CN114276653B - Epoxy resin composition and application thereof, epoxy resin and preparation method thereof - Google Patents
Epoxy resin composition and application thereof, epoxy resin and preparation method thereof Download PDFInfo
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- CN114276653B CN114276653B CN202111654717.4A CN202111654717A CN114276653B CN 114276653 B CN114276653 B CN 114276653B CN 202111654717 A CN202111654717 A CN 202111654717A CN 114276653 B CN114276653 B CN 114276653B
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- tetraphenylphosphonium salt
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 85
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 application thereof Substances 0.000 claims abstract description 24
- 239000011256 inorganic filler Substances 0.000 claims abstract description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 229910001410 inorganic ion Inorganic materials 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 239000002516 radical scavenger Substances 0.000 claims abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 27
- 239000005011 phenolic resin Substances 0.000 claims description 27
- 229920001568 phenolic resin Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 239000012184 mineral wax Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012178 vegetable wax Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of semiconductor packaging materials, and discloses an epoxy resin composition, application thereof, epoxy resin and a preparation method thereof. The composition comprises the following components in parts by weight: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenylphosphonium salt complex modified curing agent, 0.1-1.5 parts of accelerator, 80-90 parts of inorganic filler, 0.5-1.5 parts of flame retardant, 0.03-1.5 parts of release agent, 0.05-0.5 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier. The epoxy resin contains a specific tetraphenylphosphonium salt complex modified curing agent, so that the composition has proper viscosity and curing speed, has high fluidity, and can effectively inhibit the generation of air holes when the epoxy resin is prepared; the proportions of the components in the composition are synergistic, so that the stress and viscosity of the composition are further improved, and the epoxy resin prepared from the composition has the characteristic of low warpage.
Description
Technical Field
The invention relates to the technical field of semiconductor packaging materials, in particular to an epoxy resin composition, application thereof, epoxy resin and a preparation method thereof.
Background
A large-area bare pad is usually arranged at the bottom center of a QFN (Quad Flat No-leaded package) for conducting heat, and the pad can be used as a direct heat dissipation channel for conducting heat generated by the operation of a chip in the package; the bonding pad is directly welded on the circuit board after being surface-mounted, and the PCB heat dissipation holes can diffuse redundant power consumption into the copper grounding plate to absorb redundant heat, so that the heat dissipation of the chip is greatly improved. The QFN package is different from the conventional DIP or SOP package having the europaea-like leads, and has a short conductive path between the pins and the PCB pads after surface mounting, and has a low self-inductance and wiring resistance in the package, so that it can provide good electrical performance.
In order to better meet the flowability requirement, the epoxy resin composition for the conventional QFN package and DFN (dual flat no-lead package) package generally adopts a combination of high Tg (glass transition temperature) and low filler content or low Tg and high filler content, and both the combinations result in high stress and low viscosity of the epoxy resin composition, so that the package warpage and air holes are easy to exceed the standards.
Disclosure of Invention
The invention aims to solve the problems of package warpage and air hole exceeding standards in the prior art, and provides an epoxy resin composition, application thereof, epoxy resin and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides an epoxy resin composition, characterized in that the composition comprises, in parts by weight: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenylphosphonium salt complex modified curing agent, 0.1-1.5 parts of accelerator, 80-90 parts of inorganic filler, 0.5-1.5 parts of flame retardant, 0.03-1.5 parts of release agent, 0.05-0.5 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier.
The second aspect of the invention provides a method for preparing an epoxy resin, which is characterized in that the method comprises the following steps: and heating and mixing the epoxy resin composition to obtain a mixture, and forming and demolding the mixture to obtain the epoxy resin.
In a third aspect, the invention provides an epoxy resin, which is characterized in that the epoxy resin is prepared by the method.
In a fourth aspect, the present invention provides the use of the above composition or epoxy in QFN and/or DFN packages.
Through the technical scheme, the invention has the following beneficial effects: the epoxy resin contains a specific tetraphenylphosphonium salt complex modified curing agent, so that the composition has proper viscosity and curing speed, has high fluidity, and can effectively inhibit the generation of air holes when the epoxy resin is prepared; furthermore, the proportions of the components in the composition are synergistic, so that the stress and viscosity of the composition can be further improved, and the epoxy resin prepared from the composition has the characteristic of low warpage and is particularly suitable for QFN packaging.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides an epoxy resin composition characterized by comprising, in parts by weight: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenylphosphonium salt complex modified curing agent, 0.1-1.5 parts of accelerator, 80-90 parts of inorganic filler, 0.5-1.5 parts of flame retardant, 0.03-1.5 parts of release agent, 0.05-0.5 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier.
