CN107337900B - A kind of composition epoxy resin and its preparation method and application - Google Patents
A kind of composition epoxy resin and its preparation method and application Download PDFInfo
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- CN107337900B CN107337900B CN201611206445.0A CN201611206445A CN107337900B CN 107337900 B CN107337900 B CN 107337900B CN 201611206445 A CN201611206445 A CN 201611206445A CN 107337900 B CN107337900 B CN 107337900B
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 155
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 155
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 77
- -1 promotor Substances 0.000 claims abstract description 60
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 32
- 239000011256 inorganic filler Substances 0.000 claims abstract description 26
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 26
- 239000003086 colorant Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 18
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 17
- 239000001993 wax Substances 0.000 claims description 17
- 229940126062 Compound A Drugs 0.000 claims description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 150000004693 imidazolium salts Chemical class 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- HZEOUPCNUWSUFL-UHFFFAOYSA-N 4,5,5-trimethyl-4-pentan-3-yl-1H-imidazole Chemical class C(C)C(C1(N=CNC1(C)C)C)CC HZEOUPCNUWSUFL-UHFFFAOYSA-N 0.000 claims description 4
- PIDFOSKVJNSMDO-UHFFFAOYSA-N C(C)C(COP(=O)(OCC(CCCC)CC)O)CCCC.CC(CCC)P(CCCC)CCCC Chemical compound C(C)C(COP(=O)(OCC(CCCC)CC)O)CCCC.CC(CCC)P(CCCC)CCCC PIDFOSKVJNSMDO-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920002050 silicone resin Polymers 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- SKODXSIPSBUETK-UHFFFAOYSA-N P.P(O)(O)(=S)S Chemical compound P.P(O)(O)(=S)S SKODXSIPSBUETK-UHFFFAOYSA-N 0.000 claims 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 2
- UZPWKTCMUADILM-UHFFFAOYSA-N 3-methylcyclohexene Chemical compound CC1CCCC=C1 UZPWKTCMUADILM-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 239000010426 asphalt Substances 0.000 claims 1
- 238000004040 coloring Methods 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 238000010309 melting process Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 19
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 15
- 230000035882 stress Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 2
- RXPFLKNOPWWRFL-UHFFFAOYSA-N P(=O)(OC)(OC)O.CC(CCC)P(CCCC)CCCC Chemical compound P(=O)(OC)(OC)O.CC(CCC)P(CCCC)CCCC RXPFLKNOPWWRFL-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- HQWDILUMZXPFNW-UHFFFAOYSA-N 2-cyano-2-nitroacetamide Chemical compound NC(=O)C(C#N)[N+]([O-])=O HQWDILUMZXPFNW-UHFFFAOYSA-N 0.000 description 1
- MAQIPNRKAZZHBJ-UHFFFAOYSA-N 2-ethyl-5-methylhexanoic acid Chemical compound CCC(C(O)=O)CCC(C)C MAQIPNRKAZZHBJ-UHFFFAOYSA-N 0.000 description 1
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- LEKYFHLNAFECMX-UHFFFAOYSA-N phosphanium dimethyl phosphate Chemical compound [PH4+].COP([O-])(=O)OC LEKYFHLNAFECMX-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to LED support encapsulating material fields, disclose a kind of composition epoxy resin and its preparation method and application, it is characterized in that, the composition epoxy resin includes epoxy resin, curing agent, promotor, inorganic filler, colorant, stress modifying agent and release agent；The epoxy resin has the structure as shown in formula (1)；Wherein, n 1-10, R1For the linear or branched alkyl group of H or C1-C5, the straight chained alkyl of preferably H or C1-C3, further preferably H or methyl；R2For H orR ' is the linear or branched alkyl group of H or C1-C6, and preferably R ' is the straight chained alkyl of H or C1-C4, and further preferred R ' is methyl or ethyl.The composition epoxy resin continuously shaped property with higher and reflectivity.
Description
Technical field
The present invention relates to LED support encapsulating material fields, and in particular, to a kind of composition epoxy resin and its preparation side
Method and application.
Background technique
In recent years, the features such as LED industry undergoes an unusual development rapidly, and LED lamp bead is with its luminous efficiency high, energy conservation and environmental protection obtains
The favor of ordinary consumer, and have the tendency that replacing traditional lighting industry completely greatly.But as the power of LED chip constantly mentions
It rises, the requirement for the high temperature resistant of auxiliary material such as bracket, packaging plastic etc., resistance to ultraviolet ability and reliability is also constantly promoted.It passes
The heat-resisting material of system such as PPA, PCT etc. are used for a long time at high temperature, it may appear that serious xanthochromia problem.Simultaneously because at present
The organic silicon packaging glue of mainstream is low for the surface bonding force of the thermoplastics such as PPA, causes the air-tightness of lamp bead insufficient, seriously
Influence the lamp bead service life.Epoxy resin is mixed with curing agent, filler and all kinds of modifying agent as the common resin material of electronic device
Composition after conjunction, have the characteristics that color inhibition, curing rate fast, forming, it is at low cost, be suitable for large-scale production, be novel
The focus on research direction of LED support material.
The related patents that the country has disclosed at present, such as the patent (Authorization Notice No. of Hitachi Chemical Co., Ltd.
