CN115895551B - Underfill with high reliability and preparation method thereof - Google Patents
Underfill with high reliability and preparation method thereof Download PDFInfo
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- CN115895551B CN115895551B CN202211431592.3A CN202211431592A CN115895551B CN 115895551 B CN115895551 B CN 115895551B CN 202211431592 A CN202211431592 A CN 202211431592A CN 115895551 B CN115895551 B CN 115895551B
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- epoxy resin
- underfill
- diglycidyl ether
- high reliability
- poss
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- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical group O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 12
- 239000005022 packaging material Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 20
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 20
- JEBWAOITKHXCBF-BEAPMJEYSA-N (3s,3ar,6r,6ar)-3,6-bis(oxiran-2-ylmethoxy)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan Chemical compound O([C@@H]1[C@H]2OC[C@H]([C@H]2OC1)OCC1OC1)CC1CO1 JEBWAOITKHXCBF-BEAPMJEYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229960002479 isosorbide Drugs 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 2
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims description 2
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004100 electronic packaging Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 18
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 16
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 16
- 238000001723 curing Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- -1 aminopropyl Chemical group 0.000 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 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention provides an underfill with high reliability, a preparation method and application thereof. The epoxy resin containing POSS and isosorbide chain segments is prepared to increase crosslinking points in a system, so that the fluidity and the bonding strength are improved, and meanwhile, the underfill has excellent bonding strength, good fluidity, low thermal expansion coefficient and high glass transition temperature through the synergistic effect of the POSS modified epoxy resin and the epoxy resin, so that the reliability of the underfill is improved, and the underfill is used in the field of electronic device packaging materials.
Description
Technical Field
The invention belongs to the technical field of filling glue, and particularly relates to an underfill with high reliability and a preparation method thereof.
Background
With the development of science and technology, the integration level of electronic components in portable intelligent electronic products and vehicle-mounted electronic devices is higher and higher, the chip area is enlarged continuously, the pin count of an integrated circuit is increased continuously, and meanwhile, the packaging size of the chip is required to be further miniaturized and miniaturized, and the integrated circuit is developed towards lighter, thinner and smaller directions, so that a plurality of new packaging technologies and packaging forms are developed. Flip chip (flip chip) interconnection technology is one of the most dominant packaging technologies, and flip chip technology connects an IC chip and a printed wiring board by small and thin solder bumps. However, thermal stress is likely to occur during cold and hot impact tests due to the difference in thermal expansion coefficients of the chip, the printed wiring board, and the solder. In particular, local thermal stress is easily concentrated in the solder bumps farther from the center of the chip, and the solder balls are easily cracked, and the reliability of the circuit performance is greatly reduced. Therefore, in order to alleviate thermal stress, an underfill is formed by the liquid thermosetting resin composition, which can function to protect the chip return surface and solder balls.
The underfill is a material suitable for the underfill technology of flip chips, and is generally permeated into the gap between the chip and the substrate by utilizing the capillary action principle, and then gradually solidified and filled in the gap between the chip and the substrate by thermal curing, so as to protect the high-density welding bumps and the chip between the chip and the substrate. However, the adhesion force between the underfill material formed after the curing of the existing underfill and the chip, the substrate and the solder bumps is not strong enough, the linear thermal expansion coefficient is too high, and the glass transition temperature is not sufficient, so that the underfill material is often cracked or peeled off from the chip, the substrate and/or the solder bumps, and the chip cannot be continuously protected, so that the chip is damaged.
Therefore, in view of the above problems, there is a need to find an underfill having good adhesion strength, high glass transition temperature and low linear thermal expansion coefficient with high reliability, so as to meet the requirement of chip protection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an underfill with high reliability and a preparation method thereof, and aims to solve the technical problem that the reliability of the existing underfill is not high.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the underfill with high reliability comprises the following components in percentage by mass:
15% -25% of epoxy resin;
5% -15% of POSS modified epoxy resin;
30 to 50 percent of silicon dioxide
5 to 15 percent of curing agent
5 to 15 percent of diluent
3% -5% of accelerator.
The epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic type epoxy resin, alicyclic epoxy resin and dicyclopentadiene phenol type epoxy resin.
The particle size of the silicon dioxide is 30-50 mu m.