In the invention, the proportions of the components in the composition are synergistic, so that the stress of the composition can be reduced, the viscosity and the fluidity of the composition are improved, and the epoxy resin prepared from the composition has the characteristics of low warpage and less surface air holes.
According to the invention, the composition comprises, in parts by weight: 4-8 parts of epoxy resin, 3-7.5 parts of tetraphenylphosphonium salt complex modified curing agent, 0.3-1.2 parts of accelerator, 85-90 parts of inorganic filler, 0.03-1 part of release agent, 0.05-0.2 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier.
In the invention, when each component in the composition meets the proportion, the epoxy resin prepared from the composition has more excellent comprehensive performance.
Further, the composition also contains 0.2 to 0.8 parts of a colorant, preferably 0.3 to 0.7 parts of a colorant.
In the present invention, the colorant is not particularly limited, and may be selected as desired, for example, the colorant in the present invention is carbon black.
According to the invention, the epoxy resin has an epoxy value of 0.3-0.8 and an epoxy equivalent of 160-280 g/equivalent.
In the invention, when the epoxy value, the epoxy equivalent and the molecular weight of the epoxy resin meet the above ranges, the composition can have proper viscosity and fluidity, and the epoxy resin prepared from the composition has the characteristics of low warpage and less air holes on the surface.
Further, the epoxy resin has an epoxy value of 0.48 to 0.63 and an epoxy equivalent of 160 to 210.
According to the invention, the preparation method of the tetraphenylphosphonium salt complex modified curing agent comprises the following steps:
(1) And (3) batching: uniformly mixing the tetraphenylphosphonium salt complex and phenolic resin in the presence of a solvent to obtain a mixture;
(2) The reaction: after the mixture is reacted in a protective atmosphere, removing the solvent to obtain a tetraphenylphosphonium salt complex modified curing agent precursor;
(3) And (3) drying: drying the precursor of the tetraphenylphosphonium salt complex modified curing agent to prepare the tetraphenylphosphonium salt complex modified curing agent.
In the present invention, the modified curing agent obtained by modifying the phenolic resin with the tetraphenylphosphonium salt complex by the above-mentioned method can adjust the viscosity of the composition to an appropriate level in the epoxy resin composition, thereby improving the fluidity of the epoxy resin composition.
According to the invention, the phenolic resin has a hydroxyl equivalent weight of 100-210 g/equivalent.
Further, the phenolic resin has a hydroxyl equivalent weight of 150-205 g/equivalent.
According to the invention, the hydroxyl equivalent of the tetraphenylphosphonium salt complex modified curing agent is 90-200 g/equivalent, and the viscosity at 150 ℃ is 0.2-2 Pa.s.
In the invention, when the viscosity of the tetraphenylphosphonium salt complex modified curing agent satisfies the above range, the viscosity of the composition is suitable, the fluidity is good, and further, the epoxy resin prepared from the composition has the characteristics of low warpage and few bubbles on the surface.
Further, the hydroxyl equivalent of the tetraphenylphosphonium salt complex modified curing agent is 140-195 g/equivalent, and the viscosity at 150 ℃ is 0.5-1.5 Pa.s.
According to the invention, the tetraphenylphosphonium salt complex is selected from (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide and/or (2, 3-dihydroxynaphthyl) tetraphenylphosphonium chloride.
According to the present invention, the phenolic resin is at least one selected from the group consisting of a multifunctional phenolic resin, a novolac resin, a biphenyl type phenolic resin and an XY-lock phenolic resin.
In the invention, when the tetraphenylphosphonium salt complex and the phenolic resin are selected from the above types, the prepared modified curing agent has the characteristics of proper viscosity and proper stress.
According to the invention, the mass ratio of the tetraphenylphosphonium salt complex to the phenolic resin to the solvent is 1 (5-25): 20-30.
In the invention, when the tetraphenylphosphonium salt complex, the phenolic resin and the solvent meet the above ranges, the tetraphenylphosphonium salt complex and the phenolic resin can be fully and uniformly dissolved, so that the tetraphenylphosphonium salt complex modified curing agent has proper viscosity.