CN101461070B being proposed in) using fulminuric acid three-glycidyl amine (TGIC) is basic resin, and is solid with acid anhydrides
Agent, the resulting composition epoxy resin of mixture of white pigment.But the solidification intensity of this resin combination is low, poor toughness, adds
Epoxy resin small molecule presence, it is poor in turn result in continuously shaped property without easy mold release for easily pollution mold when making its molding
(less than 100 moulds) are not suitable with current LED support packing forms.
Summary of the invention
The purpose of the present invention is overcome the composition epoxy resin company in the prior art applied to LED support encapsulating material
The defect of continuous insufficient formability provides a kind of composition epoxy resin and its preparation method and application.
To achieve the goals above, the present invention provides a kind of composition epoxy resin, wherein the composition epoxy resin
Including epoxy resin, curing agent, promotor, inorganic filler, colorant, stress modifying agent and release agent；The epoxy resin tool
Just like structure shown in formula (1)；
Wherein, n 1-10, R1For the linear or branched alkyl group of H or C1-C5, the straight chained alkyl of preferably H or C1-C3, into
One step is preferably H or methyl；R2For H orR ' is the linear or branched alkyl group of H or C1-C6, and preferably R ' is H
Or the straight chained alkyl of C1-C4, further preferred R ' are methyl or ethyl.
The present invention also provides a kind of preparation methods of composition epoxy resin, wherein the preparation method includes: (1) system
Standby epoxy resin；(2) by the epoxy resin and curing agent, promotor, inorganic filler, colorant, stress modifying agent and demoulding
Agent is kneaded；Wherein, prepare epoxy resin the following steps are included:
A. formula (2) compound represented is reacted with compound A；
B. the reaction product of step a is reacted with formula (3) compound represented；
Wherein, compound A is water or R4COOH, R3For the linear or branched alkyl group of H or C1-C5, preferably H or C1-C3's
Straight chained alkyl, further preferably H or methyl；R4For the linear or branched alkyl group of H or C1-C6, preferably H or C1-C4's is straight
Alkyl group, preferably methyl or ethyl.
The present invention also provides the composition epoxy resins prepared by preparation method of the present invention.
Application the present invention also provides composition epoxy resin of the present invention as LED support encapsulating material.
Modified epoxy in composition epoxy resin of the present invention is compared with isocyanuric acid three-glycidyl ester (TGIC)
Itself there is biggish molecular weight, and softening point with higher and viscosity, to improve the continuous of composition epoxy resin
Mouldability (continuously shaped number is greater than 200), and there is high reflectivity.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of composition epoxy resins, wherein the composition epoxy resin includes epoxy resin, consolidates
Agent, promotor, inorganic filler, colorant, stress modifying agent and release agent；The epoxy resin has as shown in formula (1)
Structure；
Wherein, n 1-10, R1For the linear or branched alkyl group of H or C1-C5, the straight chained alkyl of preferably H or C1-C3, into
One step is preferably H or methyl；R2For H orR ' is the linear or branched alkyl group of H or C1-C6, and preferably R ' is H
Or the straight chained alkyl of C1-C4, further preferred R ' are methyl or ethyl.
In the present invention, the C1-C5Linear or branched alkyl group specific example include but is not limited to: methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl or neopentyl.
In the present invention, the C1-C6Linear or branched alkyl group specific example include but is not limited to: methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl or different
Hexyl.
Epoxy resin of the present invention for example can be any one in table 1, but the selection being not limited in table 1.
Table 1
| Structure | n | R1 | R2 |
| Epoxy resin 1 | 10 | Methyl | H |
| Epoxy resin 2 | 8 | Methyl | CH3-CO- |
| Epoxy resin 3 | 9 | H | H |
| Epoxy resin 4 | 7 | Ethyl | H |
| Epoxy resin 5 | 5 | Methyl | C2H5-CO- |
| Epoxy resin 6 | 6 | Tert-butyl | CH3-CO- |
| Epoxy resin 7 | 3 | Isopentyl | C3H7-CO- |
In the present invention, modified TGIC epoxy resin has biggish molecular weight relative to TGIC itself, to make institute
State epoxy resin softening point with higher and viscosity.The softening point of the epoxy resin is 30-120 DEG C, preferably 50-110
DEG C, more preferably 60-100 DEG C；Viscosity at 150 DEG C is 10-5000cp, preferably 120-4500cp, more preferably 1000-
4000cp。
In the present invention, by the total weight of the composition epoxy resin be 100 parts by weight in terms of, the content of the epoxy resin
For 5-15 parts by weight (preferably 8-13 parts by weight), the content of the curing agent is 3-12 parts by weight (preferably 7-10 parts by weight), institute
The content for stating promotor is 0.05-1 parts by weight (preferably 0.1-0.5 parts by weight), and the content of the inorganic filler is 30-80 weight
The content of part (preferably 40-60 parts by weight), the colorant is 10-50 parts by weight (preferably 15-35 parts by weight), and the stress changes
Property agent content be 0.1-2 parts by weight (preferably 0.8-1.5 parts by weight), the content of the release agent be 0.1-1 parts by weight (preferably
0.3-0.8 parts by weight).
In the present invention, the curing agent is preferably alicyclic acid anhydrides, such as the curing agent can be tetrahydrophthalic anhydride, methyl
One of tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyl hexahydrophthalic anhydride are a variety of, further preferably hexahydrophthalic anhydride and/or methyl six
Hydrogen phthalic anhydride, most preferably hexahydrophthalic anhydride.In above-mentioned most preferred situation, the resistance to of composition epoxy resin can be further improved
Ageing properties.