The curing agent is one or more selected from dicyandiamide, diaminodiphenyl methane, diaminodiphenyl ether, diaminodiphenyl sulfone and derivatives of diaminodiphenyl sulfone.
The accelerator is at least one selected from imidazole latent accelerator and amine latent accelerator.
The diluent is selected from one or more of phenyl glycidyl ether, o-tolyl glycidyl ether, benzyl glycidyl ether, p-tert-butyl phenyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
The POSS modified epoxy resin is obtained by reacting amino-terminated POSS and isosorbide diglycidyl ether in a solvent. The molar ratio of the amino-terminated POSS to the isosorbide diglycidyl ether is 1:8-10.
The amino-terminated POSS is amino-terminated octapolysilsesquioxane and amino-terminated decapolysilsesquioxane.
The isosorbide diglycidyl ether is obtained by reacting isosorbide with epichlorohydrin. The molar ratio of the isosorbide to the epichlorohydrin is 1:2.
further, the POSS modified epoxy resin is prepared by the following steps:
the terminal amino POSS and isosorbide diglycidyl ether react for 10 to 15 hours at the temperature of 80 to 90 ℃ in toluene solution, and toluene solvent is removed in vacuum at the temperature of 100 to 110 ℃ to obtain the POSS modified epoxy resin.
The isosorbide diglycidyl ether is specifically prepared by the following steps:
heating isosorbide and epichlorohydrin in a container to react for 5-8h at 60-70 ℃, distilling under reduced pressure to separate out a reaction product, adding the reaction product into a NaOH saturated aqueous solution, reacting for 3-5h at 30-40 ℃, washing with water, separating out an oil layer, and distilling under reduced pressure to obtain the isosorbide diglycidyl ether.
The second object of the present invention is to provide a method for preparing an underfill having high reliability, comprising the steps of:
s1, weighing raw materials of all components according to a formula;
s2, adding the epoxy resin, the POSS modified epoxy resin and the diluent in the formula amount into a reaction kettle, and stirring and mixing for 30-60 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30-60 minutes after the addition is finished;
s4, adding the curing agent and the accelerator into the reaction kettle in the step S3, and stirring for 60-120 minutes at the rotating speed of 300-1000 r/min and the temperature of 15-20 ℃ and the vacuum degree of 0.05-0.08MPa to obtain the finished product.
A third object of the present invention is to provide a highly reliable underfill application in electronic packaging devices, particularly as flip chip packaging materials.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the glycidyl ether containing the isosorbide chain segment is creatively introduced into the amino POSS to form hyperbranched POSS modified epoxy resin, so that more crosslinking sites are provided, on one hand, the further improvement of the crosslinking degree of the system is brought, and the bonding strength of the underfill is further improved; on the other hand, the high glass transition temperature, low linear thermal expansion coefficient and good flow property of the system are brought.
(2) The inventors creatively found that both POSS modified epoxy resin and epoxy resin produced a synergistic effect in the underfill system, resulting in an improvement in the adhesive strength of the underfill, a reduction in the coefficient of linear thermal expansion, and a high reliability of the underfill.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Preparation example 1:
preparation of POSS modified epoxy resin (POSS-EP 1):
(1) Preparation of isosorbide diglycidyl ether:
adding 0.1mol of isosorbide into a three-neck flask equipped with a stirrer, a thermometer and a nitrogen-introducing device, heating to 45 ℃, slowly dropwise adding 0.2mol of epichlorohydrin, reacting for 5 hours after the dropwise adding is completed within 30 minutes at the temperature of 65 ℃, distilling under reduced pressure to separate out a reaction product, adding the reaction product into the three-neck flask of NaOH saturated aqueous solution, reacting for 3 hours at 40 ℃, washing with water, separating an oil layer, and distilling under reduced pressure to obtain the isosorbide diglycidyl ether.
(2) Preparing POSS modified epoxy resin:
300g of toluene is added into a three-neck flask equipped with a stirrer, a thermometer and a nitrogen-introducing device, 0.01mol of aminopropyl decapolysilsesquioxane and 0.1mol of isosorbide diglycidyl ether are added into the three-neck flask, the mixture is heated to 85 ℃ for reaction for 10 hours, and toluene solvent is removed in vacuum at 100-110 ℃ to obtain POSS modified epoxy resin POSS-EP1.
