number
- CN116875244B CN116875244B CN202310874112.9A CN202310874112A CN116875244B CN 116875244 B CN116875244 B CN 116875244B CN 202310874112 A CN202310874112 A CN 202310874112A CN 116875244 B CN116875244 B CN 116875244B
- Authority
- CN
- China
- Prior art keywords
- temperature
- epoxy resin
- agent
- biphenyl
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 47
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 47
- RUIZXJNYLMYDLB-UHFFFAOYSA-N [P].C1=CC=CC=C1C1=CC=CC=C1 Chemical group [P].C1=CC=CC=C1C1=CC=CC=C1 RUIZXJNYLMYDLB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 60
- 150000002221 fluorine Chemical class 0.000 claims description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000000713 high-energy ball milling Methods 0.000 claims description 11
- 229920006295 polythiol Polymers 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 2
- 125000001153 fluoro group Chemical class F* 0.000 abstract 2
- 238000007711 solidification Methods 0.000 abstract 2
- 230000008023 solidification Effects 0.000 abstract 2
- 125000006267 biphenyl group Chemical group 0.000 description 9
- -1 thiol ions Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000007133 aluminothermic reaction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002743 phosphorus functional group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006258 conductive agent 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- 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
- C08G59/66—Mercaptans
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明提供一种耐高温快固环氧胶粘剂,按重量比计算:包括A组分:15‑25%的环氧树脂、12‑27%的改性含氟磷联苯环氧树脂、15‑35%的改性纳米粒子增韧剂、15‑25%的稀释剂及1‑1.5%的偶联剂;B组分:12‑15%的固化剂、30‑45%的无机填料、5‑7%的触变剂、35‑55%的导热剂、5‑10%的促进剂及5‑7%的增塑剂。本发明还提供该耐高温快固环氧胶粘剂的制备方法,包括步骤S100改性含氟磷联苯环氧树脂的制备;步骤S200制备A组分;步骤S300制备B组分;步骤S400共混A组分和B组分制备耐高温快固环氧胶粘剂。本发明制得的耐高温快固环氧胶粘剂韧性高、高导热系数、耐热(高Tg值)、室温可固化、固化时间及最大转化率时间短。
Description
技术领域
本发明涉及高分子材料技术领域,具体地,涉及一种耐高温快固环氧胶粘剂及其制备方法。
背景技术