In the present invention, the promotor is one of organic phosphine compound, tertiary amine compound or imidazolium compounds or more
Kind, further preferably organic phosphine compound and tertiary amine compound；Since organic phosphine compound has more than tertiary amine compound
Excellent yellowing-resistant ability, therefore, promotor is preferably organic phosphine compound.
In the present invention, the organic phosphine compound be triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt, tetrabutyl O,
One of O- diethyldithioposphoric acid phosphine is a variety of；The tertiary amine compound is tri- (diformazan of triethanolamine and/or 2,4,6-
Aminomethyl) phenol；The imidazolium compounds is one of methylimidazole, diethyl tetramethyl imidazoles and diphenyl-imidazole
Or it is a variety of.
In the present invention, the inorganic filler be SiO 2 powder, aluminium oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and
One of fumed silica is a variety of, preferably SiO 2 powder and/or aluminium oxide.Since of the invention is applied to
The loading of the inorganic filler of the composition epoxy resin of LED support encapsulating material it is higher to resist epoxy resin cure when generation
Contraction, and since the mobility of SiO 2 powder is preferable, in most preferred situation, the inorganic filler is dioxy
SiClx powder.
In the present invention, the colorant helps to improve the reflectivity of the composition epoxy resin, under preferable case, institute
Stating colorant is one of titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide or a variety of, more preferably titanium dioxide
At least one of titanium, barium sulfate and antimony oxide, further preferably titanium dioxide.
In the present invention, the stress modifying agent facilitates the stress for reducing cure shrinkage and generating when expanding with heat and contract with cold, preferably
In the case of, the stress modifying agent is one of organic silicon modified by polyether oil, rubber and silicone resin or a variety of, is more preferably gathered
Ether modification organic silicon oil.
In the present invention, the release agent helps to be removed from the mold composition epoxy resin smoothly, under preferable case,
The release agent is one of Brazil wax, polyethylene wax, polypropylene wax and esterified wax or a variety of；In order to reduce release agent
Influence to the reflectivity of composition epoxy resin, in further preferred situation, the release agent is polyethylene wax.
The present invention also provides a kind of preparation methods of composition epoxy resin, wherein the preparation method includes: (1) system
Standby epoxy resin；(2) by the epoxy resin and curing agent, promotor, inorganic filler, colorant, stress modifying agent and demoulding
Agent is kneaded；Wherein, prepare epoxy resin the following steps are included:
A. formula (2) compound represented is reacted with compound A；
B. the reaction product of step a is reacted with formula (3) compound represented；
Wherein, compound A is water or R4COOH, R3For the linear or branched alkyl group of H or C1-C5, preferably H or C1-C3's
Straight chained alkyl, further preferably H or methyl；R4For the linear or branched alkyl group of H or C1-C6, preferably H or C1-C4's is straight
Alkyl group, preferably methyl or ethyl.
In the present invention, the C1-C5Linear or branched alkyl group specific example include but is not limited to: methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl or neopentyl.
In the present invention, the C1-C6Linear or branched alkyl group specific example include but is not limited to: methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl or different
Hexyl.
Selecting for Chinese style (2) compound represented of the present invention and compound A for example can be to combine shown in table 2, but simultaneously
It is not limited to these combinations.
Table 2
| Combination number | 2 compound represented of formula | Compound A |
| 1 | R3For methyl | Water |
| 2 | R3For methyl | Acetic acid |
| 3 | R3For H | Water |
| 4 | R3For ethyl | Water |
| 5 | R3For methyl | Propionic acid |
| 6 | R3For tert-butyl | Acetic acid |
| 7 | R3For isopentyl | Butyric acid |
In the present invention, by increasing its molecular weight to TGIC epoxy resin modification, thus make the epoxy resin have compared with
High softening point and viscosity, and then make the composition epoxy resin containing the epoxy resin that there is better continuously shaped property, together
When reflectivity with higher, LED support encapsulating material can be preferably applied to.It should be noted that chemical combination shown in formula (2)
Object is anhydride compound, which can generally be commercially available, if in the anhydride compound being commercially available in itself
Free acid (free acid content is less than 1 weight %) is contained, then can be omitted above-mentioned step when preparing the modified epoxy
Rapid a.
In the present invention, to the use of formula (2) compound represented and compound A in the step a for preparing epoxy resin
There is no particular limitation for amount, as long as dosage energy formula (2) compound represented of compound A is reacted completely.Preferable case
Under, in the step a for preparing epoxy resin, the ratio of the dosage and the dosage of compound A of formula (2) compound represented is
20-1000:1, preferably 100-500:1.
In the present invention, in the step b for preparing epoxy resin, if the dosage of formula (3) compound represented and formula (2) institute
The compound amount shown is compared excessively, it will cause wasting raw material, if shown in the dosage of formula (3) compound represented and formula (2)
Compound amount compared to very few, then epoxy resin can be made directly to solidify because generating cross-linked structure.In the case of it is therefore preferable that,
In the step b for preparing epoxy resin, the dosage of formula (3) compound represented and the ratio of formula (2) compound represented dosage
Value is 8-20:1, preferably 13-17:1.Under the preferable case, epoxy resin softening point with higher and viscosity.