Preparation example 2:
preparation of POSS modified epoxy resin (POSS-EP 2):
(1) Preparation of isosorbide diglycidyl ether:
adding 0.1mol of isosorbide into a three-neck flask equipped with a stirrer, a thermometer and a nitrogen-introducing device, heating to 45 ℃, slowly dropwise adding 0.2mol of epichlorohydrin, reacting for 5 hours after the dropwise adding is completed within 30 minutes at the temperature of 65 ℃, distilling under reduced pressure to separate out a reaction product, adding the reaction product into the three-neck flask of NaOH saturated aqueous solution, reacting for 3 hours at 40 ℃, washing with water, separating an oil layer, and distilling under reduced pressure to obtain the isosorbide diglycidyl ether.
(2) Preparing POSS modified epoxy resin:
300g of toluene is added into a three-neck flask equipped with a stirrer, a thermometer and a nitrogen-introducing device, 0.01mol of aminopropyl octapolysilsesquioxane and 0.08mol of isosorbide diglycidyl ether are added into the three-neck flask, the mixture is heated to 85 ℃ for reaction for 10 hours, and toluene solvent is removed in vacuum at 100-110 ℃ to obtain POSS modified epoxy resin POSS-EP2.
Example 1
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 25%;
POSS-EP1 5％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP1 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Example 2
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 20%;
POSS-EP1 10％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP1 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Example 3
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER 331% by weight;
POSS-EP1 15％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP1 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Example 4
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 25%;
POSS-EP2 5％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP2 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Example 5
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 20%;
POSS-EP2 10％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP2 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Example 6
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER 331% by weight;
POSS-EP2 15％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP2 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Comparative example 1
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 30%;
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331 and the diluent 1, 4-butanediol diglycidyl ether in the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Comparative example 2
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
POSS-EP1 30％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding POSS-EP1 and 1, 4-butanediol diglycidyl ether serving as diluents into a reaction kettle according to the formula amount, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Comparative example 3
Preparation of underfill with high reliability:
s1, preparing the following raw materials in percentage by mass:
bisphenol a epoxy resin DER331 10%;
POSS-EP1 20％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-ethyl-4-methylimidazole 5%
S2, adding the bisphenol A epoxy resin DER331, the POSS-EP1 and the diluent 1, 4-butanediol diglycidyl ether with the formula amount into a reaction kettle, and stirring and mixing for 30 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30 minutes after the addition is finished;
s4, adding dicyandiamide serving as a curing agent and 2-ethyl-4-methylimidazole serving as an accelerator into the reaction kettle in the step S3, and stirring for 120 minutes at the rotating speed of 500r/min and the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Sample preparation and performance testing:
tensile shear performance test: the underfill of examples 1-6, comparative examples 1-3 were applied uniformly to two sets of aluminum sheets, each having a size of 100mm (length)/25 mm (width)/1.5 mm (thickness), each of the adhered test pieces was spread with a spread length of 12.5mm, and the spread thickness was typically 0.2mm, and the aluminum sheets were adhered two by two to ensure precise alignment of the two adhered test pieces and to make the thickness of the adhesive layer uniform as much as possible.
The aluminum sheet coated with the adhesive is placed in an oven at 120 ℃ for 2 hours to be cured and molded, and the shearing strength is tested according to GB/T7124-2008.
Flow performance test: the square glass sheet with the width of 20mm and the thickness of 0.5mm is stuck on a glass slide by using double-sided adhesive with the thickness of 50um (simulating packaging chips), then the glass slide is placed on an electric heating plate with the temperature of 90 ℃, the glass slide is preheated for 3 minutes, the underfill to be measured is transversely smeared along one edge of the square glass sheet by adopting a thin steel needle, meanwhile, the timing is started, the underfill can flow at the bottom of the glass sheet under the action of capillary force, and the time from the underfill to half (10 mm) of the edge length of the glass sheet is recorded.
Coefficient of thermal expansion test (CTE) Thermal Mechanical Analysis (TMA) was used according to ASTMD696 standard, wherein the rate of temperature rise was 10 ℃/min, units ppm/. Degree.C.