环氧树脂是一种先进复合材料树脂基体,其性能优异,尤其表现在耐磨性、机械性、粘接性、化学稳定性、电绝缘性以及对基材的黏附性等方面,但环氧树脂交联固化后形成立体网状结构,交联密度增大,内应力提高,出现固化物硬脆、韧性差易开裂。同时,对用于新能源汽车及半导体封装的环氧树脂材料,对环氧树脂的速固性、低应力和耐热性也有更高的性能要求。
发明内容
为解决现有技术中环氧树脂韧性差、固化温度高、耐热性有待提高的技术问题,本发明提供一种耐高温快固环氧胶粘剂及其制备方法。
第一方面,本发明提供一种耐高温快固环氧胶粘剂,按重量比计算:包括A组分:15-25%的环氧树脂、12-27%的改性含氟磷联苯环氧树脂、15-35%的改性纳米粒子增韧剂、15-25%的稀释剂、1-1.5%的偶联剂;B组分:12-15%的固化剂、30-45%的无机填料、5-7%的触变剂、35-55%的导热剂、5-10%的促进剂、5-7%的增塑剂;
所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、邻苯二甲酸二缩水甘油酯中的至少一种;
所述改性含氟磷联苯环氧树脂通过六氟丙酮和苯膦酰二氯与联苯反应制得含氟磷联苯预聚体,含氟磷联苯预聚体再与环氧氯丙烷开环聚合制得。
所述改性含氟磷联苯环氧树脂的结构式为:
(其中R1、R2、R3、R4为碳原子1-6的烷基或烯基);
所述改性纳米粒子增韧剂为55-250nm粒径的铝粉和SiO2,其中铝粉和SiO2的比例为(2-5):1;
所述稀释剂为辛基缩水甘油醚、缩水甘油醚中的至少一种;
所述偶联剂为硅烷或酞酸酯中的至少一种;
所述固化剂为聚硫醇、聚醚胺、咪唑的共混有机溶液,按重量分数计算,比例为(0.5-1.5):(0.5-1):1;
所述无机填料为包覆有三氧化铁粉体、氧化铜粉体、氧化镁粉体至少一种粉体的高岭土或碳酸钙,所述三氧化铁粉体、氧化铜粉体、氧化镁粉体中的至少一种在在高岭土或碳酸钙的质量占比为25-55%;
在B组分中所述三氧化铁粉体、氧化铜粉体、氧化镁粉体通过高能球磨制得粉径为250-600nm的粉体,在混合A组分和B组分时,固化体系释放的能量可激发A组分中的nm级铝粉与B组分中nm级的所述三氧化铁粉体、氧化铜粉体、氧化镁粉体发生铝热反应,室温条件释放能量,促进反应进程,并激发需较高固化温度的固化剂咪唑参与反应,进一步加快固速度。
所述触变剂为气相二氧化硅。
所述导热剂为球状氮化硼、氮化铝、氮化硅中的至少一种,通过高能球磨制得粒径为150nm-550nm的所述导热剂。
所述导热剂采用nm级尺寸的球形导热材料,具有相较于片状更高的导热系数,同时采用的氮化硼、氮化铝、氮化硅导热系数高于碳基材料及部分金属粉体。
所述促进剂为有机胺固化促进剂或咪唑固化促进剂,所述有机胺固化促进剂为三-(二甲氨基甲基)苯酚、1,8-二氮杂环[5,4,0]十一碳-7-烯、三乙胺中至少一种;所述咪唑固化促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的至少一种。
咪唑不仅可以作为环氧体系的固化剂,因其高反应活性,还常被用作固化促进剂,具有用量少、毒性低、固化活性高等特点,固化产物耐化学腐蚀、耐热、电绝缘且机械性能优越。
所述增塑剂为含能增塑剂,优选的,所述增塑剂为(2,2-二硝基丙基)-2-己基癸酸酯硝基类含能增塑剂,该分子结构中既有链节较长的烷基可提供良好的分子柔顺性和低的玻璃化转变温度,又有硝基含能特性。在A组分与B组分共混固化过程中,所述增塑剂既起到增塑作用,同时硝基含能特性可产生高能热量促进反应进程,并激发需较高固化温度的固化剂咪唑参与反应,进一步加快固速度。
第二方面,本发明提供一种耐高温快固环氧胶粘剂的制备方法:
S100:改性含氟磷联苯环氧树脂的制备:
1)按摩尔比为1:2称取联苯与六氟丙酮,在催化剂氯化铝的催化下进行取代反应,充分反应30-60min,丙酮有机溶液洗涤,烘干,将产物与苯膦酰二氯按摩尔比为(2-2.5):1的比例共混溶解,在催化剂氯化亚铜、铂盐及Et3N的催化下,制得含氟磷联苯预聚体;
2)将制得的含氟磷联苯预聚体酸化,含氟磷联苯预聚体与环氧氯丙烷按摩尔比为(0.5-1):1的比例称取,加入环氧氯丙烷开环聚合,充分反应1-3小时,有机溶液洗涤,过滤,烘干,制得所述改性含氟磷联苯环氧树脂;
S200:制备A组分:
按重量份数计算,称取15-25%的环氧树脂、12-27%的改性含氟磷联苯环氧树脂、15-35%的改性纳米粒子增韧剂、15-25%的稀释剂、1-1.5%的偶联剂,将所述环氧树脂与所述改性含氟磷联苯环氧树脂共混熔融,超声波分散30-45min,充分搅拌,加入已由所述偶联剂进行表面改性的改性纳米粒子增韧剂,充分搅拌后加入所述稀释剂,制得A组分;
S300:制备B组分:
按重量份数计算,称取12-15%的固化剂、30-45%的无机填料、5-7%的触变剂、35-55%的导热剂、5-10%的促进剂、5-7%的增塑剂,将所述无机填料及导热剂分别进行初次高能球磨,球磨2-5小时,球磨比10:1,将高能球磨制得的所述无机填料及导热剂二次高能球磨1-2小时,球磨比10:1,加入所述固化剂、触变剂、促进剂及增塑剂,超声波分散30-45min,制得B组分;
S400:制备耐高温快固环氧胶粘剂:
将制得的A组分和B组分按(0.8-1.5):1的质量比共混,超声波分散,固化温度为25-150℃,升温速率为5-20℃/min。
本发明取得的有益效果有:
1)改性含氟磷联苯环氧树脂中引入了刚性的联苯基团,抑制了分子链的旋转,进而提高整体系的耐热性能,随着改性含氟磷联苯环氧树脂的加入量递增,刚性的联苯基团在整体系的质量占比随之递增,进而增加了玻璃转化温度,提升了体系的耐热性能;
2)氟元素具有最大的电负性,电子与核之间的作用力大,与其他原子间化学键的键能大,含氟聚合物的耐热性更高,改性含氟磷联苯环氧树脂中引入氟元素,增强了环氧树脂体系的耐热性能,同时氟元素还提高了环氧胶粘剂的疏水性能,使得环氧胶粘剂具备低吸湿率;
3)联苯基团与六氟丙酮进行取代反应,六氟丙酮在联苯的取代点对称度高,增强了改性含氟磷联苯环氧树脂体系的对称度,增强了体系的耐热性能;
4)改性纳米铝粉与无机填料中的氧化物发生铝热反应,升温过程激发铝热反应,瞬间释放能量,激发了咪唑剧烈的中温固化进程,有利于在体系的黏度流动性降低时,促进反应进程,缩短固化时间及最大转化率时间;
5)在A组分与B组分共混固化过程中,所述增塑剂既起到增塑作用,同时硝基含能特性可产生高能热量促进反应进程,并激发需较高固化温度的固化剂咪唑参与反应,进一步加快固速度;
6)将含磷基团的苯膦酰二氯与联苯聚合,自组装引入含磷基团,通过调控反应苯膦酰二氯投料,控制P元素在环氧胶粘剂中的质量比重,进而根据不同的应用场景调配出含本位阻燃的环氧胶粘剂,减少阻燃无机粒子投料影响环氧胶粘剂的黏度及出胶;
7)调配固化剂为聚硫醇、聚醚胺、咪唑的共混有机溶液,重量分数比例为(0.5-1.5):(0.5-1):1,通过聚醚胺作为固化促进剂,聚硫醇的巯基可形成巯基离子,反应速率迅速提高,同时咪唑作为中温固化剂,可实现在室温条件下,通过聚硫醇固化放热及铝热反应放热,提供反应活化能,激发咪唑中温固化,缩短固化时间及最大转化率时间。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本实施例中一种耐高温快固环氧胶粘剂的制备方法的流程图;
图2为本实施例中一种耐高温快固环氧胶粘剂的拉伸断面SEM图。
具体实施方式
为了能够更清楚地理解本发明的上述目的、特征和优点,下面结合附图和实施例对本发明做进一步说明。需要说明的是,在不冲突的情况下,本申请的实施例及实施例中的特征可以相互组合。
下面结合附图和具体实施例对本发明作进一步说明。
如图1,为一种耐高温快固环氧胶粘剂的制备方法的流程图。
实施例1:提供一种耐高温快固环氧胶粘剂的制备方法:
S100:改性含氟磷联苯环氧树脂的制备:
1)按摩尔比为1:2称取联苯与六氟丙酮,在催化剂氯化铝的催化下进行反应,充分反应30-60min,采用丙酮有机溶液重复洗涤三次,烘干,将产物与苯膦酰二氯按摩尔比为2:1的比例共混溶解,在催化剂氯化亚铜、铂盐及Et3N的催化下,制得含氟磷联苯预聚体;
2)将制得的含氟磷联苯预聚体酸化,含氟磷联苯预聚体与环氧氯丙烷按摩尔比为0.5:1的比例称取,加入环氧氯丙烷开环聚合,充分反应3小时,有机丙酮溶液重复洗涤三次,过滤,烘干,制得改性含氟磷联苯环氧树脂;
S200:制备A组分:
按重量份数计算,称取25%的双酚A型环氧树脂、25%步骤S100制得的改性含氟磷联苯环氧树脂、30%的铝粉和SiO2(其中铝粉和SiO2的比例为2:1)、18.5%的辛基缩水甘油醚、1.5%的酞酸酯,将双酚A型环氧树脂与改性含氟磷联苯环氧树脂共混熔融,超声波分散30min,充分搅拌,加入已由酞酸酯进行表面改性的铝粉和SiO2,充分搅拌30min后加入所述辛基缩水甘油醚,低压脱泡,制得A组分;
S300:制备B组分:
按重量份数计算,称取15%的聚硫醇、聚醚胺、咪唑的共混有机溶液(按重量分数计算,比例为0.5:0.5:1)、30%的填充有三氧化铁粉体的高岭土、5%的气相二氧化硅、40%的球状氮化硼、5%的2-甲基咪唑、5%的(2,2-二硝基丙基)-2-己基癸酸酯,将三氧化铁及球状氮化硼分别进行初次高能球磨,球磨5小时,球磨比10:1,将高能球磨制得的三氧化铁及球状氮化硼二次高能球磨2小时,球磨比10:1,将制得的三氧化铁粉体与高岭土共混形成无机填料,加入聚硫醇、聚醚胺、咪唑的共混有机溶液、气相二氧化硅、2-甲基咪唑及(2,2-二硝基丙基)-2-己基癸酸酯,超声波分散30-45min,制得B组分;
