CN118206952A - Underfill for inhibiting silicon dioxide sedimentation, preparation method and application thereof - Google Patents
Underfill for inhibiting silicon dioxide sedimentation, preparation method and application thereof Download PDFInfo
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- CN118206952A CN118206952A CN202410631965.4A CN202410631965A CN118206952A CN 118206952 A CN118206952 A CN 118206952A CN 202410631965 A CN202410631965 A CN 202410631965A CN 118206952 A CN118206952 A CN 118206952A
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- epoxy resin
- underfill
- filler
- silica
- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 39
- 238000004062 sedimentation Methods 0.000 title claims abstract description 30
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 81
- 239000000945 filler Substances 0.000 claims abstract description 40
- 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 abstract description 24
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 30
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical group C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 13
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 235000015110 jellies Nutrition 0.000 claims description 8
- 239000008274 jelly Substances 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 9
- 238000013007 heat curing Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000047 product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- -1 however Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The application discloses an underfill for inhibiting silicon dioxide sedimentation, a preparation method and application thereof, wherein the underfill comprises the following components in percentage by weight based on 100 percent: 60-65% of filler, 16-23% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment; the filler is selected from polypropylene oxide grafted modified silicon dioxide; the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber. The underfill of the application can inhibit the silica sedimentation phenomenon during the heat curing process.
Description
Technical Field
The application relates to the technical field of semiconductor chip underfill, in particular to an underfill for inhibiting silicon dioxide sedimentation, a preparation method and application thereof.
Background
The underfill is mainly composed of epoxy resin and inorganic filler, and is used for underfilling chips in BGA and CSP packaging modes, and a filling layer is formed after heating and curing so as to fill the bottom gap of the chip. Most underfills use silica as an inorganic filler, however, silica has a strong affinity for water on the surface, and when silica is in contact with humid air, the silicon atoms on the surface "react" with water to maintain tetrahedral coordination with oxygen, satisfying the valence of the surface silicon atoms, with water molecules irreversibly adsorbed on its surface, making it difficult to wet and disperse in the organic phase. In addition, in the dispensing process, the viscosity of the filling glue is suddenly reduced due to high-temperature heating, the intermolecular friction force is reduced along with the viscosity suddenly reduced, and the gravity of the silicon dioxide is larger than the acting force between the silicon dioxide and the epoxy resin, so that the sedimentation phenomenon occurs, the phenomenon is that the density of the silicon dioxide at the upper layer is low, the density of the silicon dioxide at the lower layer is high, and the physical property and the stability of the material are seriously influenced. Referring to fig. 1, a schematic diagram showing the distribution of silica particles 1 in a resin matrix 2 before and after heat curing is shown, which shows the sedimentation phenomenon of silica particles 1 during heat curing.
Disclosure of Invention
It is an object of the present application to provide an underfill that inhibits silica settling, comprising, based on 100% total weight: 60-65% of filler, 16-23% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment; the filler is selected from polypropylene oxide grafted modified silicon dioxide; the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
In some embodiments, the underfill of the present application comprises, on a total weight basis of 100%: 62.5-65% of filler, 16-20% of epoxy resin, 17-18.5% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment; the filler is selected from polypropylene oxide grafted modified silicon dioxide; the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
In some embodiments, the underfill of the present application comprises, on a total weight basis of 100%: 60-62.5% of filler, 20-23% of epoxy resin, 16.5-17% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment; the filler is selected from polypropylene oxide grafted modified silicon dioxide; the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
In some embodiments, the bulking agent is selected from the Japanese Dou Ma model SE203G-SEJ and/or the Zhejiang three time period model EQH1605-SED products.
In some embodiments, the epoxy resin is selected from mitsubishi chemical model number YX7105 product and/or mitsubishi chemical model number product YX7400.
In some embodiments, the curative is selected from amine-based curatives such as 3,3' -dimethyl-4, 4' -diaminodicyclohexylmethane or 4,4' -diaminodicyclohexylmethane.
In some embodiments, the accelerator is selected from imidazole accelerators, such as 2-ethyl-4 methylimidazole or N-methylimidazole.
In some embodiments, the pigment is selected from carbon black.
The second object of the present application is to provide a method for preparing the underfill, comprising:
mixing and stirring the raw materials according to the proportion to obtain jelly;
Dispersing the jelly by using three rollers;
stirring and vacuum defoaming are carried out, and the underfill product is obtained.
It is a further object of the present application to provide the use of the underfill adhesive described above for underfilling BGA chips or CSP chips.
Compared with the prior art, the application has the following advantages and beneficial effects:
According to the application, polypropylene oxide grafted modified silicon dioxide is selected as the filler, an epoxy group is grafted on the surface of the modified silicon dioxide, and the modified silicon dioxide has stronger compatibility with epoxy resin and is easier to disperse in an epoxy resin substrate according to a similar compatibility principle; and the acting force between the epoxy resin and the epoxy resin can be enhanced, which is beneficial to reducing sedimentation.
According to the application, the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile-butadiene rubber, active functional groups are arranged at two ends of a molecular chain of the carboxyl-terminated nitrile-butadiene rubber, and in a heating curing process, carboxyl on the molecular chain of the nitrile-butadiene rubber can react with epoxy groups in the epoxy resin to form a block polymer, and the block polymer is provided with a strong-polarity-CN group, so that acting force between the block polymer and modified silicon dioxide can be further enhanced, and the sedimentation of the silicon dioxide in the heating curing process is avoided.
Drawings
FIG. 1 is a schematic representation of the sedimentation of silica in an underfill wherein (a) and (b) are schematic representations of the dispersion of silica particles before and after heat curing, respectively; in the figure, 1-silica particles, 2-resin matrix;
FIG. 2 is a schematic structural diagram of modified silica in the examples;
FIG. 3 is a schematic molecular structure of Mitsubishi chemical type YX7105 product in the examples;
FIG. 4 is a schematic molecular structure of Mitsubishi chemical type YX7400N product in the example;
FIG. 5 is an SEM photograph of the product of example 1 after a sedimentation experiment;
fig. 6 is an SEM photograph of the product of comparative example 1 after a sedimentation experiment.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantageous effects of the present application more apparent.
The underfill for inhibiting silica sedimentation provided by the embodiment of the application comprises the following components in percentage by weight based on 100 percent: 60-65% of filler, 16-23% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment.
In some embodiments, the underfill comprises, based on 100% total weight: 62.5-65% of filler, 16-20% of epoxy resin, 17-18.5% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment.
In some embodiments, the underfill comprises, based on 100% total weight: 60-62.5% of filler, 20-23% of epoxy resin, 16.5-17% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment.
In the application, the curing agent is used for carrying out a crosslinking reaction with the epoxy resin under the action of a certain temperature and an accelerator, so that the material system is changed from a flowing state to a solid state; the accelerator is used as a catalyst for the crosslinking reaction; the curing agent and the accelerator are selected according to the conventional method and added according to the conventional dosage. In some embodiments, the curing agent may be selected from amine-based curing agents, such as 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane, and the like. In some embodiments, the accelerator may be selected from imidazole-type accelerators, such as 2-ethyl-4-methylimidazole, N-methylimidazole, and the like.
In the present application, the filler is selected from polypropylene oxide graft-modified silica, for example, modified silica of model SE203G-SEJ of Japanese ya Dou Ma, modified silica of model EQH1605-SED of Zhejiang three hours, and the like. The structural schematic of the polypropylene oxide graft modified silica is shown in fig. 2, in which 1,2,3 each represent a polypropylene oxide molecular chain but each represent a different polypropylene oxide molecular chain, wherein 1 represents a grafted polypropylene oxide molecular chain, 2 represents a hydrolyzable polypropylene oxide molecular chain, and 3 represents a free polypropylene oxide molecular chain.
In the present application, the epoxy resin is selected from carboxyl terminated nitrile liquid rubber modified bisphenol a type epoxy resin, such as modified bisphenol a type epoxy resin of Mitsubishi chemical model YX7105, polybutylene glycol diglycidyl ether of Mitsubishi chemical model YX7400N, and molecular structure schematic diagrams of model YX7105 and model YX7400N products are respectively shown in FIG. 3 and FIG. 4. The CAS number of the carboxyl terminated nitrile liquid rubber is 25265-19-4. The epoxy resin is modified by adopting carboxyl-terminated nitrile rubber, active functional groups are carboxyl groups at two ends of a molecular chain of the carboxyl-terminated nitrile rubber, and the carboxyl groups can react with epoxy groups in the epoxy resin to form a block polymer and have strong-polarity-CN groups in the heating and curing process of the filling rubber.
The strong hydrophilicity of silica makes it more difficult to wet and disperse in the organic phase, so the filler in the underfill most selectively modifies the silica, but most use a silane coupling agent to graft the silica, while improving the dispersibility of the silica in the resin substrate to some extent, it has no obvious effect on inhibiting the sedimentation of the silica.
According to the application, polypropylene oxide grafted modified silicon dioxide is selected as the filling glue, namely, epoxy groups are grafted on the surface of the modified silicon dioxide, and according to the principle of similar compatibility, the modified silicon dioxide and an epoxy resin base material have stronger compatibility, so that the modified silicon dioxide is easier to uniformly disperse in the epoxy resin base material, and the acting force between the surface of the modified silicon dioxide and the epoxy resin is stronger. Further, the epoxy resin is selected from bisphenol a type epoxy resin modified by carboxyl-terminated nitrile liquid rubber, is a block polymer polymerized by the carboxyl-terminated nitrile liquid rubber and the bisphenol a type epoxy resin, has a strong-polar-CN group, and can generate stronger acting force with modified silicon dioxide of which the surface is grafted with the epoxy group. In this way, when the underfill is dispensed, the viscosity of the underfill is suddenly reduced by high temperature heating, which results in a reduction in intermolecular friction, but the silica is effectively prevented from settling due to the stronger forces between the surface of the modified silica and the epoxy resin.
The preparation method of the underfill provided by the application comprises the following steps:
(1) Taking and stirring the raw materials according to the proportion to ensure that the raw materials are primarily mixed to obtain jelly;
in some embodiments, the step is specifically: taking all the raw materials according to the proportion, adding the raw materials into a stirring cup, and adopting a centrifugal stirrer for carrying out; the rotation and revolution speeds of the centrifugal stirrer are respectively 800-1000 r/min and 1000-1200 r/min, preferably 900 r/min and 1100 r/min, and the stirring time is 125 s-260 s;
(2) Dispersing the jelly by using three rollers to obtain uniformly dispersed underfill;
In some embodiments, the three rollers have a feed gap of 10um to 20um and a discharge gap of 5um to 10um.
(3) And (5) carrying out vacuum defoamation on the uniformly dispersed underfill to obtain an underfill product.
In some embodiments, vacuum defoaming is performed by using a centrifugal mixer, and rotation and revolution speeds of the centrifugal mixer are respectively 800-1000 r/min and 1000-1200 r/min, preferably 900 r/min and 1100 r/min, and vacuum defoaming time is 45 s-60 s.
The raw materials used in the examples and comparative examples are specifically as follows:
Filler: modified silica of model SE203G-SEJ of Japanese elegant Dou Ma, with particle size ranging from 0.6um to 3um; unmodified silicon dioxide with the grain diameter ranging from 0.6um to 3um;
Epoxy resin: modified bisphenol epoxy resin of Mitsubishi chemical type YX7105, viscosity 10 Pa.s (25 ℃/50 rpm); epoxy resin E-51, viscosity 8 Pa.s (25 ℃ C./50 rpm);
curing agent: 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane.
And (3) an accelerator: 2-ethyl-4 methylimidazole.
Examples and comparative examples provided by the present application are as follows:
Example 1
The raw materials and the amounts of the raw materials in this example were as follows:
Filler: 62.5%;
Epoxy resin: 20% of a base;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 17%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
in this example, modified silica SE203G-SEJ was used as the filler, and modified bisphenol type epoxy YX7105 was used as the epoxy resin.
Example 2
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 60 percent;
Epoxy resin: 23%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 16.5%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
in this example, modified silica SE203G-SEJ was used as the filler, and modified bisphenol type epoxy YX7105 was used as the epoxy resin.
Example 3
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 65%;
Epoxy resin: 16%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 18.5%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
in this example, modified silica SE203G-SEJ was used as the filler, and modified bisphenol type epoxy YX7105 was used as the epoxy resin.
Comparative example 1
The raw materials and the amounts of the raw materials in this example were as follows:
Filler: 62.5%;
Epoxy resin: 20% of a base;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 17%;
2-ethyl-4 methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, unmodified silica was used as the filler, and modified bisphenol type epoxy resin YX7105 was used as the epoxy resin.
Comparative example 2
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 60 percent;
Epoxy resin: 23%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 16.5%;
2-ethyl-4 methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, unmodified silica was used as the filler, and modified bisphenol type epoxy resin YX7105 was used as the epoxy resin.
Comparative example 3
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 65%;
Epoxy resin: 16%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 18.5%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, unmodified silica was used as the filler, and modified bisphenol type epoxy resin YX7105 was used as the epoxy resin.
Comparative example 4
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 66%;
epoxy resin: 17%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 16.5%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, modified silica SE203G-SEJ was used as the filler, and modified bisphenol type epoxy YX7105 was used as the epoxy resin.
Comparative example 5
The raw materials and the amounts of the raw materials in this example were as follows:
filler: 59%;
Epoxy resin: 23%;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 17.5%;
2-ethyl-4-methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, modified silica SE203G-SEJ was used as the filler, and modified bisphenol type epoxy YX7105 was used as the epoxy resin.
Comparative example 6
The raw materials and the amounts of the raw materials in this example were as follows:
Filler: 62.5%;
epoxy resin E-51: 20% of a base;
3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane: 17%;
2-ethyl-4 methylimidazole: 0.3%;
Carbon black: 0.2%;
In this comparative example, modified silica SE203G-SEJ was used as the filler, and the epoxy resin E-51 was an unmodified bisphenol A type epoxy resin.
The raw materials and amounts of the examples and comparative examples are shown in the following tables 1 to 2, respectively
TABLE 1 raw materials and amounts of examples 1-3
TABLE 2 raw materials and amounts of comparative examples 1 to 6
The preparation processes of the above examples and comparative examples are the same as follows:
Step one, adding the raw materials of all the components into a stirring cup according to the proportion;
Stirring for 160s by adopting a centrifugal stirrer, wherein the rotating speed is set as follows: rotation is 900 r/min, revolution is 1100 r/min; the preparation method comprises the steps of carrying out preliminary mixing on raw materials to obtain jelly;
Step three, adding the jelly into three rollers for dispersion treatment to obtain uniformly dispersed underfill; wherein, the feeding gap of the three rollers is 10 um, and the discharging gap is 5 um.
Fourthly, vacuum defoamation is carried out on the uniformly dispersed underfill by using a centrifugal mixer, and a final product is obtained; wherein, the vacuum defoamation time of the centrifugal mixer is 55 s, and the rotating speed is set as: rotation is 900 r/min, revolution is 1100 r/min.
The detection method of each performance parameter of the products of the examples and the comparative examples is as follows:
1. fluidity:
Square glass sheets with the width of 20mm and the thickness of 0.5 mm are stuck on four corners by using double-sided adhesive with the thickness of 30um, the four corners are stuck on glass slides, the glass slides are placed on an electric heating plate with the temperature of 90 ℃, the glass slides are preheated for three minutes, the underfill to be measured is transversely smeared along one edge of the square glass sheets by adopting a thin steel needle, simultaneously, the timing is started, the underfill can flow at the bottom of the glass sheets under the action of capillary force, and the time from flowing to half the length of the edge and the time when the underfill flows are recorded.
2. Silica sedimentation experiment:
The sample piece subjected to the fluidity test is placed on an electric hot plate, kept at the temperature of 110 ℃ for 30min, and then placed in an oven, and kept at the temperature of 165 ℃ for 2h for curing. And cutting the cured sample, polishing the cut surface, and directly observing the sedimentation condition of the silicon dioxide by adopting a scanning electron microscope.
3. Storage modulus
Using DMA test, reference standard: ASTM E2254-2018, take 165 ℃,2h cured complete sample, prepare test sample size 55mm x 10mm x 2mm, measurement mode: double cantilever mode (dual cantilever mode), vibration frequency: 1Hz, amplitude: 10 μm, rate of temperature rise: 5 ℃/min;
4. coefficient of thermal expansion and glass transition temperature:
Reference standard: ASTM E831-2019, take 165 ℃ and cure the complete sample for 2 hours, prepare test samples 5mm by 3mm in size. Samples were tested for coefficient of thermal expansion and glass transition Temperature (TMA) using TMA (compression mode). Parameter setting of TMA: preloading force: 0.05N, first scan: the temperature is raised at the temperature of between room temperature and 260 ℃ at the speed of 20 ℃/min; second scan: the temperature is increased by 5 ℃/min at the room temperature to 260 ℃, and curve data of a second heating section is obtained; the glass transition temperature is obtained from the second temperature rise section curve data.
Test data for the products of the above examples and comparative examples are shown in table 3 below:
TABLE 3 data on performance parameters of examples and comparative products
From the performance parameter data in table 3, it can be inferred from the performance parameter data that the silica in examples 1 to 3 is more uniformly dispersed in the epoxy resin substrate and is more stably bonded with the epoxy resin substrate, compared with the comparative examples 1 to 3, the examples 1 to 3 solve the problem of sedimentation of silica during the heat curing process, and have a larger storage modulus and a smaller thermal expansion coefficient.
Comparative examples 4 and 5, although the same as examples 1 to 3, also used a combination of polypropylene oxide graft modified silica and modified bisphenol type epoxy resin, the amount of the components was not within a specific amount range, and although the problem of sedimentation of silica during the heat curing process was solved as well, the other properties of the product were poor, and it was difficult to satisfy the use requirements.
In comparative example 6, polypropylene oxide grafted modified silica is adopted as the filler, but unmodified bisphenol epoxy resin is adopted as the epoxy resin, the silica sedimentation phenomenon still exists in the heating and curing process of the product of comparative example 6, and other performance parameters are poor.
Referring also to fig. 5 and 6, SEM photographs of the products of example 1 and comparative example 1 after sedimentation experiments are shown, respectively, wherein box (b) in fig. 6 is a partially enlarged schematic view of box (a). As can be seen from the figure, there is a significant sedimentation of the silica particles in the comparative example 1 product, whereas there is substantially no sedimentation of the silica particles in the example 1 product.
In summary, when polypropylene oxide grafted modified silica and modified bisphenol type epoxy resin are adopted at the same time, the dispersion of the silica in the epoxy resin base material can be promoted, and the combination stability of the silica and the epoxy resin base material can be enhanced, so that the sedimentation phenomenon of the silica in the heating and curing process can be further avoided. And when the modified silicon dioxide and the modified bisphenol type epoxy resin are used in specific amounts, other performances can be ensured.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (10)
1. An underfill to inhibit silica settling, characterized by:
comprises the following components by weight percent based on 100 percent: 60-65% of filler, 16-23% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment;
the filler is selected from polypropylene oxide grafted modified silicon dioxide;
the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
2. The silica sedimentation-inhibiting underfill of claim 1, wherein:
Comprises the following components by weight percent based on 100 percent: 62.5-65% of filler, 16-20% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment;
the filler is selected from polypropylene oxide grafted modified silicon dioxide;
the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
3. The silica sedimentation-inhibiting underfill of claim 1, wherein:
Comprises the following components by weight percent based on 100 percent: 60-62.5% of filler, 20-23% of epoxy resin, 13-19% of curing agent, 0.2-0.4% of accelerator and 0-0.3% of pigment;
the filler is selected from polypropylene oxide grafted modified silicon dioxide;
the epoxy resin is bisphenol type epoxy resin modified by carboxyl-terminated nitrile liquid rubber.
4. The silica sedimentation inhibiting underfill of any one of claims 1-3 wherein:
the curing agent is an amine curing agent.
5. The silica sedimentation-inhibiting underfill of claim 4 wherein:
the curing agent is 3,3' -dimethyl-4, 4' -diamino dicyclohexylmethane or/and 4,4' -diamino dicyclohexylmethane.
6. The silica sedimentation inhibiting underfill of any one of claims 1-3 wherein:
the accelerator is imidazole accelerator.
7. The silica sedimentation inhibiting underfill of claim 6 wherein:
The promoter is selected from 2-ethyl-4-methylimidazole or N-methylimidazole.
8. The silica sedimentation inhibiting underfill of any one of claims 1-3 wherein:
the pigment is carbon black.
9. The method of preparing an underfill according to any one of claims 1 to 8, comprising:
mixing and stirring the raw materials according to the proportion to obtain jelly;
Dispersing the jelly by using three rollers;
stirring and vacuum defoaming are carried out, and the underfill product is obtained.
10. Use of the underfill of any one of claims 1-8 for underfilling BGA chips or CSP chips.
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