CN114276653A - 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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- CN114276653A CN114276653A CN202111654717.4A CN202111654717A CN114276653A CN 114276653 A CN114276653 A CN 114276653A CN 202111654717 A CN202111654717 A CN 202111654717A CN 114276653 A CN114276653 A CN 114276653A
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- epoxy resin
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- composition
- salt complex
- tetraphenylphosphonium
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 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 45
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 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 8
- 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 7
- 239000003063 flame retardant Substances 0.000 claims abstract description 7
- 239000002516 radical scavenger Substances 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims description 26
- -1 (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide Chemical group 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-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
- 239000002245 particle Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 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
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 150000002460 imidazoles Chemical class 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
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 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
- 239000005060 rubber Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000012178 vegetable wax Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 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 2
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000005022 packaging material Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 230000009044 synergistic interaction Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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
- 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
- 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
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 238000001291 vacuum drying 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 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
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000010992 reflux Methods 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
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of semiconductor packaging materials, and discloses an epoxy resin composition and application thereof, an 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 tetraphenyl phosphonium 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 and high fluidity, and can effectively inhibit the generation of pores when the epoxy resin is prepared; the components in the composition are proportioned to realize synergistic interaction, the stress and the 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 and application thereof, an epoxy resin and a preparation method thereof.
Background
A large-area exposed bonding pad is usually arranged at the central position of the bottom of a Quad Flat No-lead package (QFN) and used for conducting heat, and the bonding pad can be used as a direct heat dissipation channel and used for conducting heat generated by the chip in a package body during working; the pad is welded directly on the circuit board after surface mounting, and the PCB heat dissipation hole can absorb unnecessary heat to the copper earth plate to unnecessary consumption diffusion, has greatly promoted the thermal diffusivity of chip. QFN packages differ from conventional DIP or SOP packages with euro-wing pins in that they also provide good electrical performance due to the short electrical path between the pins and the PCB pads, low self-inductance and low wiring resistance within the package after surface mounting.
In order to better satisfy the requirement of fluidity, 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 the combination of the two will cause the epoxy resin composition to have high stress and low viscosity, thereby easily causing package warpage and air holes to exceed the standard.
Disclosure of Invention
The invention aims to solve the problems of package body warpage and air hole exceeding standards in the prior art, and provides an epoxy resin composition, application thereof, an 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, comprising: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenyl phosphonium 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 present invention provides a method for producing an epoxy resin, characterized in that the method comprises: and heating and mixing the epoxy resin composition to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
The third aspect of the present invention provides an epoxy resin, wherein the epoxy resin is prepared by the above method.
In a fourth aspect, the present invention provides a use of the above composition or epoxy resin in QFN and/or DFN packaging.
Through the technical scheme, the invention has the following beneficial effects: the epoxy resin contains a specific tetraphenylphosphonium complex modified curing agent, so that the composition has relatively proper viscosity and curing speed, and high fluidity, and can effectively inhibit the generation of pores when the epoxy resin is prepared; furthermore, the components in the composition are in a synergistic ratio, the stress and the 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an epoxy resin composition, which is characterized by comprising the following components in parts by weight: 3-9 parts of epoxy resin, 2.5-8 parts of tetraphenyl phosphonium 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.
According to the invention, the components in the composition are proportioned to realize synergistic effect, so that the stress of the composition can be reduced, the viscosity and the fluidity of the composition can be improved, and the epoxy resin prepared from the composition has the characteristics of low warpage and less surface pores.
According to the invention, the composition comprises, in parts by weight: 4-8 parts of epoxy resin, 3-7.5 parts of tetraphenyl phosphonium 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 trapping agent, 0.5-1 part of coupling agent and 0.4-1 part of modifier.
In the invention, when the components in the composition meet the mixture ratio, the epoxy resin prepared from the composition has more excellent comprehensive performance.
Further, the composition also comprises 0.2 to 0.8 parts of colorant, and preferably comprises 0.3 to 0.7 parts of colorant.
In the present invention, the colorant is not particularly limited and may be selected as needed, and for example, the colorant in the present invention is carbon black.
According to the invention, the epoxy value of the epoxy resin is 0.3-0.8 and the epoxy equivalent is 160-280 g/eq.
In the present invention, when the epoxy value, epoxy equivalent and molecular weight of the epoxy resin satisfy the above ranges, the composition can have suitable viscosity and fluidity, and the epoxy resin prepared from the composition has the characteristics of low warpage and few pores on the surface.
Further, the epoxy value of the epoxy resin is 0.48-0.63, and the epoxy equivalent is 160-210.
According to the invention, the preparation method of the tetraphenylphosphonium salt complex modified curing agent comprises the following steps:
(1) preparing materials: in the presence of a solvent, uniformly mixing a tetraphenylphosphonium complex and phenolic resin to obtain a mixture;
(2) reaction: after the mixture is reacted under a protective atmosphere, removing the solvent to obtain a tetraphenylphosphonium salt complex modified curing agent precursor;
(3) and (3) drying: and drying the tetraphenylphosphonium salt complex modified curing agent precursor to prepare the tetraphenylphosphonium salt complex modified curing agent.
In the present invention, the modified curing agent obtained by modifying a phenol resin with a tetraphenylphosphonium salt complex by the above method can adjust the viscosity of the composition to an appropriate level in an epoxy resin composition, thereby improving the fluidity of the epoxy resin composition.
According to the invention, the hydroxyl equivalent weight of the phenolic resin is 100-210 g/equivalent.
Further, the phenolic resin has a hydroxyl equivalent weight of 150-205 g/eq.
According to the invention, the tetraphenylphosphonium salt complex modified curing agent has a hydroxyl equivalent weight of 90-200 g/equivalent and a viscosity of 0.2-2 pas at 150 ℃.
In the present invention, when the viscosity of the tetraphenylphosphonium salt complex-modified curing agent satisfies the above range, the composition has a suitable viscosity and good fluidity, and further, an epoxy resin prepared from the composition has characteristics of low warpage and few bubbles on the surface.
Further, the tetraphenylphosphonium salt complex-modified curing agent has a hydroxyl equivalent of 140-195 g/equivalent and a viscosity of 0.5 to 1.5 Pa.s at 150 ℃.
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 phenol resin is at least one selected from the group consisting of a multifunctional phenol resin, a novolac phenol resin, a biphenyl type phenol resin and an XY-lock phenol resin.
In the present invention, when the tetraphenylphosphonium salt complex and the phenol resin are selected from the above-mentioned groups, the modified curing agent obtained has the characteristics of appropriate viscosity and appropriate stress.
According to the invention, the mass ratio of the tetraphenylphosphonium salt complex to the phenolic resin to the solvent is 1 (5-25) to (20-30).
In the present invention, when the tetraphenylphosphonium salt complex, the phenol resin and the solvent satisfy the above ranges, the tetraphenylphosphonium salt complex and the phenol resin can be sufficiently and uniformly dissolved so that the tetraphenylphosphonium salt complex-modified curing agent has an appropriate viscosity.
According to the invention, the mass ratio of the tetraphenylphosphonium salt complex to the phenolic resin to the solvent is 1 (10-20): 30.
According to the present 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: under stirring, the temperature is 120 ℃ and 160 ℃, the pressure is-0.1 MPa to-0.5 MPa, and the reaction lasts for 2-36 h.
According to the invention, the conditions for removing the solvent comprise: distilling at 70-90 deg.C under reduced pressure for 2-15 h.
According to the invention, in step (3), drying is carried out for 1-4h at-0.096 MPa to 0MPa and at 50-120 ℃.
According to the present invention, the epoxy resin is selected from at least two of a phenol type epoxy resin, a bisphenol a type structure epoxy resin, a biphenyl type structure epoxy resin, a naphthalene type structure epoxy resin, an o-cresol type structure epoxy resin, a cycloaliphatic epoxy resin, a bisphenol F type structure epoxy resin, a DCPD type structure epoxy resin, and a multifunctional type structure epoxy resin.
In the invention, the epoxy resin is selected from at least two of the epoxy resins, so that the beneficial effects of high strength and low water absorption can be obtained.
According to the present invention, the inorganic filler is at least one selected from the group consisting of silica, alumina and magnesia.
In the present invention, the inorganic filler is selected from the above-mentioned kinds, and can have good fluidity.
According to the invention, the particle size of the inorganic filler is 0.1 to 75 μm.
In the invention, the particle size of the inorganic filler meets the 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 particle diameter of the inorganic filler is 0.1 to 55 μm, more preferably 0.1 to 45 μm.
According to the invention, the inorganic filler is of crystalline and/or molten spherical type.
According to the present invention, the accelerator is selected from at least one of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and derivatives thereof, aromatic ureido derivatives, and aliphatic ureido derivatives.
In the present invention, the accelerator is selected from the above compounds, and synergistically acts with the tetraphenylphosphonium salt complex-modified curing agent to further improve the viscosity of the composition and to provide more suitable fluidity.
According to the present invention, the flame retardant is selected from at least one of metal hydroxides, hydrated metal compounds, metal oxides, molybdates, borates, phosphates, phosphorus-containing compounds, and nitrogen-containing compounds.
According to the invention, the release agent is selected from at least one of mineral waxes, vegetable waxes, polyethylene and polyamide waxes.
According to the present invention, the inorganic ion scavenger is at least one selected from the group consisting of a hydrated metal oxide, an acidic metal salt and an aluminum magnesium compound.
According to the invention, the coupling agent is selected from at least one of gamma-epoxypropylethertrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane.
According to the invention, the modifier is selected from rubbers and/or organosilanes.
The second aspect of the present invention provides a method for producing an epoxy resin, characterized in that the method comprises: and heating and mixing the epoxy resin composition to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
According to the invention, the conditions of said heating and mixing comprise: heating and mixing at 80-110 deg.C for 7-9 min.
In the present invention, the mixing apparatus is not particularly limited, and for example, the heating and mixing may be carried out in a two-roll mill, a single-screw extruder, a twin-screw extruder, a kneader, or a stirrer.
According to the invention, the forming conditions comprise: molding at 170-180 deg.C and 12-16 MPa.
The third aspect of the present invention provides an epoxy resin, wherein the epoxy resin is prepared by the above method.
In a fourth aspect, the present invention provides a use of the above composition or epoxy resin in QFN and/or DFN packaging.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
curing time: preheating an electric heating disc to 175 ℃, taking a certain amount of epoxy resin composition powder to be placed on the disc, starting to change the powder into fluid, timing by using a stopwatch, reading the time required for the powder to change into a gel state, repeating the operation twice in the same way, and taking the average value of the time as s;
viscosity: testing by a cone-plate viscometer under the test conditions of 150 ℃ and 400 rpm;
epoxy resin A:
o-cresol epoxy resin a1, CYDCN205, available from yueyang petrochemicals;
biphenyl type epoxy resin a2, YX4000, available from japan DIC corporation;
naphthalene structure-containing epoxy resin A3, HP4700, available from Nippon DIC;
bisphenol F epoxy resin A4, SQE-104, available from Shandong Shengquan chemical Co., Ltd;
bisphenol A epoxy resin A5, YL-6810, available from Mitsubishi, Japan;
tetraphenylphosphonium chloride complex a6, 5003, available from tokyo transaxle, tokyo;
acetone, available from semer fei biochemicals ltd;
curing agent:
multifunctional phenol-formaldehyde resin DB2, MEH-7851SS, available from Nippon Ming and Chemicals;
accelerator (b):
2-methylimidazole, available from four national chemical industry co;
aromatic dimethyl urea, U-CAT3512T, available from Mitsubishi, Japan;
inorganic filler:
fused sphere silica, available from Jiangsu Lineary technologies, Inc.;
fused angle silica available from Jiangsu Birui science and technology Ltd
Flame retardant:
nitrogen-containing phenol formaldehyde, PF8705, available from shengquan chemical corporation;
aluminum hydroxide, available from light metals japan;
releasing agent:
carnauba wax, purchased from a tree company;
glyceryl monostearate, available from alatin reagent, inc;
inorganic ion scavenger:
DHT-4A available from Nippon Kyoho chemical industries, Inc
Coupling agent:
KH560, available from cheng optical technology ltd, Jiangsu;
KH550, available from chenguan technologies ltd, jiang;
modifying agent:
carboxyl-terminated liquid nitrile rubber CTBN, available from the Dow group of America;
colorant:
carbon black, available from Shandong Deblue chemical Co., Ltd;
preparation example 1
Tetraphenylphosphonium salt complex modified curing agent B1, which has a hydroxyl equivalent of 200 g/equivalent and a viscosity of 0.7 Pa.s at 150 ℃, and is prepared from tetraphenylphosphonium salt complex and phenolic resin by the following method;
(1) preparing materials: weighing (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide, MEH-7851SS and acetone according to the weight ratio of 1: 12: 30.
(2) reaction: and (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide precursor is obtained by refluxing and stirring the mixture of the ingredient (1) in a constant temperature circulator at 150 ℃ for 5h under nitrogen atmosphere, and then distilling the mixture at 80 ℃ under reduced pressure for 8h under-0.2 MPa.
(3) And (3) drying: the (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide precursor prepared in the reaction (2) was placed in a vacuum oven at-0.096 MPa and dried at 80 ℃ for 3 hours to prepare (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide modified curing agent B1.
Preparation example 2
Tetraphenylphosphonium salt complex modified curing agent B2, which has a hydroxyl equivalent of 200 g/equivalent and a viscosity of 0.65 pas at 150 ℃, and is prepared from tetraphenylphosphonium salt complex and phenolic resin by the following method;
(1) preparing materials: weighing (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide, MEH-7851SS and tetrahydrofuran according to the weight ratio of 1: 12: 30.
(2) reaction: the mixture of the ingredient (1) is refluxed, stirred and reacted in a constant temperature circulator at the temperature of 150 ℃ for 5 hours under the nitrogen atmosphere, and then is distilled under the pressure of minus 0.2MPa at the temperature of 80 ℃ for 8 hours.
(3) And (3) drying: and (3) putting 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 the temperature of 80 ℃ for 3 hours to prepare the tetraphenylphosphonium salt complex modified curing agent B2.
Preparation example 3
Tetraphenylphosphonium salt complex modified curing agent B3, which has a hydroxyl equivalent of 200 g/equivalent and a viscosity of 0.6 pas at 150 ℃, and is prepared from tetraphenylphosphonium salt complex and phenolic resin by the following method;
(1) preparing materials: (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide, MEH-7851SS, acetone in a weight ratio of 1: 15: 30.
(2) reaction: the mixture of the ingredient (1) is refluxed, stirred and reacted in a constant temperature circulator at the temperature of 150 ℃ for 5 hours under the nitrogen atmosphere, and then is distilled under the pressure of minus 0.2MPa at the temperature of 80 ℃ for 8 hours.
(3) And (3) drying: and (3) putting 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 the temperature of 80 ℃ for 3 hours to prepare the tetraphenylphosphonium salt complex modified curing agent B3.
Preparation example 4
Tetraphenylphosphonium salt complex modified curing agent B4, hydroxyl equivalent of 90 g/equivalent, viscosity of 0.5 pas at 150 ℃.
In accordance with preparation example 1, except that the phenolic resin had a hydroxyl equivalent of 95 g/equivalent. To obtain tetraphenylphosphonium salt complex modified curing agent B4.
Comparative preparation example 1
A curing agent DB1 modified with a triphenyl phosphonium salt complex having a hydroxyl equivalent of 195 g/equivalent and a viscosity of 0.7 pas at 150 ℃ was prepared in accordance with B1 except that (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide was replaced with (2, 3-dihydroxynaphthyl) triphenylphosphonium bromide.
The formulations of the epoxy resin compositions of the examples of the present invention and the comparative examples are shown in tables 1 and 2.
TABLE 1
TABLE 1 (continuation)
TABLE 2
Test example
The epoxy compositions were prepared by the above-described compounding examples and comparative examples in the following manner:
the components in table 1, table 1 (continuous) and table 2 were pulverized and mixed uniformly at room temperature using a pulverizer, mixed for 8min at 80 ℃ on an open mill, and then pulverized and mixed to obtain the epoxy composition.
Viscosity of the composition:
the test conditions were 150 ℃ and 400rpm using a cone and plate viscometer.
The epoxy resin samples were prepared from the above epoxy composition by the following method:
the compositions in table 1, table 1 (continuous) and table 2 were placed on a QFN copper frame (258mm × 78mm) and encapsulated by transfer molding 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 tests in which the curing time, warpage and surface porosity are shown in Table 3.
And (3) warpage testing: and (3) carrying out warpage test on the epoxy resin sample by using a warpage tester, wherein the surface of the plastic package body is upward during the test, the two ends of the plastic package body are downward warped to be positive, and the two ends of the plastic package body are upward warped to be negative.
Surface pore test:
the epoxy resin sample was placed on a QFN copper frame (258mm × 78mm), packaged by transfer molding at 175 ℃, and after demolding, the stomata were observed using an optical microscope.
TABLE 3
As can be seen from the results in Table 1, examples 1 to 3 and 5 to 8 of the present invention have significantly better effects, are suitable for the viscosity and curing time to have better fluidity, have a smaller warpage degree, have an absolute value of warpage of not more than 1.2mm, have a surface pore volume of not more than 21, and have a diameter of not more than 80 μm.
In comparative examples 1 to 6, the number of surface pores was 30 or more, and the diameters of pores were 110 μm or more; in addition, the warpage degree of comparative examples 1, 2, 4-5 is more than 1.5mm, which seriously affects the use.
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 above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. 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 tetraphenyl phosphonium 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.
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 tetraphenyl phosphonium salt complex modified curing agent, 0.3-1.2 parts of accelerator, 85-89 parts of inorganic filler, 0.03-1 part of release agent, 0.05-0.2 part of inorganic ion trapping agent, 0.5-1 part of coupling agent and 0.4-1 part of modifier;
preferably, the composition further comprises 0.2 to 0.8 parts, preferably 0.3 to 0.7 parts of a colorant.
3. The composition as claimed in claim 1 or 2, wherein the epoxy resin has an epoxy value of 0.3 to 0.8 and an epoxy equivalent of 160-280 g/eq.
4. The composition of any of claims 1-3, wherein the tetraphenylphosphonium salt complex modified curing agent is prepared by a process comprising the steps of:
(1) preparing materials: in the presence of a solvent, uniformly mixing a tetraphenylphosphonium complex and phenolic resin to obtain a mixture;
(2) reaction: after the mixture is reacted under a protective atmosphere, removing the solvent to obtain a tetraphenylphosphonium salt complex modified curing agent precursor;
(3) and (3) drying: drying the tetraphenylphosphonium salt complex modified curing agent precursor to prepare a tetraphenylphosphonium salt complex modified curing agent;
preferably, the phenolic resin has a hydroxyl equivalent weight of 100-210 g/equivalent;
preferably, the tetraphenylphosphonium salt complex modified curing agent has a hydroxyl equivalent weight of 90 to 200 g/equivalent and a viscosity of 0.2 to 2 pas at 150 ℃.
5. The composition according to claim 4, wherein in step (1), the tetraphenylphosphonium salt complex is selected from (2, 3-dihydroxynaphthyl) tetraphenylphosphonium bromide and/or (2, 3-dihydroxynaphthyl) tetraphenylphosphonium chloride;
preferably, the phenolic resin is selected from at least one of multifunctional phenolic resin, linear phenolic resin, biphenyl type phenolic resin and XY-lock phenolic resin;
preferably, the mass ratio of the tetraphenylphosphonium salt complex to the phenolic resin to the solvent is 1 (5-25): 20-30, preferably 1 (10-20): 30;
preferably, in the step (1), the solvent is at least one selected from the group consisting of acetone, tetrahydrofuran and N, N-dimethylformamide;
preferably, in step (2), the reaction conditions include: under stirring, the temperature is 120 ℃ and 160 ℃, the pressure is-0.1 MPa to-0.5 MPa, and the reaction lasts for 2-36 h;
preferably, the solvent removal conditions include: distilling at 70-90 deg.C under reduced pressure for 2-15 h;
preferably, in the step (3), the drying conditions include: drying at-0.096 MPa to 0MPa and 50-120 deg.C for 1-4 h.
6. The composition according to any one of claims 1 to 5, wherein the epoxy resin is selected from at least two of a phenol type epoxy resin, a bisphenol A type structure epoxy resin, a biphenyl type structure epoxy resin, a naphthalene type structure epoxy resin, an o-cresol type structure epoxy resin, a cycloaliphatic epoxy resin, a bisphenol F type structure epoxy resin, a DCPD type structure epoxy resin, and a multifunctional type structure epoxy resin;
preferably, the inorganic filler is selected from at least one of silica, alumina and magnesia;
preferably, the inorganic filler has a particle size of 0.1 to 75 μm, preferably 0.1 to 55 μm, more preferably 0.1 to 45 μm;
preferably, the accelerator is selected from at least one of organic phosphorus compounds, imidazole compounds, tertiary amine compounds and derivatives thereof, aromatic ureido derivatives, and aliphatic ureido derivatives;
preferably, the flame retardant is selected from at least one of metal hydroxides, hydrated metal compounds, metal oxides, molybdates, borates, phosphates, phosphorus-containing compounds, and nitrogen-containing compounds;
preferably, the release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax;
preferably, the inorganic ion scavenger is selected from at least one of a hydrated metal oxide, an acidic metal salt and an aluminum magnesium compound;
preferably, the coupling agent is selected from at least one of gamma-epoxypropylethertrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-aminopropyltrimethoxysilane;
preferably, the modifier is selected from rubbers and/or organosilanes.
7. A method of preparing an epoxy resin, the method comprising: heating and mixing the epoxy resin composition of any one of claims 1 to 6 to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
8. The production method according to claim 7, wherein the conditions for the heating and mixing include: heating and mixing at 80-110 deg.C for 7-9 min;
the molding conditions include: molding at 170-180 deg.C and 12-16 MPa.
9. An epoxy resin prepared by the method of claim 7 or 8.
10. Use of a composition according to any one of claims 1 to 6 in QFN packaging and/or DFN packaging.
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