S400:制备耐高温快固环氧胶粘剂:
将制得的A组分和B组分按1:1的质量比共混,超声波分散,脱泡,固化温度为25℃,升温速率为5℃/min。
如图2,左图a为实施例制得的耐高温快固环氧胶粘剂的拉伸断面SEM图,在左图a中可以看出,该环氧胶粘剂并未出现引入纳米无机颗粒铝粉和SiO2导致颗粒团聚,进而出现韧窝,断截面也未出现典型的环氧树脂脆性断面形貌;右图b为脊区域的高倍放大图,从图中可以看出,出现塑性形变,表明拉伸时基体产生塑性形变吸收大量能量,有利于提高该环氧胶粘剂的拉伸性能。同时,从图2可以看出,引入联苯基团,与双酚A型环氧树脂相比,韧性有明显的提高。
实施例2:热学性能测试
1)DSC和DMA测试耐高温快固环氧胶粘剂的Tg值:
在实施例1中,将A组分中仅包括双酚A型环氧树脂作为对照组R1(不包含改性含氟磷联苯环氧树脂),设置含12%、20%、27%的改性含氟磷联苯环氧树脂为实验组R2、R3、R4,其他反应条件及组分保持一致,由DSC和DMA(动态力学分析仪DMA测试固化物的损耗角正tanδ,tanδ处对应的温度为玻璃化转变温度)测试耐高温快固环氧胶粘剂的Tg值,结果如表1:
表1
由表1可知,实验组中加入改性含氟磷联苯环氧树脂的玻璃转化温度均高于对照组中不加入改性含氟磷联苯环氧树脂的玻璃转化温度,原因有:1)改性含氟磷联苯环氧树脂中引入了刚性的联苯基团,抑制了分子链的旋转,进而提高整体系的耐热性能,随着改性含氟磷联苯环氧树脂的加入量递增,刚性的联苯基团在整体系的质量占比随之递增,进而增加了玻璃转化温度,提升了体系的耐热性能;2)氟元素具有最大的电负性,电子与核之间的作用力大,与其他原子间化学键的键能大,含氟聚合物的耐热性更高,改性含氟磷联苯环氧树脂中引入氟元素,增强了环氧树脂体系的耐热性能;3)联苯基团与六氟丙酮进行取代反应,六氟丙酮在联苯的取代点对称度高,增强了改性含氟磷联苯环氧树脂体系的对称度,增强了体系的耐热性能。
2)测试不同固化剂配比对耐高温快固环氧胶粘剂固化时间及力学性能的影响:
将实施例1中固化剂聚硫醇、聚醚胺、咪唑的共混有机溶液重量分数比例调整为0.5:0.5:1、1:0.5:1、1.5:0.5:1、0.5:1:1作为实验组R1、R2、R3、R4,测试不同固化剂配比对耐高温快固环氧胶粘剂固化时间及力学性能的影响,结果如表2:
表2
由表2可知,在室温条件下,随着聚硫醇在固化剂中的比例增加,适用中温固化的咪唑比例下降,固化时间变长,这主要是由于固化进程,体系的黏度流动性降低,已固化的环氧胶会抑制固化反应速率,同时引入刚性的联苯基团,抑制了分子链的旋转,进而提高整体系的耐热性能,固化时间变长;而中温固化的咪唑比例上升,在反应体系放热升温过程,由于改性纳米铝粉与无机填料中的氧化物发生铝热反应,升温过程激发铝热反应,瞬间释放能量,激发了咪唑剧烈的中温固化进程,有利于在体系的黏度流动性降低时,促进反应进程,缩短固化时间及最大转化率时间;
同时,从R3与R4的数据可以看出,聚硫醇固化物的有效交联密度较低,力学性能剪切强度也相对较差,采用聚醚胺固化剂来调节其固化速率和增加其交联密度,室温时硫醇单独与环氧树脂反应的活性较低,但有聚醚胺作为固化促进剂,巯基可形成巯基离子,反应速率迅速提高。
本实施例制得的耐高温快固环氧胶粘剂具有Tg值高、室温可固化且通过引入联苯基团和改性纳米无机粒子实现增韧。
通过上面具体实施方式,技术领域的技术人员可容易的实现本发明。但是应当理解,本发明并不限于上述的具体实施方式。在公开的实施方式的基础上,技术领域的技术人员可任意组合不同的技术特征,从而实现不同的技术方案。
Claims (6)
1.一种耐高温快固环氧胶粘剂的制备方法,其特征在于:
S100:改性含氟磷联苯环氧树脂的制备:
1)按摩尔比为1:2称取联苯与六氟丙酮,在催化剂氯化铝的催化下进行取代反应,充分反应30-60min,丙酮有机溶液洗涤,烘干,将产物与苯膦酰二氯按摩尔比为(2-2.5):1的比例共混溶解,在催化剂氯化亚铜、铂盐及Et3N的催化下,制得含氟磷联苯预聚体;
2)将制得的含氟磷联苯预聚体酸化,含氟磷联苯预聚体与环氧氯丙烷按摩尔比为(0.5-1):1的比例称取,加入所述环氧氯丙烷开环聚合,充分反应1-3小时,有机溶液洗涤,过滤,烘干,制得所述改性含氟磷联苯环氧树脂;
S200:制备A组分:
按重量份数计算,称取15-25%的环氧树脂、12-27%步骤S100制得的改性含氟磷联苯环氧树脂、15-35%的改性纳米粒子增韧剂、15-25%的稀释剂、1-1.5%的偶联剂,将所述环氧树脂与所述改性含氟磷联苯环氧树脂共混熔融,超声波分散30-45min,充分搅拌,加入已由所述偶联剂进行表面改性的改性纳米粒子增韧剂,充分搅拌后加入所述稀释剂,制得A组分;
S300:制备B组分:
按重量百分数数计算,称取12-15%的固化剂、30-45%的无机填料、5-7%的触变剂、35-55%的导热剂、5-10%的促进剂、5-7%的增塑剂,将所述无机填料及导热剂分别进行初次高能球磨,球磨2-5小时,球磨比10:1,将高能球磨制得的所述无机填料及导热剂二次高能球磨1-2小时,球磨比10:1,加入所述固化剂、触变剂、促进剂及增塑剂,超声波分散30-45min,制得B组分;
S400:制备耐高温快固环氧胶粘剂:
将制得的A组分和B组分按(0.8-1.5):1的质量比共混,超声波分散,固化温度为25-150℃,升温速率为5-20℃/min,制得所述耐高温快固环氧胶粘剂;
其中,所述固化剂为聚硫醇、聚醚胺、咪唑的共混有机溶液,按重量分数计算,比例分别为(0.5-1.5):(0.5-1):1;
所述改性纳米粒子增韧剂为55-250nm粒径的铝粉和SiO2,其中铝粉和SiO2的比例为(2-5):1;
所述增塑剂为(2,2-二硝基丙基)-2-己基癸酸酯硝基类含能增塑剂。
2.如权利要求1所述耐高温快固环氧胶粘剂的制备方法,其特征在于:所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、邻苯二甲酸二缩水甘油酯中的至少一种。
3.如权利要求1所述耐高温快固环氧胶粘剂的制备方法,其特征在于:所述无机填料为包覆有三氧化铁粉体、氧化铜粉体、氧化镁粉体至少一种粉体的高岭土或碳酸钙,所述三氧化铁粉体、氧化铜粉体、氧化镁粉体中的至少一种在所述高岭土或所述碳酸钙中的质量占比为25-55%。
4.如权利要求1所述耐高温快固环氧胶粘剂的制备方法,其特征在于:所述导热剂为球状氮化硼、氮化铝、氮化硅中的至少一种,所述导热剂粒径为150nm-550nm。
5.如权利要求1所述耐高温快固环氧胶粘剂的制备方法,其特征在于:所述促进剂为有机胺固化促进剂或咪唑固化促进剂;所述有机胺固化促进剂为三-(二甲氨基甲基)苯酚、1,8-二氮杂环[5,4,0]十一碳-7-烯、三乙胺中至少一种;所述咪唑固化促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑中的至少一种。
6.如权利要求1-5任意一项所述耐高温快固环氧胶粘剂的制备方法制备得到的耐高温快固环氧胶粘剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310874112.9A CN116875244B (zh) | 2023-07-17 | 2023-07-17 | 一种耐高温快固环氧胶粘剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310874112.9A CN116875244B (zh) | 2023-07-17 | 2023-07-17 | 一种耐高温快固环氧胶粘剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116875244A CN116875244A (zh) | 2023-10-13 |
CN116875244B true CN116875244B (zh) | 2024-02-09 |
Family
ID=88258315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310874112.9A Active CN116875244B (zh) | 2023-07-17 | 2023-07-17 | 一种耐高温快固环氧胶粘剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116875244B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20130094970A (ko) * | 2012-02-17 | 2013-08-27 | 인하대학교 산학협력단 | 초고내열성 에폭시 수지 조성물 |
CN111087762A (zh) * | 2020-01-02 | 2020-05-01 | 广东盈骅新材料科技有限公司 | 含氟环氧树脂复合材料及其应用 |
CN113292852A (zh) * | 2021-06-07 | 2021-08-24 | 珠海宏昌电子材料有限公司 | 含磷苯双酚聚合物的树脂组合物及其制备方法和应用 |
