CN114276652B - Epoxy resin composition and application thereof, epoxy resin and preparation method and application thereof - Google Patents
Epoxy resin composition and application thereof, epoxy resin and preparation method and application thereof Download PDFInfo
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- CN114276652B CN114276652B CN202111652386.0A CN202111652386A CN114276652B CN 114276652 B CN114276652 B CN 114276652B CN 202111652386 A CN202111652386 A CN 202111652386A CN 114276652 B CN114276652 B CN 114276652B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 139
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 139
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000004593 Epoxy Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 16
- 239000004305 biphenyl Substances 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229920001568 phenolic resin Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- -1 imidazole compound Chemical class 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000001993 wax Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-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
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 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
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000012184 mineral wax Substances 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012178 vegetable wax Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 1
- 238000005476 soldering Methods 0.000 abstract description 18
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920006336 epoxy molding compound Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 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 thermosetting plastics, and discloses an epoxy resin composition, an epoxy resin, a preparation method and application thereof. The composition comprises the following components in parts by weight: 4-15 parts of organosilicon modified biphenyl type epoxy resin, 2-10 parts of curing agent, 0.01-2 parts of accelerator, 60-90 parts of inorganic filler, 0.05-3 parts of release agent and 0.01-2 parts of low-stress modifier; wherein the usage amount of the organosilicon modified biphenyl type epoxy resin and the curing agent is such that the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the curing agent is 0.8-1.2. The epoxy resin composition contains the organosilicon modified biphenyl type epoxy resin, and can be matched with other components in a synergistic way, so that the epoxy resin prepared from the epoxy resin composition has excellent mechanical property and low linear expansion coefficient, and has low warpage and no layering phenomenon after reflow soldering.
Description
Technical Field
The invention relates to the technical field of thermosetting plastics, in particular to an epoxy resin composition, an epoxy resin, a preparation method and application thereof.
Background
Compared with the QFN of the previous generation packaging form, the BGA form fully utilizes the bottom area to form more interconnection pins, so that the area utilization rate of the packaging is finally improved, and the plane size of the product is reduced.
The final process flow of the BGA product is to solder on a circuit board in a reflow soldering mode to complete interconnection of pins, and the peak temperature range of heating is just larger than 220 ℃ based on the fact that the melting point of a tin ball is about 220 ℃. Warpage of the BGA may occur at any time during the heating and subsequent cooling cycles. This situation may cause the BGA to have a bow with a lower center and two raised sides.
Since BGA products are mainly made of plasticAnd the packaging material, the chip and the PCB. In the reflow soldering process, the BGA product is warped due to the fact that the linear expansion coefficients of the plastic package material, the chip and the PCB are inconsistent at different temperatures. The chip has smaller volume in the BGA product, so that the expansion coefficients of the injection molding sealing material and the PCB after reflow soldering are more relevant for better solving the problem of warpage of the BGA product after reflow soldering. The closer the expansion coefficients of the plastic package material and the PCB are after reflow soldering, the smaller the warpage of the BGA product is after reflow soldering. Tg of PCB board for BGA product is 180-260 deg.C, linear expansion coefficient alpha 1 Between 4 and 8, the Tg of the epoxy molding compound for BGA is between 100 and 160 ℃, and the linear expansion coefficient alpha is 1 Between 10 and 18, the linear expansion coefficient alpha of the two materials is between 1 The BGA products are extremely easy to warp after reflow soldering because of the large phase difference.
To reduce the linear expansion coefficient alpha between the plastic package material and the PCB 1 The plastic package material is modified by introducing the organosilicon modified epoxy resin, and the organosilicon has the advantages of good thermal stability, low linear expansion coefficient, oxidation resistance, high dielectric strength and the like. The organic silicon modified epoxy resin can reduce the internal stress of the epoxy resin and increase the toughness of the epoxy resin, but the excessive addition can cause the deterioration of the mechanical property and the adhesive force of the epoxy resin.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical properties and poor adhesive force of epoxy resin in the prior art, and provides an epoxy resin composition, an epoxy resin, a preparation method and application 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: 4-15 parts of organosilicon modified biphenyl type epoxy resin, 2-10 parts of curing agent, 0.01-2 parts of accelerator, 60-90 parts of inorganic filler, 0.05-3 parts of release agent and 0.01-2 parts of low-stress modifier;
wherein the ratio of the epoxy equivalent of the organosilicon modified biphenyl type epoxy resin to the hydroxyl equivalent in the curing agent is 0.8-1.2.