In the present invention, to the reaction condition in the step a for preparing epoxy resin, there is no particular limitation, can be this
The selection of field routine, under preferable case, in the step a for preparing epoxy resin, the condition of the reaction includes: that temperature is
10-80 DEG C, preferably 30-60 DEG C；Time is 1-30min, preferably 5-15min.
In the present invention, in the step b for preparing epoxy resin, the condition of the reaction may include: that temperature is 60-
180 DEG C, preferably 100-150 DEG C；Time is 5-60min, preferably 20-40min.It under the reaction conditions, can be by formula (3)
Epoxy group open loop in compound represented is simultaneously sufficiently reacted with the reaction product that step a is obtained, to obtain having higher
Softening point and viscosity epoxy resin.
A preferred embodiment of the invention, described the step of preparing epoxy resin can also include: by step a
Reaction product reacted with formula (3) compound represented before first by formula (3) compound represented melt, it is described to melt
The temperature of journey is 100-150 DEG C.
In the present invention, by the total weight of the composition epoxy resin be 100 parts by weight in terms of, the dosage of the epoxy resin
For 5-15 parts by weight (preferably 8-13 parts by weight), the dosage of the curing agent is 3-12 parts by weight (preferably 7-10 parts by weight), institute
The dosage for stating promotor is 0.05-1 parts by weight (preferably 0.1-0.5 parts by weight), and the dosage of the inorganic filler is 30-80 weight
The dosage of part (preferably 40-60 parts by weight), the colorant is 10-50 parts by weight (preferably 15-35 parts by weight), and the stress changes
Property agent dosage be 0.1-2 parts by weight (preferably 0.8-1.5 parts by weight), the dosage of the release agent be 0.1-1 parts by weight (preferably
0.3-0.8 parts by weight).
In the present invention, the curing agent is preferably alicyclic acid anhydrides, such as the curing agent can be tetrahydrophthalic anhydride, methyl
One of tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyl hexahydrophthalic anhydride are a variety of, further preferably hexahydrophthalic anhydride and/or methyl six
Hydrogen phthalic anhydride, most preferably hexahydrophthalic anhydride.In above-mentioned most preferred situation, the resistance to of composition epoxy resin can be further improved
Ageing properties.
In the present invention, the promotor is one of organic phosphine compound, tertiary amine compound or imidazolium compounds or more
Kind, further preferably organic phosphine compound and tertiary amine compound；Since organic phosphine compound has more than tertiary amine compound
Excellent yellowing-resistant ability, therefore, promotor is preferably organic phosphine compound.
In the present invention, the organic phosphine compound be triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt, tetrabutyl O,
One of O- diethyldithioposphoric acid phosphine is a variety of；The tertiary amine compound is tri- (diformazan of triethanolamine and/or 2,4,6-
Aminomethyl) one of phenol or a variety of；The imidazolium compounds is methylimidazole, diethyl tetramethyl imidazoles and hexichol
One of base imidazoles is a variety of.
In the present invention, the inorganic filler be SiO 2 powder, aluminium oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and
One of fumed silica is a variety of, preferably SiO 2 powder and/or aluminium oxide.Since of the invention is applied to
The loading of the inorganic filler of the composition epoxy resin of LED support encapsulating material it is higher to resist epoxy resin cure when generation
Contraction, and since the mobility of SiO 2 powder is preferable, in most preferred situation, the inorganic filler is dioxy
SiClx powder.
In the present invention, the colorant helps to improve the reflectivity of the epoxy resin, under preferable case, the coloring
Agent is one of titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide or a variety of, more preferably titanium dioxide, sulfuric acid
At least one of barium and antimony oxide, further preferably titanium dioxide.
In the present invention, the stress modifying agent facilitates the stress for reducing cure shrinkage and generating when expanding with heat and contract with cold, preferably
In the case of, the stress modifying agent one of oily, rubber and silicone resin or a variety of for organic silicon modified by polyether, more preferably
Organic silicon modified by polyether oil.
In the present invention, the release agent helps to be removed from the mold composition epoxy resin smoothly, under preferable case,
The release agent is one of Brazil wax, polyethylene wax, polypropylene wax, esterified wax or a variety of；In order to reduce release agent
Influence to the reflectivity of composition epoxy resin, in further preferred situation, the release agent is polyethylene wax.
According to another preferred method of implementation of the present invention, the process of the mixing includes:
(1) first time dispersion is carried out after mixing inorganic filler and colorant；
(2) promotor and stress modifying agent are sequentially added in the mixture obtained after dispersing to first time, are carried out second
Dispersion；
(3) epoxy resin, curing agent and release agent are added in the mixture obtained after dispersing to second, carries out third time
Dispersion；
(4) mixture obtained after dispersing third time is kneaded.
During above-mentioned mixing, the time of dispersion can be 4-8 minute for the first time, and second time dispersed can be with
It is 4-8 minutes, the time of third time dispersion can be 8-15 minutes；The mode of promotor and stress modifying agent is added preferably with
Spray mode is implemented；Preferably, epoxy resin and curing agent are first ground into partial size before epoxy resin and curing agent are added
Less than 30 mesh powders.The process that the mixture obtained after third time is dispersed is kneaded is specifically as follows: by third time point
In the mixture investment storage tank obtained after dissipating, uniformly it is delivered in double screw extruder with feeder, is carried out at 80-90 DEG C
It is kneaded 10-30min；Material after mixing forms flow-like and flows out from extruder mouth, until flakiness is calendered on rolling mill roller,
It is hardened, then is crushed after cooling, it is final to obtain the graininess composition epoxy resin that maximum particle diameter is 10 mesh.