CN115418187A (zh) * | 2022-08-30 | 2022-12-02 | 海程新材料(芜湖)有限公司 | 一种双组分动力电池用高导热环氧结构胶及其制备方法 |
-
2023
- 2023-07-17 CN CN202310874112.9A patent/CN116875244B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20130094970A (ko) * | 2012-02-17 | 2013-08-27 | 인하대학교 산학협력단 | 초고내열성 에폭시 수지 조성물 |
CN111087762A (zh) * | 2020-01-02 | 2020-05-01 | 广东盈骅新材料科技有限公司 | 含氟环氧树脂复合材料及其应用 |
CN113292852A (zh) * | 2021-06-07 | 2021-08-24 | 珠海宏昌电子材料有限公司 | 含磷苯双酚聚合物的树脂组合物及其制备方法和应用 |
CN115418187A (zh) * | 2022-08-30 | 2022-12-02 | 海程新材料(芜湖)有限公司 | 一种双组分动力电池用高导热环氧结构胶及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN116875244A (zh) | 2023-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1260551B1 (en) | Flame-retardant epoxy resin composition and laminate made with the same | |
JP3092103B2 (ja) | 熱硬化性成分及び熱可塑性成分を含む成形組成物の製造方法 | |
JP2016204626A (ja) | 組成物、エポキシ樹脂硬化剤、エポキシ樹脂組成物、熱硬化性組成物、硬化物、半導体装置、および層間絶縁材料 | |
CN114634785A (zh) | 一种高导热覆铜铝基板用石墨烯复合胶液及其制备方法 | |
KR20190075217A (ko) | 고내열 속경화 에폭시 수지 조성물 및 이를 포함하는 프리프레그 | |
JP2009114325A (ja) | 封止用エポキシ樹脂成形材料及び半導体装置 | |
JP2003055435A (ja) | 電気絶縁用樹脂組成物、電子材料用絶縁材料およびその製造方法 | |
JP2003041123A (ja) | 熱硬化性樹脂組成物、その製造方法及び懸濁液状混合物 | |
CN116875244B (zh) | 一种耐高温快固环氧胶粘剂及其制备方法 | |
CN115651579B (zh) | 一种可快速固化的环氧胶及其制备方法 | |
WO2002100951A1 (fr) | Composition de resine thermodurcissable | |
JP4114048B2 (ja) | エポキシ樹脂組成物及びその製法 | |
JPH06136093A (ja) | エポキシ樹脂組成物 | |
JP7404127B2 (ja) | エポキシ樹脂組成物 | |
JPS6326128B2 (zh) | ||
JP3151826B2 (ja) | 電子部品封止用エポキシ樹脂成形材料 | |
JPS60115622A (ja) | エポキシ樹脂系組成物 | |
JP3807188B2 (ja) | エポキシ樹脂と無機成分の複合体及びその製造方法 | |
JP2019194345A (ja) | プリント配線板用樹脂組成物、プリプレグ、金属張積層板およびプリント配線板 | |
JPS6315846A (ja) | カーボン繊維含浸用熱硬化性樹脂組成物 | |
JP3543853B2 (ja) | エポキシ樹脂硬化促進剤および硬化エポキシ樹脂の製造方法 | |
JP3247368B2 (ja) | 電子部品封止用エポキシ樹脂成形材料 | |
JP7182370B2 (ja) | 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料及び成形体 | |
JP3205915B2 (ja) | 含金属エポキシ樹脂組成物およびその製造方法 | |
CN115725055A (zh) | 环氧树脂组合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |