CN114276652A - 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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- CN114276652A CN114276652A CN202111652386.0A CN202111652386A CN114276652A CN 114276652 A CN114276652 A CN 114276652A CN 202111652386 A CN202111652386 A CN 202111652386A CN 114276652 A CN114276652 A CN 114276652A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 136
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 136
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004593 Epoxy Substances 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 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
- 238000000034 method Methods 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000004305 biphenyl Substances 0.000 claims description 13
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- -1 imidazole compound Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 238000003756 stirring Methods 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
- 239000003086 colorant Substances 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
- 239000000377 silicon dioxide Substances 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 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
- 239000012178 vegetable 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
- 238000005476 soldering Methods 0.000 abstract description 16
- 230000032798 delamination 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
- 238000005452 bending Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 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
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 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 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 229920006336 epoxy molding compound Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 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
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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, and a preparation method and application thereof. The composition comprises the following components in parts by weight: 4-15 parts of organic silicon modified biphenyl 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 epoxy resin and the curing agent enables the ratio of epoxy equivalent of the epoxy resin to hydroxyl equivalent of the curing agent to be 0.8-1.2. The epoxy resin composition contains the organosilicon modified biphenyl epoxy resin, and can be cooperatively matched with other components, so that the epoxy resin prepared from the epoxy resin composition has excellent mechanical properties and low linear expansion coefficient, and is low in warpage and free of delamination after reflow soldering.
Description
Technical Field
The invention relates to the technical field of thermosetting plastics, and particularly relates to an epoxy resin composition, an epoxy resin, and a preparation method and application thereof.
Background
The BGA is a ball grid array package, and compared with a previous generation package type QFN, the BGA type more fully utilizes the area of the bottom to form more interconnection pins, so that the area utilization rate of the package is finally improved, and the plane size of a product is reduced.
The final technological process of the BGA product is to solder the BGA product on a circuit board in a reflow soldering mode to complete interconnection of pins, and based on that the melting point of a solder ball is about 220 ℃, the peak temperature interval of heating is just higher than 220 ℃. The BGA may warp at all times during the heating and subsequent cooling cycles. This condition causes the BGA to be bowed with a lower center and two raised sides.
The BGA product mainly comprises three parts, namely a plastic package material, a chip and a PCB. In the reflow soldering process, the BGA product warps due to the fact that 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 the expansion coefficient of the plastic package material and the PCB after reflow soldering is more concerned for better solving the problem of warping of the BGA product after reflow soldering. The closer the expansion coefficients of the plastic package material and the PCB after reflow soldering are, the smaller the warpage of the BGA product after reflow soldering is. The Tg of the PCB for the common BGA product is 180-260 ℃, and the linear expansion coefficient alpha is1Between 4 and 8, the Tg of the epoxy molding compound for BGA is 100-160 ℃, and the linear expansion coefficient alpha is1Between 10 and 18, due to the linear expansion coefficient alpha of the two materials1The difference is large, so that the BGA product is easy to warp after reflow soldering.
In order to reduce the linear expansion coefficient alpha between the plastic package material and the PCB1The difference of the prior art, the plastic packaging 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 organosilicon modified epoxy resin can reduce the internal stress of the epoxy resin and increase the toughness of the epoxy resin, but the mechanical property of the epoxy resin is caused by excessive addition,The adhesion becomes poor.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property and poor adhesive force of epoxy resin in the prior art, and provides an epoxy resin composition, 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, comprising: 4-15 parts of organic silicon modified biphenyl 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 epoxy resin to the hydroxyl equivalent of the curing agent is 0.8-1.2.
The second aspect of the present invention provides a method for producing an epoxy resin, characterized in that the method comprises: 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, characterized in that the epoxy resin is obtained by the above method.
The fourth aspect of the present invention provides the use of the above epoxy resin composition and/or epoxy resin 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 epoxy resin, and can be cooperatively matched with other components, so that the epoxy resin prepared from the epoxy resin composition has excellent mechanical properties, a low linear expansion coefficient, and low warpage and no delamination after reflow soldering.