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 mixing the epoxy resin composition to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
In a third aspect, the present invention provides an epoxy resin, characterized in that the epoxy resin is prepared by the above method.
A fourth aspect of the present invention provides the use of the epoxy resin composition and/or epoxy resin described above in chip packaging.
Through the technical scheme, the epoxy resin composition, the epoxy resin and the preparation method and application thereof provided by the invention have the following beneficial technical effects: the epoxy resin composition provided by the invention contains the organosilicon modified biphenyl type epoxy resin, and can be matched with other components in a synergistic way, so that the epoxy resin prepared from the epoxy resin composition has excellent mechanical properties, low linear expansion coefficient and low warpage without layering phenomenon after reflow soldering.
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: 4-15 parts of organosilicon modified biphenyl type epoxy resin, 2-10 parts of curing agent, 0.01-2 parts of accelerator, 60-90 parts of inorganic filler, 0.05-3 parts of release agent and 0.01-2 parts of low-stress modifier;
wherein the ratio of the epoxy equivalent of the organosilicon modified biphenyl type epoxy resin to the hydroxyl equivalent in the curing agent is 0.8-1.2.
In the epoxy resin composition, the organic silicon modified biphenyl type epoxy resin and other components are synergistically enhanced, wherein the organic silicon modified biphenyl type epoxy resin has the advantages of good thermal stability, low surface energy, low-temperature flexibility, weather resistance, hydrophobicity, oxidation resistance and high dielectric strength, the internal stress of the epoxy resin can be effectively reduced, the toughness and the high temperature resistance of the epoxy resin are improved, and the epoxy resin prepared from the epoxy resin composition has excellent mechanical properties, low linear expansion coefficient and low warpage without layering phenomenon after reflow soldering, and the ratio of the epoxy equivalent of the organic silicon modified biphenyl type epoxy resin to the hydroxyl equivalent in a curing agent is within the range of 0.8-1.2.
According to the invention, the composition comprises, in parts by weight: 4-10 parts of organosilicon modified biphenyl type epoxy resin, 3-8 parts of curing agent, 0.1-0.3 part of accelerator, 82-86 parts of inorganic filler, 0.1-0.5 part of release agent and 0.1-0.5 part of low-stress modifier.
In the invention, when each component in the epoxy resin composition meets the above range, the prepared epoxy resin has more excellent comprehensive performance.
Further, the composition further comprises 0.1 to 0.5 parts of a colorant.
In the present invention, the colorant is not particularly limited, and may be selected according to actual needs, and carbon black is preferred in the present invention.
Further, the composition further comprises 0.2 to 0.4 parts of a colorant.
Further, the ratio of the epoxy equivalent of the organosilicon modified biphenyl type epoxy resin to the hydroxyl equivalent in the curing agent is 0.9-1.15.
According to the invention, the preparation method of the organosilicon modified biphenyl type epoxy resin comprises the following steps:
(1) And (3) batching: uniformly mixing the organosilicon modified epoxy resin, the biphenyl epoxy resin and the first solvent to obtain a mixture;
(2) The reaction: removing the first solvent after the mixture is subjected to a first reaction to obtain an organosilicon modified biphenyl type epoxy resin precursor;
(3) And (3) drying: and drying the organosilicon modified biphenyl type epoxy resin precursor to obtain the organosilicon modified biphenyl type epoxy resin.
Further, the epoxy value of the organosilicon modified epoxy resin is 0.42-0.54 equivalent/100 g, the epoxy equivalent is 185-238 g/equivalent, and the viscosity at 25 ℃ is 11000-14000 mPa.s.
Further, the epoxy value of the organosilicon modified biphenyl type epoxy resin is 0.52-0.55 equivalent/100 g, the epoxy equivalent is 180-192 g/equivalent, the viscosity at 150 ℃ is 100-105 mPa.s, and the melting point is 105-107 ℃.
According to the invention, the weight ratio of the organosilicon modified epoxy resin to the biphenyl epoxy resin to the first solvent is 1: (5-25): (25-30).
In the invention, when the weight ratio of the organosilicon modified epoxy resin to the biphenyl epoxy resin to the first solvent is 1: (5-25): and (25-30), fully dissolving the organosilicon modified epoxy resin and the biphenyl epoxy resin, and ensuring uniform resin mixing.
Further, the weight ratio of the organosilicon modified epoxy resin to the biphenyl epoxy resin to the first solvent is 1: (10-20): 30.
in the invention, the epoxy value of the biphenyl type epoxy resin is 170-195 equivalent/100 g, the epoxy equivalent is 0.52-0.58 g/equivalent, the viscosity at 150 ℃ is 105-110 mPa.s, and the melting point is 105-112 ℃.
In the present invention, the type of the first solvent is not particularly limited, and different solvents may be selected according to the type of the epoxy resin, and may be methanol, ethanol or acetone, for example, and preferably methanol.
According to the present invention, in step (2), the conditions of the first reaction include: reacting for 2-36 hours at 120-160 ℃ under stirring; the conditions for removing the first solvent include: vacuum distilling at 70-90deg.C and-0.01-0.9 MPa for 2-15 hr.
According to the present invention, in step (3), the drying conditions include: drying at 50-190 deg.C under-0.01-0.9 MPa for 1-4 hr.
In the present invention, the source of the silicone-modified epoxy resin is not particularly limited, and for example, it may be purchased from the market or homemade, and preferably, it is prepared according to the following method:
the organic siloxane, the epoxy resin and the second solvent are mixed according to the weight ratio of 1: (10-20): 30 are placed in a three-neck flask, stirred and refluxed, the pH value is regulated to 5-6, the reflux temperature is 70-80 ℃, the reflux time is 3-6 hours, and the organosilicon modified epoxy resin is obtained by reduced pressure distillation after the reaction is completed.
In the present invention, the second solvent is not particularly limited, and may be at least one of methanol, ethanol, and water, for example.
According to the invention, the curing agent is selected from phenolic resins.
In the present invention, the phenolic resin has a hydroxyl equivalent weight of 140 to 160 g/equivalent, preferably 145 to 155 g/equivalent.
According to the present invention, the phenolic resin is at least one selected from the group consisting of bisphenol a type phenolic resin, XY-lock type phenolic resin, DCPD type phenolic resin, biphenyl type phenolic resin and multifunctional type phenolic resin.
According to the present invention, the accelerator is selected from at least one of an organic phosphorus compound, an imidazole compound and a tertiary amine compound.
According to the present invention, the inorganic filler is selected from at least one of silica, titania, alumina, and magnesia.
According to the present invention, the inorganic filler is at least one of a crystalline type, a molten angle type, and a molten spherical type.
According to the present invention, the release agent is at least one selected from the group consisting of mineral wax, vegetable wax, polyethylene and polyamide wax.
According to the invention, the low-stress modifier is at least one of liquid silicone oil, silicone rubber powder, propyl trimethoxysilane and gamma-amino propyl triethoxysilane.
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 mixing the epoxy resin composition to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
In the invention, the epoxy resin has high mechanical property, adhesive force and low linear expansion coefficient, and has low warpage and no layering phenomenon after reflow soldering.
In the present invention, the mode of mixing and molding is not particularly limited, and for example, the mixing and molding can be performed by heating using a processing device such as a twin roll mill, a single screw extruder, a twin screw extruder, a kneader, or a stirrer.
In the invention, the mixing conditions are as follows: mixing at 75-85deg.C for 7-9min, wherein the molding conditions include: shaping at 170-180deg.C and 180-190 t.
In a third aspect, the present invention provides an epoxy resin, characterized in that the epoxy resin is prepared by the above method.
A fourth aspect of the present invention provides the use of the epoxy resin composition and/or epoxy resin described above in chip packaging.
The present invention will be described in detail by examples. In the following examples of the present invention,
curing time: the electric heating plate is preheated to 175 ℃, a certain amount of powder of the epoxy resin composition is put on the plate, the time required for the powder to become gel state is read out by counting from the beginning of the powder becoming fluid by using a stopwatch, the same operation is repeated twice, and the average value is taken as the unit of s.
Spiral flow length: the test conditions were: temperature: 175 ℃, pressure: 7MPa, dwell time: 110s. The spiral flow length is a parameter for evaluating fluidity, and the larger the value is, the better the fluidity is, in cm.
Bending properties: the flexural strength of standard bars was measured in a universal tester, and the flexural strength is a parameter for evaluating the flexural resistance of an epoxy composition, and the larger the value is, the greater the strength of a packaged semiconductor device is in MPa.
Adhesive strength: the bonding strength between the sample and the copper sheet is measured by a universal testing machine, and the larger the bonding strength is, the better the bonding performance between the epoxy resin composition and the copper sheet is, and the unit is GPa.
Tg test: the Tg of the epoxy resin was measured in terms of degrees Celsius using TMA.
Warpage test: the test is carried out by adopting a warp radian tester, the warp is a parameter for evaluating the plane bending deformation of the packaging body, and the smaller the value is, the better the value is, and the unit is mm.
Coefficient of linear expansion alpha 1 : obtained by TMA test, unit is 10 -6 /℃。
The organosilicon modified epoxy resin has an epoxy value of 0.45 equivalent/100 g, an epoxy equivalent of 222 g/equivalent, a viscosity of 11000 mPa.s at 25 ℃, and a self-made preparation method as follows:
the weight ratio of the organic siloxane to the methanol to the 128 epoxy resin is 1:30:10 is placed in a three-neck flask, stirred and refluxed, the pH value is regulated to 6, the reflux temperature is 70 ℃, the reflux time is 3 hours, and the organosilicon modified epoxy resin is obtained by reduced pressure distillation after the reaction is completed.
Unmodified biphenyl epoxy resin D1, epoxy value 0.57, epoxy equivalent 175 g/equivalent, viscosity 108 mPa.s at 150℃and melting point 110℃available from Mitsubishi corporation of Japan under the trade name YX4000;
phenolic novolac resin, hydroxyl equivalent 150 g/equivalent, viscosity 8 mPa-s at 150 ℃, melting point 65 ℃, trade name MEH7851 from DIC corporation;
2-phenyl-4-methylimidazole, available from four kingdoms chemical industry Co., ltd;
fused silica of 75 μm particle size available from Jiangsu-associated technologies, inc.;
polyethylene wax, available from the chemical industry, co.ltd, of clariant;
propyltrimethoxysilane, available from Jiangsu morning light technologies, inc.;
carbon black, available from Shandong blue chemical Co., ltd.
Preparation example 1
The organosilicon modified biphenyl type epoxy resin A1 has an epoxy value of 0.52 equivalent/100, an epoxy equivalent of 192 g/equivalent and a viscosity of 100 mPa.s at 150 ℃ and is prepared by the following steps:
(1) The organic silicon modified epoxy resin EP1, biphenyl type epoxy resin and methanol are mixed according to the weight ratio of 1:10:30 was added to a three-necked flask and mixed to obtain a mixture.
(2) And (3) reacting the mixture in a constant temperature circulator at 120 ℃ for 8 hours, and then distilling the mixture at 70 ℃ under reduced pressure for 4 hours to remove methanol to obtain the organosilicon modified biphenyl type epoxy resin precursor.
(3) And (3) drying: and (3) placing the organosilicon modified biphenyl epoxy resin prepared in the reaction (2) into a vacuum drying oven, and drying at 120 ℃ for 2 hours to prepare the organosilicon modified biphenyl epoxy resin A1.
Preparation example 2
The preparation method of the organosilicon modified biphenyl type epoxy resin A2 is identical to A1, except that the methanol is replaced by acetone. A2 has an epoxy value of 0.52, an epoxy equivalent of 192 equivalents/100 g and a viscosity of 103 mPa.s at 150 ℃.
Preparation example 3
The preparation method of the organosilicon modified biphenyl type epoxy resin A3 is the same as A1, except that the organosilicon modified epoxy resin EP1, the biphenyl type epoxy resin and the methanol are prepared according to the weight ratio of 1:5: 20. a3 has an epoxy value of 0.52, an epoxy equivalent of 192 equivalents/100 g and a viscosity of 102 mPa.s at 150 ℃.
Preparation example 4
The preparation method of the organosilicon modified biphenyl type epoxy resin A4 is the same as A1, except that in the step (2), the reaction is carried out for 8 hours at 120 ℃, and then the reduced pressure distillation is carried out for 4 hours at 90 ℃. A4 has an epoxy value of 0.52, an epoxy equivalent of 192 equivalents/100 g and a viscosity of 100 mPas at 150 ℃.
Preparation example 5
The organosilicon modified biphenyl type epoxy resin A5 was identical to preparation example 1, except that the organosilicon modified epoxy resin EP2 had an epoxy value of 0.55 equivalents/100 g, an epoxy equivalent of 182 g/equivalent and a viscosity of 100 mPas at 150 ℃.
Preparation example 6
The organosilicon modified biphenyl type epoxy resin A6 was identical to preparation example 1, except that the biphenyl type epoxy resin had an epoxy value of 0.58 equivalents/100 g, an epoxy equivalent of 172 g/equivalent and a viscosity of 102 mPas at 150 ℃.
Comparative preparation example 1
In accordance with preparation example 1, except that the silicone modified epoxy resin EP1 was replaced with YX4000 epoxy resin, epoxy resin D2 was prepared. D2 has an epoxy value of 0.57, an epoxy equivalent of 175 g/equivalent and a viscosity of 108 mPas at 150 ℃.
The epoxy resin compositions of examples and comparative examples of the present invention are shown in tables 1, 1 (follow) 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.
The epoxy composition was prepared into an epoxy resin sample by the following method:
cutting a substrate for encapsulation into a pattern strip with the size of 18mm multiplied by 35mm, placing the pattern strip under a warping mold, heating the mold to 175 ℃, taking 30g of composition powder into a hopper, performing injection molding by an injection molding machine, demolding and curing in an oven at 175 ℃, thus obtaining a sample.
Reflow soldering test conditions: the set temperatures of the four areas of reflow soldering are 135/165/192/250 ℃, the lengths of the four temperature areas are 25cm, and the moving speed of the conveyor belt is 140mm/min.
The above samples were subjected to performance tests in which curing time, spiral flow length, bending properties, adhesive strength, glass transition temperature (Tg), and warpage are shown in table 3.
TABLE 3 Table 3
From the data, the embodiments 1-4 and 7-10 provided by the invention have better technical effects, have larger bending strength and bonding strength, lower linear expansion coefficient and smaller warping degree after reflow soldering, and are suitable for being applied to the BAG packaging field.
In comparative examples 1 to 2, the ratio of epoxy equivalent to hydroxyl equivalent was not in the range of 0.8 to 1.2, which resulted in an increase in fluidity, a decrease in adhesion, flexural strength, tg, and an increase in warpage after reflow soldering; in comparative example 3, the addition of both the unmodified biphenyl epoxy resin and the organosilicon modified biphenyl epoxy resin resulted in poor fluidity, reduced adhesion and Tg, and increased warpage after reflow soldering; comparative example 4 has a small amount of polyethylene wax, and the warpage after reflow soldering becomes large although the bending strength is not much different; comparative example 5 replaces the silicone modified biphenyl type epoxy resin with biphenyl type epoxy resin YX4000, which also causes the warpage after reflow soldering to become large, and is not suitable for BGA package.
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 (12)
1. An epoxy resin composition characterized in that it comprises, in parts by weight: 4-15 parts of organosilicon modified biphenyl type epoxy resin, 2-10 parts of curing agent, 0.01-2 parts of accelerator, 60-90 parts of inorganic filler, 0.05-3 parts of release agent and 0.01-2 parts of low-stress modifier;
wherein the usage amount of the organosilicon modified biphenyl type epoxy resin and the curing agent is such that the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the curing agent is 0.8-1.2;
the preparation method of the organosilicon modified biphenyl type epoxy resin comprises the following steps:
(1) And (3) batching: uniformly mixing the organosilicon modified epoxy resin, the biphenyl epoxy resin and the first solvent to obtain a mixture;
(2) The reaction: removing the first solvent after the mixture is subjected to a first reaction to obtain an organosilicon modified biphenyl type epoxy resin precursor;
(3) And (3) drying: drying the organosilicon modified biphenyl type epoxy resin precursor to obtain organosilicon modified biphenyl type epoxy resin;
the weight ratio of the organosilicon modified epoxy resin to the biphenyl epoxy resin to the first solvent is 1: (5-25): (20-30);
the epoxy value of the organosilicon modified epoxy resin is 0.42-0.54, the epoxy equivalent is 185-238 g/equivalent, and the viscosity at 25 ℃ is 11000-14000 mPa.s;
the epoxy value of the biphenyl type epoxy resin is 170-195 equivalents/100 g, the epoxy equivalent is 0.52-0.58 g/equivalent, the viscosity at 150 ℃ is 105-110 mPa.s, and the melting point is 105-112 ℃;
the epoxy value of the organosilicon modified biphenyl type epoxy resin is 0.52-0.55, the epoxy equivalent is 180-192 g/equivalent, the viscosity at 150 ℃ is 100-105 mPa.s, and the melting point is 105-107 ℃.