The present invention also provides the composition epoxy resins prepared by preparation method of the present invention.The epoxy resin group
Object continuously shaped property with higher is closed, and keeps high reflectivity.
Application the present invention also provides composition epoxy resin of the present invention as LED support encapsulating material.This
The invention composition epoxy resin continuously shaped property with higher, and high reflectivity is kept, it is highly suitable for conduct
LED support encapsulating material.
The present invention will be described in detail by way of examples below.In following preparation example, embodiment and comparative example,
The performance measurement of epoxy resin:
1, softening point: being measured by ring and ball method, specifically according to GB 12007.6-1989 epoxy resin softening point measurement method
Ring and ball method measurement；
2, the viscosity at 150 DEG C: being measured by cone-plate viscosimeter, specifically: 0.2g sample is taken, using cone-plate viscosimeter
Measure the viscosity at 150 DEG C.
The performance measurement of composition epoxy resin:
1, measuring reflectance:
(1) composition epoxy resin of preparation is used into mould under 175 DEG C of mold temperature, the process conditions of curing time 120s
Press transmitting injection molding is allowed to the thin slice that curing molding is 1mm thickness into specific mold；
(2) initial reflectance: by the thin slice after 150 DEG C solidify 4 hours, integrating sphere type spectrophotometer V770 is used
Reflectivity under test wavelength 550nm；
(3) aging back reflection rate: by the thin slice of step (2) using 130 DEG C after aging 1000 hours, test wavelength again
Reflectivity under 550nm.
2, forming ability (continuously shaped number) measures:
(1) composition epoxy resin of preparation is used into mould under 175 DEG C of mold temperature, the process conditions of curing time 120s
Press transmitting injection molding is allowed to the cylindrical body that curing molding is diameter 5mm, height 5mm into specific mold；
(2) off-type force is tested: after above-mentioned composition epoxy resin molding, immediately being taken out mold, with hand-held thrust meter
Molding cylindrical body is released, maximum thrust at this time is off-type force；
(3) every 50 mould tests off-type force, until off-type force is greater than 100N, mould number at this time is continuously shaped number.
In following preparation example, embodiment and comparative example, TGIC is the commercially available product that the Nissan Chemical company trade mark is TEPIC-S；
Methyl hexahydrophthalic anhydride is the commercially available product that the Puyang Hui Cheng company trade mark is Me-HHPA；
Curing agent hexahydrophthalic anhydride is the commercially available product that the Puyang Hui Cheng company trade mark is HHPA；
Promotor methyl tributyl phosphine dimethyl phosphate salt is the city that Nippon Chemical Ind's trade mark is PX-4MP
Sell product；
Inorganic filler SiO 2 powder is the commercially available product that the trade mark of Jiangsu Lian Rui company is DQ1200；
Colorant titania powder is the commercially available product that the trade mark of Shi Yuan chemical company is R780；
Stress modifying agent polyether modified silicon oil is the commercially available product that the trade mark of Dow Corning Corporation is SF8421；
Release agent polyethylene wax is the commercially available product that the trade mark of Klein company is PE520.
Preparation example 1
(1) by the methyl hexahydrophthalic anhydride of 1 parts by weight (formula (2) compound represented, wherein R3For methyl) and 0.01 weight
The water mixing of part reacts 5min at being 30 DEG C in temperature；
(2) TGIC of 13 parts by weight (formula (3) compound represented) is put into reaction kettle, opens and heats and temperature is set
It is 150 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reaction kettle,
30min is reacted at being 125 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A1 (has and tie as shown in formula (1)
Structure, R1For methyl, R2For H, n=10).
The softening point and viscosity of A1 are measured, the results are shown in Table 3.
Preparation example 2
(1) by the methyl hexahydrophthalic anhydride of 1 parts by weight (formula (2) compound represented, wherein R3For methyl) and 0.05 weight
(compound A is R to the acetic acid of part4COOH, wherein R4For methyl) mixing, 15min is reacted at being 60 DEG C in temperature；
(2) TGIC of 17 parts by weight (formula (3) compound represented) is put into reaction kettle, opens and heats and temperature is set
It is 120 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reaction kettle,
40min is reacted at being 150 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A2 (has and tie as shown in formula (1)
Structure, R1For methyl, R2It is methyl, n=8 for R '-CO-, R ').
The softening point and viscosity of A2 are measured, the results are shown in Table 3.
Preparation example 3
(1) by the hexahydrophthalic anhydride of 1 parts by weight (formula (2) compound represented, wherein R3It is that H) and the water of 0.03 parts by weight are mixed
It closes, reacts 10min at being 50 DEG C in temperature；
(2) TGIC of 15 parts by weight (formula (3) compound represented) is put into reaction kettle, opens and heats and temperature is set
It is 100 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reaction kettle,
200min is reacted at being 100 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A3 (has as shown in formula (1)
Structure, R1For H, R2For H, n=9).
The softening point and viscosity of A3 are measured, the results are shown in Table 3.
Preparation example 4
Epoxy resin is prepared according to the method for preparation example 1, unlike, step (3) reaction temperature is 50 DEG C.Obtain epoxy
Resin A 4.
The softening point and viscosity of A4 are measured, the results are shown in Table 3.
Preparation example 5
Epoxy resin is prepared according to the method for preparation example 1, unlike, step (3) reaction time is 2min.Obtain epoxy
Resin A 5.
The softening point and viscosity of A5 are measured, the results are shown in Table 3.
Compare preparation example 1
Epoxy resin is prepared according to the method for preparation example 1, unlike, methyl is replaced using the acetic anhydride of identical weight part
Hexahydrophthalic anhydride obtains epoxy resin D1.
The softening point and viscosity of D1 are measured, the results are shown in Table 3.
Table 3
| Project | A1 | A2 | A3 | A4 | A5 | D1 | TGIC |
| Softening point/DEG C | 100 | 110 | 90 | 80 | 70 | 20 | -- |
| Viscosity/cp | 2000 | 1500 | 1700 | 1300 | 1200 | 100 | 5 |
Embodiment 1
(1) 12 parts by weight epoxy resin A1 and 9 parts by weight hexahydrophthalic anhydride are crushed using pulverizer respectively, obtains grain
Diameter is less than 30 mesh powders；
(2) 52 parts by weight of silica powder and 25 parts by weight of titanium dioxide powder are put into high-speed mixer respectively,
Start high-speed mixer, two kinds of materials is made to carry out first time dispersion；
(3) when first time dispersion process is carried out to 5min, 0.3 parts by weight methyl tributyl is successively added with spray mode
Phosphine dimethyl phosphate salt, 1.2 parts by weight polyether modified silicon oils carry out second of dispersion 5min；
(4) smashed epoxy resin A1 and hexahydrophthalic anhydride, 0.5 weight account polyethylene wax are put into respectively, carry out third time
Disperse 10min, obtains uniform powder mixture；
(5) it in the mixture investment storage tank obtained step (4), is uniformly delivered in double screw extruder with feeder
Mixing 15min is carried out at 80 DEG C, the material after mixing forms flow-like and flows out from extruder mouth, until being pressed on rolling mill roller
Prolong flakiness, be hardened after cooling, then is crushed, it is final to obtain the composition epoxy resin Z1 that maximum particle diameter is 10 mesh.It surveys
Determine the reflectivity and continuously shaped number of Z1, the results are shown in Table 4.
Embodiment 2-5
Prepare composition epoxy resin according to the method for embodiment 1, unlike, be respectively adopted identical weight part A2,
A3, A4, A5 replace epoxy resin A1.Respectively obtain Z2, Z3, Z4, Z5.Measure the reflectivity of Z2, Z3, Z4, Z5 and continuously shaped
Number, as a result as described in Table 4.
Embodiment 6
(1) the epoxy resin A1 and hexahydrophthalic anhydride of parts by weight same as Example 1 are crushed using pulverizer respectively,
Partial size is obtained less than 30 mesh powders；
(2) the epoxy resin A1 powder, hexahydrophthalic anhydride powder and the parts by weight same as Example 1 that obtain step (1)
SiO 2 powder, titania powder, methyl tributyl phosphine dimethyl phosphate salt, polyether modified silicon oil and polyethylene wax are mixed
It closes, obtained mixture is put into storage tank, is uniformly delivered in double screw extruder with feeder and is mixed at 80 DEG C
15min is refined, the material after mixing forms flow-like and flows out from extruder mouth, until flakiness is calendered on rolling mill roller, through cold
But it is hardened, then is crushed afterwards, it is final to obtain the composition epoxy resin Z6 that maximum particle diameter is 10 mesh.Measure Z6 reflectivity and
Continuously shaped number, the results are shown in Table 4.
Embodiment 7
Composition epoxy resin is prepared according to the method for embodiment 1, unlike, the dosage of epoxy resin A1 is 15 weight
Part, the dosage of curing agent hexahydrophthalic anhydride is 5 parts by weight.It is final to obtain the composition epoxy resin Z8 that maximum particle diameter is 10 mesh.It surveys
Determine the reflectivity and continuously shaped number of Z8, the results are shown in Table 4.
Comparative example 1
Composition epoxy resin is prepared according to the method for embodiment 1, unlike, it is replaced using the TGIC of identical weight part
Epoxy resin A1.Obtain DZ1.The reflectivity and continuously shaped number of DZ1 are measured, as a result as described in Table 4.
Comparative example 2
Composition epoxy resin is prepared according to the method for embodiment 1, unlike, the D1 generation of identical weight part is respectively adopted
For epoxy resin A1.Respectively obtain DZ2.The reflectivity and continuously shaped number of DZ2 are measured, as a result as described in Table 4.
Table 4
Result as shown in Table 3 can be seen that modified epoxy of the present invention with high softening point and viscosity；
Result as shown in Table 4 can be seen that composition epoxy resin of the present invention with high continuously shaped ability, have simultaneously
High reflectivity.Epoxy containing epoxy resin of the present invention it can be seen from the measurement result of embodiment 1 and comparative example 1
Resin combination reflectivity compared with the composition epoxy resin containing TGIC is suitable, but contains epoxy resin of the present invention
Composition epoxy resin have higher continuously shaped ability；It can relatively be seen by the measurement result of embodiment 1 and comparative example 2
Out, the composition epoxy resin containing epoxy resin of the present invention has more preferable continuously shaped ability.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (26)
1. a kind of composition epoxy resin, which is characterized in that the composition epoxy resin includes epoxy resin, curing agent, rush
Into agent, inorganic filler, colorant, stress modifying agent and release agent；The epoxy resin has the structure as shown in formula (1)；
Wherein, n 1-10, R1For the linear or branched alkyl group of H or C1-C5, R2For H orR ' is H or C1-C6
Linear or branched alkyl group.