According to the invention, the mass ratio of the tetraphenylphosphonium salt complex, the phenolic resin and the solvent is 1 (10-20): 30.
According to the invention, in step (1), the solvent is selected from at least one of acetone, tetrahydrofuran and N, N-dimethylformamide, preferably acetone.
According to the invention, in step (2), the reaction conditions include: the reaction is carried out for 2 to 36 hours under the condition of stirring, the temperature is 120 to 160 ℃, the pressure is-0.1 MPa to-0.5 MPa.
According to the invention, the conditions for removing the solvent include: distilling under reduced pressure at 70-90deg.C for 2-15h.
According to the invention, in step (3), drying is carried out at 50-120℃for 1-4h at-0.096 MPa to 0 MPa.
According to the present invention, the epoxy resin is selected from at least two of a novolac type epoxy resin, a bisphenol a type structural epoxy resin, a biphenyl type structural epoxy resin, a naphthalene type structural epoxy resin, an o-cresol type structural epoxy, an alicyclic epoxy resin, a bisphenol F type structural epoxy resin, a DCPD type structural epoxy resin, and a multifunctional type structural epoxy resin.
In the invention, the epoxy resin is selected from at least two of the above, and the beneficial effects of high strength and low water absorption can be obtained.
According to the present invention, the inorganic filler is selected from at least one of silica, alumina and magnesia.
In the present invention, the inorganic filler is selected from the above-mentioned types, and can have good fluidity.
According to the invention, the inorganic filler has a particle size of 0.1-75. Mu.m.
In the invention, the particle size of the inorganic filler satisfies the above range, so that the filling property of the epoxy resin composition is better and more uniform, and the comprehensive performance of the composition is further improved.
Further, the inorganic filler has a particle diameter of 0.1 to 55. Mu.m, more preferably 0.1 to 45. Mu.m.
According to the invention, the inorganic filler is crystalline and/or fused spherical.
According to the present invention, the accelerator is selected from at least one of an organic phosphorus compound, an imidazole compound, a tertiary amine compound and derivatives thereof, an aromatic ureido derivative and an aliphatic ureido derivative.
In the present invention, the accelerator is selected from the above compounds, and cooperates with the tetraphenylphosphonium salt complex modified curing agent to further improve the viscosity of the composition and provide more suitable fluidity.
According to the present invention, the flame retardant is selected from at least one of metal hydroxide, hydrated metal compound, metal oxide, molybdate, borate, phosphate, phosphorus-containing compound, and nitrogen-containing compound.
According to the present invention, the release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax.
According to the present invention, the inorganic ion scavenger is selected from at least one of hydrated metal oxides, acidic metal salts, and aluminum magnesium compounds.
According to the present invention, the coupling agent is selected from at least one of gamma-epoxypropyl ether trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane.
According to the invention, the modifier is selected from rubber and/or organosilane.
The second aspect of the invention provides a method for preparing an epoxy resin, which is characterized in that the method comprises the following steps: and heating and mixing the epoxy resin composition to obtain a mixture, and forming and demolding the mixture to obtain the epoxy resin.
According to the invention, the conditions for heating and mixing include: heating and mixing at 80-110deg.C for 7-9min.
In the present invention, the mixing equipment is not particularly limited, and for example, heating and mixing may be performed in a twin-roll mill, a single-screw extruder, a twin-screw extruder, a kneader or a stirrer.
According to the invention, the molding conditions include: molding at 170-180deg.C and 12-16 MPa.
In a third aspect, the invention provides an epoxy resin, which is characterized in that the epoxy resin is prepared by the method.
In a fourth aspect, the present invention provides the use of the above composition or epoxy in QFN and/or DFN packages.
The present invention will be described in detail by examples. In the following examples of the present invention,
curing time: preheating an electric heating disc to 175 ℃, putting a certain amount of epoxy resin composition powder on the disc, counting the time required for the powder to change into gel state by using a stopwatch from the beginning of changing into fluid, repeating the same operation twice, and taking the average value of the powder as s;
viscosity: testing by cone plate viscometer under 150 ℃ and 400rpm;
epoxy resin a:
o-cresol type epoxy resin A1, CYDCN205, purchased from Yueyang petrochemical industry;
biphenyl epoxy resin A2, YX4000, available from japan DIC corporation;
naphthalene-containing structural epoxy resins A3, HP4700, available from japan DIC corporation;
bisphenol F type epoxy resin A4, SQE-104, available from Shandong St. Spring chemical Co., ltd;
bisphenol A type epoxy resin A5, YL-6810, available from Mitsubishi corporation of Japan;
tetraphenyl phosphonium chloride complex A6, 5003, available from south tokyo flat bridge company;
acetone, available from zemoer biochemicals inc;
curing agent:
multifunctional phenolic resin DB2, MEH-7851SS, available from Ming dynasty chemical Co., ltd;
and (3) an accelerator:
2-methylimidazole, available from four kingdoms chemical industry Co., ltd;
aromatic dimethylurea, U-CAT3512T, available from Mitsubishi, japan;
inorganic filler:
fused silica spheres available from Jiangsu-nii technologies, inc.;
fused silica, available from Jiangsu-niu technologies Co., ltd
Flame retardant:
nitrogen-containing phenolic, PF8705, available from san francisco, inc;
aluminum hydroxide, available from japan light metals corporation;
and (3) a release agent:
carnauba wax, available from a tree company;
glycerol monostearate, available from ala Ding Shiji limited;
inorganic ion scavenger:
DHT-4A available from Japanese Kogyo chemical Co., ltd
Coupling agent:
KH560, available from Jiangsu morning light technologies, inc.;
KH550, available from Jiangsu morning light technologies, inc.;
and (3) a modifier:
carboxyl-terminated liquid nitrile rubber CTBN, available from the american dow group;
coloring agent:
carbon black, available from Shandong blue chemical Co., ltd;
preparation example 1
Tetraphenylphosphonium salt complex modified curing agent B1, wherein the hydroxyl equivalent is 200 g/equivalent, the viscosity is 0.7 Pa.s at 150 ℃, and the tetraphenylphosphonium salt complex modified curing agent B1 is prepared by the following method with phenolic resin;
(1) And (3) batching: weighing (2, 3-dihydroxynaphthyl) tetraphenyl phosphonium bromide, MEH-7851SS and acetone according to the weight ratio of 1:12:30.
(2) The reaction: and (3) carrying out reflux stirring reaction on the mixture of the ingredients (1) in a constant temperature circulator at 150 ℃ for 5 hours under nitrogen atmosphere, and then carrying out reduced pressure distillation at 80 ℃ for 8 hours under-0.2 MPa to obtain the (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide precursor.
(3) And (3) drying: and (3) placing the (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide precursor prepared in the reaction (2) into a vacuum drying oven with the pressure of-0.096 MPa, and drying at 80 ℃ for 3 hours to prepare the (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide modified curing agent B1.
Preparation example 2
Tetraphenylphosphonium salt complex modified curing agent B2, wherein the hydroxyl equivalent is 200 g/equivalent, the viscosity is 0.65 Pa.s at 150 ℃, and the tetraphenylphosphonium salt complex modified curing agent B2 is prepared by the following method with phenolic resin;
(1) And (3) batching: weighing (2, 3-dihydroxynaphthyl) tetraphenyl phosphonium bromide, MEH-7851SS and tetrahydrofuran according to the weight ratio of 1:12:30.
(2) The reaction: and (3) carrying out reflux stirring reaction on the mixture of the ingredients (1) in a constant temperature circulator at 150 ℃ for 5 hours under nitrogen atmosphere, and then carrying out reduced pressure distillation at 80 ℃ for 8 hours under-0.2 MPa.
(3) And (3) drying: and (3) placing the tetraphenylphosphonium salt complex modified curing agent prepared in the reaction (2) into a vacuum drying oven with the pressure of-0.096 MPa, and drying at 80 ℃ for 3 hours to prepare the tetraphenylphosphonium salt complex modified curing agent B2.
Preparation example 3
Tetraphenylphosphonium salt complex modified curing agent B3, wherein the hydroxyl equivalent is 200 g/equivalent, the viscosity is 0.6 Pa.s at 150 ℃, and the tetraphenylphosphonium salt complex modified curing agent B3 is prepared by the following method with phenolic resin;
(1) And (3) batching: (2, 3-dihydroxynaphthyl) tetraphenyl phosphonium bromide, MEH-7851SS and acetone according to the weight ratio of 1:15:30.
(2) The reaction: and (3) carrying out reflux stirring reaction on the mixture of the ingredients (1) in a constant temperature circulator at 150 ℃ for 5 hours under nitrogen atmosphere, and then carrying out reduced pressure distillation at 80 ℃ for 8 hours under-0.2 MPa.
(3) And (3) drying: and (3) placing the tetraphenylphosphonium salt complex modified curing agent prepared in the reaction (2) into a vacuum drying oven with the pressure of-0.096 MPa, and drying at 80 ℃ for 3 hours to prepare the tetraphenylphosphonium salt complex modified curing agent B3.
Preparation example 4
Tetraphenylphosphonium salt complex modified curing agent B4, the hydroxyl equivalent is 90 g/equivalent, and the viscosity is 0.5 Pa.s at 150 ℃.
The same as in preparation example 1, except that the hydroxyl equivalent of the phenolic resin was 95 g/equivalent. And obtaining the tetraphenylphosphonium salt complex modified curing agent B4.
Comparative preparation example 1
The triphenylphosphine salt complex modified curing agent DB1 has a hydroxyl equivalent of 195 g/equivalent and a viscosity of 0.7 Pa.s at 150 ℃, and the preparation method is the same as that of B1, except that (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide is replaced by (2, 3-dihydroxynaphthyl) triphenylphosphonium bromide.
The epoxy resin compositions of examples and comparative examples of the present invention are shown in tables 1 and 2.
TABLE 1
Table 1 (subsequent)
TABLE 2
Test case
The epoxy compositions were prepared by the following methods according to the above-mentioned examples and comparative examples:
the components in Table 1, table 1 (follow) and Table 2 were pulverized and uniformly mixed at room temperature by a pulverizer, mixed at 80℃for 8 minutes on an open mill, and then pulverized, and mixed to obtain an epoxy composition.
Viscosity of the composition:
the test was performed using a cone-plate viscometer at 150℃and 400rpm.
The epoxy composition was prepared into an epoxy resin sample by the following method:
the compositions of tables 1, 1 (and 2) were placed on a QFN copper frame (258 mm. Times.78 mm) and encapsulated by a transfer molding process at 175℃and after demolding, the encapsulated samples were post-cured at 175℃for 4 hours to obtain epoxy resin samples.
The above samples were subjected to performance testing, wherein the cure time, warpage and surface porosity are shown in table 3.
Warpage test: and (3) testing the epoxy resin sample by using a warpage radian tester, wherein the plastic package body faces upwards during testing, the two ends of the plastic package body are tilted downwards to be positive, and the two ends of the plastic package body are tilted upwards to be negative.
Surface air hole test:
the epoxy resin sample was placed on a QFN copper frame (258 mm. Times.78 mm), and the package was carried out by a transfer molding process at 175℃and, after releasing the mold, the blow hole observation was carried out using an optical microscope.
TABLE 3 Table 3
As can be seen from the results of Table 1, the examples 1-3 and 5-8 of the present invention have significantly better effects, the viscosity and curing time are more suitable, the fluidity is better, the degree of warpage is smaller, the absolute value of warpage is not more than 1.2mm, the surface air holes are not more than 21, and the diameter is not more than 80. Mu.m.
In comparative examples 1 to 6, the number of surface pores was 30 or more, and the pore diameters were large and were 110 μm or more; in addition, the warpage degree of comparative examples 1, 2, 4-5 is greater than 1.5mm, severely affecting use.
Therefore, the epoxy resin composition and the epoxy resin provided by the invention have excellent application in the field of QFN packaging.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. An epoxy resin composition characterized in that it comprises, in parts by weight: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenylphosphonium salt complex modified curing agent, 0.1-1.5 parts of accelerator, 80-90 parts of inorganic filler, 0.5-1.5 parts of flame retardant, 0.03-1.5 parts of release agent, 0.05-0.5 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier;
the epoxy resin is selected from at least two of phenolic aldehyde type epoxy resin, bisphenol A type structural epoxy resin, biphenyl type structural epoxy resin, naphthalene type structural epoxy resin, o-cresol type structural epoxy, alicyclic epoxy resin, bisphenol F type structural epoxy resin, DCPD type structural epoxy resin and multifunctional group type structural epoxy resin;
the preparation method of the tetraphenylphosphonium salt complex modified curing agent comprises the following steps:
(1) And (3) batching: uniformly mixing the tetraphenylphosphonium salt complex and phenolic resin in the presence of a solvent to obtain a mixture;
(2) The reaction: after the mixture is reacted in a protective atmosphere, removing the solvent to obtain a tetraphenylphosphonium salt complex modified curing agent precursor;
(3) And (3) drying: drying the precursor of the tetraphenylphosphonium salt complex modified curing agent to prepare the tetraphenylphosphonium salt complex modified curing agent;
the hydroxyl equivalent of the phenolic resin is 100-210 g/equivalent;
the inorganic filler is crystalline and/or fused spherical.
2. The composition of claim 1, wherein the composition comprises, in parts by weight: 4-8 parts of epoxy resin, 3-7.5 parts of tetraphenylphosphonium salt complex modified curing agent, 0.3-1.2 parts of accelerator, 85-89 parts of inorganic filler, 1.5 parts of flame retardant, 0.03-1 part of release agent, 0.05-0.2 part of inorganic ion scavenger, 0.5-1 part of coupling agent and 0.4-1 part of modifier;
and/or the composition further comprises 0.2-0.8 parts of a colorant.
3. The composition of claim 1, wherein the composition further comprises 0.3-0.7 parts by weight of a colorant.
4. The composition of claim 1 or 2, wherein the epoxy resin has an epoxy value of 0.3-0.8 and an epoxy equivalent of 160-280 g/equivalent.
5. The composition of claim 1, wherein the tetraphenylphosphonium salt complex modified curative has a hydroxyl equivalent weight of 90-200 g/equivalent and a viscosity of 0.2-2 Pa-s at 150 ℃.
6. The composition of claim 1, wherein in step (1), the tetraphenylphosphonium salt complex is selected from (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide and/or (2, 3-dihydroxynaphthyl) tetraphenylphosphonium chloride;
and/or the phenolic resin is selected from at least one of multifunctional phenolic resin, linear phenolic resin, biphenyl phenolic resin and XY-LOK phenolic resin;
and/or the mass ratio of the tetraphenylphosphonium salt complex to the phenolic resin to the solvent is 1 (5-25): 20-30;
and/or, in the step (1), the solvent is selected from at least one of acetone, tetrahydrofuran and N, N-dimethylformamide;
and/or, in step (2), the reaction conditions include: under stirring, the temperature is 120-160 ℃, the pressure is-0.1 MPa to-0.5 MPa, and the reaction is carried out for 2-36h;
and/or, the conditions for removing the solvent comprise: distilling under reduced pressure at 70-90deg.C for 2-15 hr;
and/or, in step (3), the drying conditions include: drying at-0.096 MPa to 0MPa and 50-120deg.C for 1-4 hr.
7. The composition according to claim 1 or 2, wherein the mass ratio of tetraphenylphosphonium salt complex, phenolic resin and solvent is 1 (10-20): 30.
8. The composition according to claim 1 or 2, wherein the inorganic filler is selected from at least one of silica, alumina and magnesia;
and/or the inorganic filler has a particle size of 0.1 to 75 μm;
and/or the accelerator is selected from at least one of an organic phosphorus compound, an imidazole compound, a tertiary amine compound and derivatives thereof, an aromatic ureido derivative and an aliphatic ureido derivative;
and/or the flame retardant is selected from at least one of metal hydroxide, hydrated metal compound, metal oxide, molybdate, borate, phosphate, phosphorus-containing compound and nitrogen-containing compound;
and/or the release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax;
and/or the inorganic ion scavenger is selected from at least one of hydrated metal oxides, acidic metal salts, and aluminum magnesium compounds;
and/or the coupling agent is selected from at least one of gamma-epoxypropyl ether trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane;
and/or the modifier is selected from rubber and/or organosilane.
9. The composition according to claim 1 or 2, wherein the inorganic filler has a particle size of 0.1-55 μm.
10. The composition according to claim 1 or 2, wherein the inorganic filler has a particle size of 0.1-45 μm.
11. A method of preparing an epoxy resin, the method comprising: heating and mixing the epoxy resin composition according to any one of claims 1-10 to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
12. The method of manufacturing according to claim 11, wherein the conditions of the heated mixing include: heating and mixing at 80-110deg.C for 7-9min;
the molding conditions include: molding at 170-180deg.C and 12-16 MPa.
13. An epoxy resin prepared by the method of claim 11 or 12.
14. Use of the composition of any one of claims 1-10 in QFN packaging and/or DFN packaging.
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