2. The composition of claim 1, wherein the silicone modified epoxy resin, biphenyl epoxy resin, first solvent are present in a weight ratio of 1: (10-20): 30.
3. the composition according to claim 1 or 2, wherein the composition comprises, in parts by weight: 4-10 parts of organosilicon modified biphenyl type epoxy resin, 3-8 parts of curing agent, 0.1-0.3 part of accelerator, 82-86 parts of inorganic filler, 0.1-0.5 part of release agent and 0.1-0.5 part of low-stress modifier.
4. The composition of claim 1 or 2, wherein the composition further comprises 0.1-0.5 parts of a colorant;
and/or the ratio of the epoxy equivalent of the organosilicon modified biphenyl type epoxy resin to the hydroxyl equivalent in the curing agent is 0.9-1.15.
5. The composition of claim 1 or 2, wherein the composition further comprises 0.2-0.4 parts of a colorant.
6. The composition of claim 1, wherein in step (2), the conditions of the first reaction comprise: reacting for 2-36 hours at 120-160 ℃ under stirring; the conditions for removing the first solvent include: distilling under reduced pressure at 70-90deg.C and-0.01-0.09 MPa for 2-15 hr;
and/or, in step (3), the drying conditions include: drying at 50-190 deg.C under-0.01-0.09 MPa for 1-4 hr.
7. The composition according to claim 1 or 2, wherein the curing agent is selected from phenolic resins;
and/or the accelerator is selected from at least one of an organic phosphorus compound, an imidazole compound and a tertiary amine compound;
and/or the inorganic filler is selected from at least one of silica, titania, alumina, and magnesia;
and/or the inorganic filler is at least one of a crystal type, a melting angle type and a melting spherical type;
and/or the release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax;
and/or the low-stress modifier is at least one of liquid silicone oil, silicone rubber powder, propyl trimethoxy silane and gamma-amino propyl triethoxy silane.
8. The composition of claim 7, wherein the curing agent is selected from bisphenol A type phenolic resin, XY-LOK type phenolic resin, DCPD type phenolic resin 、 At least one of biphenyl type phenol resin and multifunctional type phenol resin;
and/or the phenolic resin has a hydroxyl equivalent weight of 140-160 g/eq.
9. A method of preparing an epoxy resin, the method comprising: mixing the epoxy resin composition according to any one of claims 1 to 6 to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
10. The preparation method according to claim 9, wherein the mixing condition includes: mixing at 75-85deg.C for 7-9min, wherein the molding conditions include: molding at 170-180deg.C and 180-185 t.
11. An epoxy resin, characterized in that it is produced by the method of claim 9 or 10.
12. Use of the epoxy resin composition according to any one of claims 1-8 and/or the epoxy resin according to claim 11 in chip packaging.
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| JPH0481416A (en) * | 1990-07-24 | 1992-03-16 | Matsushita Electric Works Ltd | Epoxy resin composition |
| KR19980057177A (en) * | 1996-12-30 | 1998-09-25 | 김충세 | Manufacturing method of low stress modified silicone epoxy resin for semiconductor device encapsulation and resin composition for semiconductor device encapsulation containing same |
| CN111073217A (en) * | 2019-12-23 | 2020-04-28 | 科化新材料泰州有限公司 | High-thermal-conductivity low-stress epoxy plastic packaging material for semiconductor packaging |
| CN112724599A (en) * | 2020-12-28 | 2021-04-30 | 江苏科化新材料科技有限公司 | Epoxy resin composition for flip chip packaging |
| CN112724897A (en) * | 2020-12-23 | 2021-04-30 | 江苏科化新材料科技有限公司 | Light epoxy resin composition for semiconductor packaging |
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| JPH0481416A (en) * | 1990-07-24 | 1992-03-16 | Matsushita Electric Works Ltd | Epoxy resin composition |
| KR19980057177A (en) * | 1996-12-30 | 1998-09-25 | 김충세 | Manufacturing method of low stress modified silicone epoxy resin for semiconductor device encapsulation and resin composition for semiconductor device encapsulation containing same |
| CN111073217A (en) * | 2019-12-23 | 2020-04-28 | 科化新材料泰州有限公司 | High-thermal-conductivity low-stress epoxy plastic packaging material for semiconductor packaging |
| CN112724897A (en) * | 2020-12-23 | 2021-04-30 | 江苏科化新材料科技有限公司 | Light epoxy resin composition for semiconductor packaging |
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