2. composition epoxy resin according to claim 1, wherein the R1For the straight chained alkyl of H or C1-C3, the R '
For the straight chained alkyl of H or C1-C4.
3. composition epoxy resin according to claim 1, wherein the R1For H or methyl, the R ' is methyl or second
Base.
4. composition epoxy resin according to claim 1, wherein the softening point of the epoxy resin is 30-120 DEG C；
Viscosity is 10-5000cp at 150 DEG C.
5. composition epoxy resin according to claim 1, wherein the softening point of the epoxy resin is 50-110 DEG C,
Viscosity is 120-4500cp at 150 DEG C.
6. composition epoxy resin described in any one of -5 according to claim 1, wherein with the composition epoxy resin
Total weight be 100 parts by weight meters, the content of the epoxy resin is 5-15 parts by weight, and the content of the curing agent is that 3-12 is weighed
Part is measured, the content of the promotor is 0.05-1 parts by weight, and the content of the inorganic filler is 30-80 parts by weight, the coloring
The content of agent is 10-50 parts by weight, and the content of the stress modifying agent is 0.1-2 parts by weight, and the content of the release agent is
0.1-1 parts by weight.
7. composition epoxy resin according to claim 6, wherein the curing agent is alicyclic acid anhydrides；
And/or the promotor is one of organic phosphine compound, tertiary amine compound and imidazolium compounds or a variety of；
And/or the inorganic filler is one of SiO 2 powder, aluminium oxide, magnesium hydroxide, aluminium hydroxide and calcium carbonate
Or it is a variety of；
And/or the colorant is one of titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide or a variety of；
And/or the stress modifying agent is one of organic silicon modified by polyether oil, rubber and silicone resin or a variety of；
And/or the release agent is one of Brazil wax, polyethylene wax, polypropylene wax and esterified wax or a variety of.
8. composition epoxy resin according to claim 6, wherein the curing agent is tetrahydrophthalic anhydride, methyl tetrahydro benzene
One of acid anhydride, hexahydrophthalic anhydride and methyl hexahydrophthalic anhydride are a variety of；
And/or the promotor is organic phosphine compound and tertiary amine compound；
And/or the inorganic filler is SiO 2 powder and/or aluminium oxide.
9. composition epoxy resin according to claim 7 or 8, wherein the inorganic filler is fumed silica.
10. composition epoxy resin according to claim 7, wherein the curing agent is hexahydrophthalic anhydride and/or methyl six
Hydrogen phthalic anhydride；
And/or the organic phosphine compound is triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt and tetrabutyl O, O- diethyl
One of base phosphordithiic acid phosphine is a variety of；The tertiary amine compound is triethanolamine and/or (the dimethylamino first of 2,4,6- tri-
Base) phenol；The imidazolium compounds is one of methylimidazole, diethyl tetramethyl imidazoles and diphenyl-imidazole or more
Kind.
11. a kind of preparation method of composition epoxy resin, which is characterized in that the preparation method includes: that (1) prepares asphalt mixtures modified by epoxy resin
Rouge；(2) epoxy resin and curing agent, promotor, inorganic filler, colorant, stress modifying agent and release agent are mixed
Refining；Wherein, prepare epoxy resin the following steps are included:
A. formula (2) compound represented is reacted with compound A；
B. the reaction product of step a is reacted with formula (3) compound represented；
Wherein, compound A is water or R4COOH, R3For the linear or branched alkyl group of H or C1-C5；R4For H or C1-C6 straight chain or
Branched alkyl.
12. preparation method according to claim 11, wherein the R3For the straight chained alkyl of H or C1-C3, the R4For H
Or the straight chained alkyl of C1-C4.
13. preparation method according to claim 11, wherein the R3For H or methyl, the R4For methyl or ethyl.
14. preparation method according to claim 11, wherein in the step a for preparing epoxy resin, shown in formula (2)
Compound dosage and compound A dosage ratio be 20-1000:1；
In the step b for preparing epoxy resin, the dosage and formula (2) compound represented dosage of formula (3) compound represented
Ratio be 8-20:1.
15. preparation method according to claim 11, wherein in the step a for preparing epoxy resin, shown in formula (2)
Compound dosage and compound A dosage ratio be 100-500:1；In the step b for preparing epoxy resin, formula
(3) ratio of the dosage of compound represented and formula (2) compound represented dosage is 13-17:1.
16. preparation method described in any one of 1-15 according to claim 1, wherein the step a for preparing epoxy resin
In, the condition of the reaction includes: that temperature is 10-80 DEG C, time 1-30min；
In the step b for preparing epoxy resin, the condition of the reaction includes: that temperature is 60-180 DEG C, time 5-
60min。
17. preparation method according to claim 16, wherein in the step a for preparing epoxy resin, the reaction
Condition includes: that temperature is 30-60 DEG C, time 5-15min；
In the step b for preparing epoxy resin, the condition of the reaction includes: that temperature is 100-150 DEG C, time 20-
40min。
18. preparation method described in any one of 1-15 according to claim 1, wherein described the step of preparing epoxy resin
Further include: first by formula (3) compound represented before the reaction product of step a is reacted with formula (3) compound represented
Melt, the temperature of the melting process is 100-150 DEG C.