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: 4-15 parts of organic silicon modified biphenyl 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 epoxy resin to the hydroxyl equivalent of the curing agent is 0.8-1.2.
In the epoxy resin composition, the organosilicon modified biphenyl epoxy resin and other components are synergistic, wherein the organosilicon modified biphenyl epoxy resin has the advantages of good thermal stability, low surface energy, low-temperature flexibility, weather resistance, hydrophobicity, oxidation resistance and high dielectric strength, can effectively reduce the internal stress of the epoxy resin and increase the toughness and high temperature resistance of the epoxy resin, and the ratio of the epoxy equivalent of the organosilicon modified biphenyl epoxy resin to the hydroxyl equivalent in the curing agent meets the range of 0.8-1.2.
According to the invention, the composition comprises, in parts by weight: 4-10 parts of organic silicon modified biphenyl 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 the components in the epoxy resin composition meet the ranges, the prepared epoxy resin has more excellent comprehensive performance.
Further, the composition also comprises 0.1 to 0.5 part of colorant.
In the present invention, the colorant is not particularly limited and may be selected according to actual needs, and carbon black is preferable in the present invention.
Further, the composition also comprises 0.2 to 0.4 part of colorant.
Further, the ratio of the epoxy equivalent of the organosilicon-modified biphenyl type epoxy resin to the hydroxyl equivalent of the curing agent is 0.9 to 1.15.
According to the invention, the preparation method of the organosilicon modified biphenyl epoxy resin comprises the following steps:
(1) preparing materials: uniformly mixing the organic silicon modified epoxy resin, the biphenyl epoxy resin and the first solvent to obtain a mixture;
(2) reaction: removing the first solvent after the mixture is subjected to a first reaction to obtain an organosilicon modified biphenyl epoxy resin precursor;
(3) and (3) drying: and drying the organosilicon modified biphenyl epoxy resin precursor to obtain the organosilicon modified biphenyl 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 satisfies 1: (5-25): (25-30), the organic silicon modified epoxy resin and the biphenyl epoxy resin can be fully dissolved, and the resin is uniformly mixed.
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 kind of the first solvent is not particularly limited, and different solvents may be selected according to different types of epoxy resins, and may be, for example, methanol, ethanol or acetone, and preferably methanol.
According to the invention, in step (2), the conditions of the first reaction include: reacting at the temperature of 120 ℃ and 160 ℃ for 2-36 hours under stirring; the conditions for removing the first solvent include: vacuum distilling at 70-90 deg.C and-0.01-0.9 MPa for 2-15 hr.
According to the invention, in step (3), the drying conditions include: drying at-0.01 MPa to 0.9MPa and 50 to 190 ℃ for 1 to 4 hours.
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 may be prepared by the self-made method, and preferably, it is prepared by the following method:
organic siloxane, epoxy resin and a second solvent are mixed according to the weight ratio of 1: (10-20): 30, placing the mixture into a three-neck flask, stirring and refluxing, adjusting the pH value to 5-6, the reflux temperature to 70-80 ℃, refluxing for 3-6 h, and carrying out reduced pressure distillation after the reaction is finished to obtain the organic silicon modified epoxy resin.
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 hydroxyl equivalent weight of the phenolic resin is 140-160 g/eq, preferably 145-155 g/eq.
According to the present invention, the phenol resin is at least one selected from the group consisting of bisphenol a type phenol resin, XY-lock type phenol resin, DCPD type phenol resin, biphenyl type phenol resin and multifunctional type phenol resin.
According to the present invention, the accelerator is selected from at least one of an organophosphorus 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 sphere type.
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 invention, the low-stress modifier is at least one of liquid silicone oil, silicone rubber powder, propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
The second aspect of the present invention provides a method for producing an epoxy resin, characterized in that the method comprises: and mixing the epoxy resin composition to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
The epoxy resin has high mechanical property, adhesive force and low linear expansion coefficient, and is low in warpage and free of layering after reflow soldering.
In the present invention, the mixing and molding method is not particularly limited, and for example, the mixing and molding can be carried out by heating using a processing apparatus such as a two-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 for 7-9min at 75-85 ℃, wherein the molding conditions comprise: molding at the temperature of 170-180 ℃ and at the temperature of 180-190 t.
The third aspect of the present invention provides an epoxy resin, characterized in that the epoxy resin is obtained by the above method.
The fourth aspect of the present invention provides the use of the above epoxy resin composition and/or epoxy resin in chip 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 plate to 175 ℃, taking a certain amount of the epoxy resin composition powder, placing the epoxy resin composition powder on the plate, timing the powder by using a stopwatch from the time of the powder changing into a fluid state, reading the time required for the powder to change into a gel state, repeating the operation twice, and taking the average value of the two times as s.
Spiral flow length: the test conditions were: temperature: 175 ℃, pressure: 7MPa, pressure maintaining time: 110 s. The spiral flow length is a parameter for evaluating fluidity, and a larger value indicates better fluidity in cm.
Bending property: the bending strength of the standard sample strip was measured in a universal tester, and the bending strength is a parameter for evaluating the bending resistance of the epoxy composition, and the larger the value, the larger the strength of the semiconductor device after packaging, the unit is MPa.
Bonding strength: the bonding strength between the sample and the copper sheet is measured in 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 epoxy resins were tested for Tg using TMA in units of ℃.
And (3) warpage testing: and (3) testing by using a warpage tester, wherein warpage is a parameter for evaluating the size of the plane bending of the package body, and the smaller the value, the better the value, and the unit is mm.
Coefficient of linear expansion alpha1: obtained by TMA test and has a unit of 10-6/℃。
The organic silicon modified epoxy resin has an epoxy value of 0.45 equivalent/100 g, an epoxy equivalent of 222 g/equivalent and a viscosity of 11000mPa & s at 25 ℃, is prepared by a self-made method and comprises the following steps:
mixing organosiloxane, methanol and 128 epoxy resin according to a weight ratio of 1: 30: 10, placing the mixture into a three-neck flask, stirring and refluxing the mixture, adjusting the pH to 6, adjusting the reflux temperature to 70 ℃, refluxing the mixture for 3 hours, and performing reduced pressure distillation after the reaction is finished to obtain the organic silicon modified epoxy resin.
Unmodified biphenyl-type epoxy resin D1, epoxy value 0.57, epoxy equivalent 175 g/equivalent, viscosity 108mPa · s at 150 ℃, melting point 110 ℃, available from Mitsubishi, Japan under the trade name YX 4000;
a phenolic novolac resin having a hydroxyl equivalent of 150 g/equivalent, a viscosity of 8mPa · s at 150 ℃ and a melting point of 65 ℃ available from DIC corporation under the trade name MEH 7851;
2-phenyl-4-methylimidazole, available from four national chemical industry co;
fused spherical silica, 75 μm in particle size, available from Jiangsu Lirui technologies, Inc.;
polyethylene wax, available from clariant chemical (china) ltd;
propyltrimethoxysilane, available from Jiangsu Chenguang science and technology, Inc.;
carbon black, available from Shandong Deblue chemical Co., Ltd.
Preparation example 1
The organosilicon modified biphenyl epoxy resin A1 has an epoxy value of 0.52 equivalent/100, an epoxy equivalent of 192 g/equivalent, and a viscosity of 100 mPas at 150 ℃, and is prepared by the following steps:
(1) organic silicon modified epoxy resin EP1, biphenyl epoxy resin and methanol are mixed according to the weight ratio of 1: 10: 30 is added into a three-neck flask and mixed to obtain a mixture.
(2) And (3) reacting the mixture in a constant temperature circulator at 120 ℃ for 8h under the stirring state, and then distilling under reduced pressure at 70 ℃ for 4h to remove methanol, thereby obtaining the organosilicon modified biphenyl epoxy resin precursor.
(3) And (3) drying: and (3) putting the organosilicon modified biphenyl epoxy resin prepared in the reaction (2) into a vacuum drying oven, and drying for 2 hours at 120 ℃ to prepare the organosilicon modified biphenyl epoxy resin A1.
Preparation example 2
The preparation method of the organosilicon modified biphenyl epoxy resin A2 is the same as that of A1, except that the acetone is replaced by methanol. The epoxy value of A2 was 0.52, the epoxy equivalent was 192 equivalents/100 g, and the viscosity at 150 ℃ was 103 mPas.
Preparation example 3
The preparation method of the organosilicon modified biphenyl epoxy resin A3 is consistent with that of A1, and the difference is that the organosilicon modified epoxy resin EP1, the biphenyl epoxy resin and methanol are mixed according to the weight ratio of 1: 5: 20. the epoxy value of A3 was 0.52, the epoxy equivalent was 192 equivalents/100 g, and the viscosity at 150 ℃ was 102 mPas.
Preparation example 4
The organosilicon modified biphenyl epoxy resin A4 is prepared by the same method as A1, except that in the step (2), after 8 hours of reaction at 120 ℃, reduced pressure distillation is carried out for 4 hours at 90 ℃. The epoxy value of A4 was 0.52, the epoxy equivalent was 192 equivalents/100 g, and the viscosity at 150 ℃ was 100 mPas.
Preparation example 5
The silicone-modified biphenyl-type epoxy resin A5 was identical to preparation example 1, except that the silicone-modified epoxy resin EP2 had an epoxy value of 0.55 eq/100 g, an epoxy equivalent of 182 g/eq, and a viscosity of 100 mPas at 150 ℃.
Preparation example 6
An organosilicon-modified biphenyl-type epoxy resin A6 was prepared in the same manner as in preparation example 1, except that the biphenyl-type epoxy resin had an epoxy value of 0.58 eq/100 g, an epoxy equivalent of 172 g/eq and a viscosity of 102 mPas at 150 ℃.
Comparative preparation example 1
Consistent with preparation example 1, except that the silicone-modified epoxy resin EP1 was replaced with a YX4000 epoxy resin, an epoxy resin D2 was prepared. The epoxy value of D2 was 0.57, epoxy equivalent 175 g/equivalent, viscosity 108 mPas at 150 ℃.
The formulations of the epoxy resin compositions of examples of the present invention and comparative examples are shown in Table 1, Table 1 (continuous), and Table 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.
The epoxy resin samples were prepared from the above epoxy composition by the following method:
cutting the substrate for packaging into a pattern strip with the size of 18mm multiplied by 35mm, placing the pattern strip below 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 ℃ to obtain a sample.
Reflow test conditions: the set temperatures of 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 140 mm/min.
The above samples were subjected to performance tests in which the curing time, spiral flow length, bending properties, bond strength, glass transition temperature (Tg) and warpage were as shown in Table 3.
TABLE 3
From the data, the examples 1-4 and 7-10 provided by the invention have better technical effects, are higher in bending strength and bonding strength, lower in linear expansion coefficient, smaller in warping degree after reflow soldering, and not more than 0.25mm, and are suitable for being applied to the field of BAG packaging.
In the comparative examples 1 to 2, the ratio of epoxy equivalent to hydroxyl equivalent is not in the range of 0.8 to 1.2, so that the fluidity is increased, the adhesive force, the bending strength and the Tg are reduced, and the warpage is increased after reflow soldering; comparative example 3, the addition of unmodified biphenyl type epoxy resin and organosilicon modified biphenyl type epoxy resin at the same time causes deterioration of fluidity, reduction of adhesive force and Tg, and increase of warpage after reflow soldering; comparative example 4 since the amount of polyethylene wax used was small, although the difference in bending strength was not large, the warpage after reflow soldering became large; comparative example 5 replacement of the organosilicon-modified biphenyl type epoxy resin with the biphenyl type epoxy resin YX4000 also caused a large warpage after reflow soldering, which was not suitable for BGA 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: 4-15 parts of organic silicon modified biphenyl 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 epoxy resin and the curing agent enables the ratio of epoxy equivalent of the epoxy resin to hydroxyl equivalent of the curing agent to be 0.8-1.2.
2. The composition of claim 1, wherein the composition comprises, in parts by weight: 4-10 parts of organic silicon modified biphenyl 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;
preferably, the composition further comprises 0.1 to 0.5 parts of a colorant, preferably 0.2 to 0.4 parts;
preferably, the ratio of the epoxy equivalent of the organosilicon-modified biphenyl type epoxy resin to the hydroxyl equivalent of the curing agent is 0.9 to 1.15.
3. The composition according to claim 1 or 2, wherein the method for preparing the organosilicon-modified biphenyl type epoxy resin comprises the steps of:
(1) preparing materials: uniformly mixing the organic silicon modified epoxy resin, the biphenyl epoxy resin and a first solvent to obtain a mixture;
(2) reaction: removing the first solvent after the mixture is subjected to a first reaction to obtain an organosilicon modified biphenyl epoxy resin precursor;
(3) and (3) drying: drying the organosilicon modified biphenyl epoxy resin precursor to obtain organosilicon modified biphenyl epoxy resin;
preferably, 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 11000-14000mPa & s;
preferably, 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 ℃.
4. The composition according to claim 3, wherein in the step (1), the weight ratio of the organosilicon modified epoxy resin to the biphenyl type epoxy resin to the first solvent is 1: (5-25): (20-30), preferably 1: (10-20): 30.
5. the composition of claim 3 or 4, wherein in step (2), the conditions of the first reaction comprise: reacting at the temperature of 120 ℃ and 160 ℃ for 2-36 hours under stirring; the conditions for removing the first solvent include: vacuum distilling at 70-90 deg.C under-0.01-0.09 MPa for 2-15 hr;
preferably, in the step (3), the drying conditions include: drying at 50-190 deg.C under-0.01-0.09 MPa for 1-4 hr.
6. The composition according to any one of claims 1 to 5, wherein the curing agent is selected from phenolic resins, preferably at least one of bisphenol A type phenolic resins, XY-lock type phenolic resins, DCPD type phenolic resins, biphenyl type phenolic resins and multifunctional phenolic resins;
preferably, the phenolic resin has a hydroxyl equivalent weight of 140-160 g/eq;
preferably, the accelerator is selected from at least one of an organophosphorus compound, an imidazole compound and a tertiary amine compound;
preferably, the inorganic filler is selected from at least one of silica, titania, alumina, and magnesia;
preferably, the inorganic filler is at least one of a crystalline type, a molten angle type, and a molten spherical type;
preferably, the release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax;
preferably, the low stress modifier is at least one of liquid silicone oil, silicone rubber powder, propyltrimethoxysilane, and gamma-aminopropyltriethoxysilane.
7. A method of preparing an epoxy resin, the method comprising: mixing the epoxy resin composition of any one of claims 1-6 to obtain a mixture, and molding and demolding the mixture to obtain the epoxy resin.
8. The method of claim 7, wherein the mixing conditions comprise: mixing for 7-9min at 75-85 ℃, wherein the molding conditions comprise: molding at 170-180 deg.c and 180-185 t.
9. An epoxy resin, wherein the epoxy resin is produced by the method of claim 7 or 8.
10. Use of the epoxy resin composition of any one of claims 1-6 and/or the epoxy resin of claim 9 in chip packaging.
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Cited By (1)
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| CN117217503A (en) * | 2023-11-09 | 2023-12-12 | 山东华宝隆轻工机械有限公司 | Intelligent pump station pump group remote intelligent scheduling management system based on big data |
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| 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 |
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