19. preparation method described in any one of 1-15 according to claim 1, wherein with the composition epoxy resin
Total weight is 100 parts by weight meters, and the dosage of the epoxy resin is 5-15 parts by weight, and the dosage of the curing agent is 3-12 weight
Part, the dosage of the promotor is 0.05-1 parts by weight, and the dosage of the inorganic filler is 30-80 parts by weight, the colorant
Dosage be 10-50 parts by weight, the dosage of the stress modifying agent is 0.1-2 parts by weight, and the dosage of the release agent is 0.1-1
Parts by weight.
20. preparation method described in any one of 1-15 according to claim 1, wherein the curing agent is alicyclic acid anhydrides；
And/or the promotor is one of organic phosphine compound, tertiary amine compound and imidazolium compounds or a variety of；
And/or the inorganic filler is one of SiO 2 powder, aluminium oxide, magnesium hydroxide, aluminium hydroxide and calcium carbonate
Or it is a variety of；
And/or the colorant is one of titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide or a variety of；
And/or the stress modifying agent is one of organic silicon modified by polyether oil, rubber and silicone resin or a variety of；
And/or the release agent is one of Brazil wax, polyethylene wax, polypropylene wax and esterified wax or a variety of.
21. preparation method according to claim 20, wherein the curing agent is tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, six
One of hydrogen phthalic anhydride and methyl hexahydrophthalic anhydride are a variety of；
And/or the promotor is organic phosphine compound and tertiary amine compound；
And/or the inorganic filler is SiO 2 powder and/or aluminium oxide.
22. the preparation method according to claim 20 or 21, wherein the inorganic filler is fumed silica.
23. preparation method according to claim 20, wherein the curing agent is hexahydrophthalic anhydride and/or methyl hexahydrobenzene
Acid anhydride；
And/or the organic phosphine compound is triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt and tetrabutyl O, O- diethyl
One of base phosphordithiic acid phosphine is a variety of；The tertiary amine compound is triethanolamine and/or (the dimethylamino first of 2,4,6- tri-
Base) phenol；The imidazolium compounds is one of methylimidazole, diethyl tetramethyl imidazoles and diphenyl-imidazole or more
Kind.
24. preparation method described in any one of 1-15 according to claim 1, wherein the process of the mixing includes:
(1) first time dispersion is carried out after mixing inorganic filler and colorant；
(2) promotor and stress modifying agent are sequentially added in the mixture obtained after dispersing to first time, are carried out second and are dispersed；
(3) epoxy resin, curing agent and release agent are added in the mixture obtained after dispersing to second, carries out third time point
It dissipates；
(4) mixture obtained after dispersing third time is kneaded.
25. the composition epoxy resin of the preparation of the preparation method as described in any one of claim 11-24.
26. composition epoxy resin answering as LED support encapsulating material described in any one of claim 1-10 and 25
With.
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| CN109096971B (en) * | 2018-07-10 | 2021-03-19 | 西安贝克电子材料科技有限公司 | High-adhesion epoxy resin composition |
| TWI693257B (en) * | 2018-08-17 | 2020-05-11 | 景美實業股份有限公司 | Epoxy-silicone composite composition |
| CN109082256B (en) * | 2018-08-21 | 2021-03-23 | 盐城东山精密制造有限公司 | Packaging adhesive and preparation method thereof |
| CN109504328B (en) * | 2018-11-28 | 2020-08-04 | 深圳市明粤科技有限公司 | Micro L ED display screen packaging material |
| CN111944270B (en) * | 2019-05-16 | 2024-02-02 | 衡所华威电子有限公司 | Epoxy resin composition, method for producing the same and use thereof |
| CN112341755B (en) * | 2019-08-07 | 2023-01-17 | 北京科化新材料科技有限公司 | Yellowing-resistant transparent epoxy resin packaging material and preparation method and application thereof |
| CN112391034B (en) * | 2019-08-13 | 2022-12-09 | 北京科化新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
| CN111633787B (en) * | 2020-05-26 | 2021-11-26 | 长江水利委员会长江科学院 | Make smooth concrete external mold device of concrete surface mirror surface |
| CN112480847B (en) * | 2020-10-21 | 2022-10-14 | 江苏科化新材料科技有限公司 | High-heat-resistance low-stress epoxy plastic packaging material and preparation method thereof |
| CN114350112A (en) * | 2021-12-30 | 2022-04-15 | 江苏科化新材料科技有限公司 | LED support material, preparation method and application thereof |
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| US3496122A (en) * | 1967-07-14 | 1970-02-17 | Ciba Ltd | Modified triglycidylisocyanurate resins |
| CN103140536A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Epoxy resin composition, prepreg and fiber enforced complex material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496122A (en) * | 1967-07-14 | 1970-02-17 | Ciba Ltd | Modified triglycidylisocyanurate resins |
| CN103140536A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Epoxy resin composition, prepreg and fiber enforced complex material |
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