Glass transition temperature (Tg) after curing the underfill at 120℃for 30min, the glass transition temperature in the heating process from 30 to 300℃was confirmed by a Thermal Mechanical Analysis (TMA) test at a heating rate of 5℃per minute.
The properties are shown in Table 1.
TABLE 1
As can be seen from a comparison of examples 1-6 and comparative examples 1-2 in table 1, the epoxy resin and POSS modified epoxy resin have a synergistic effect, and the combination of the two improves the adhesion, flow properties and reliability of the underfill, as evidenced by an increase in tensile shear strength and glass transition temperature, and a decrease in flow time and coefficient of thermal expansion.
As can be seen from a comparison of examples 1-3,4-6 and comparative examples 1-3 in Table 1, as the amount of POSS modified epoxy resin in the underfill increases, the various properties of the underfill tend to increase, and the inclusion of POSS segments and isosorbide segments in the underfill is best illustrated by the 10% amount of POSS modified epoxy resin.
As can be seen from a comparison of examples 1-3 and 4-6 in Table 1, the more sites in the POSS modified epoxy resin to which isosorbide glycidyl ether is attached, the stronger the segment rotation ability, the more pronounced the nanoeffect imparted by POSS, and the higher the bond strength of the underfill, which is manifested as an improvement in tensile shear strength.
Finally, it should be noted that the foregoing embodiments are merely for illustrating the technical solution of the embodiments of the present invention and are not intended to limit the embodiments of the present invention, and although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the embodiments of the present invention may be modified or replaced with the same, and the modified or replaced technical solution may not deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (9)
1. The underfill with high reliability is characterized by comprising the following components in percentage by mass:
15% -25% of epoxy resin;
5% -15% of POSS modified epoxy resin;
30 to 50 percent of silicon dioxide
5 to 15 percent of curing agent
5 to 15 percent of diluent
3% -5% of a promoter;
the POSS modified epoxy resin is obtained by reacting amino-terminated POSS and isosorbide diglycidyl ether in a solvent; the isosorbide diglycidyl ether is obtained by reacting isosorbide with epichlorohydrin.
2. The high reliability underfill according to claim 1, wherein the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic type epoxy resin, alicyclic epoxy resin, dicyclopentadiene phenol type epoxy resin;
the curing agent is one or more selected from dicyandiamide, diaminodiphenyl methane, diaminodiphenyl ether and diaminodiphenyl sulfone;
the diluent is selected from one or more of phenyl glycidyl ether, o-tolyl glycidyl ether, benzyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol triglycidyl ether and trimethylolpropane triglycidyl ether;
the accelerator is at least one selected from imidazole latent accelerator and amine latent accelerator.
3. The high reliability underfill according to claim 1, wherein the silica has a particle size of 30-50 μm.
4. The high reliability underfill according to claim 1, wherein the molar ratio of isosorbide to epichlorohydrin is 1:2, wherein the mol ratio of the amino-terminated POSS to the isosorbide diglycidyl ether is 1:8-10.
5. The high reliability underfill of claim 1 wherein the amino terminated POSS is an amino terminated octapolysilsesquioxane and an amino terminated decapolysilsesquioxane.
6. The high reliability underfill according to claim 1, wherein the POSS modified epoxy resin is prepared by: reacting amino-terminated POSS and isosorbide diglycidyl ether in toluene solution at 80-90 ℃ for 10-15h, and then removing toluene solvent in vacuum at 100-110 ℃ to obtain POSS modified epoxy resin;
the isosorbide diglycidyl ether is specifically prepared by the following steps: heating isosorbide and epichlorohydrin in a container to react for 5-8h at 60-70 ℃, distilling under reduced pressure to separate out a reaction product, adding the reaction product into a NaOH saturated aqueous solution, reacting for 3-5h at 30-40 ℃, washing with water, separating out an oil layer, and distilling under reduced pressure to obtain the isosorbide diglycidyl ether.
7. A method of preparing the high reliability underfill of any one of claims 1-6, comprising the steps of:
s1, weighing raw materials of all components according to the formula of claim 1;
s2, adding the epoxy resin, the POSS modified epoxy resin and the diluent in the formula amount into a reaction kettle, and stirring and mixing for 30-60 minutes;
s3, adding silicon dioxide into the reaction kettle in the step S2, and stirring and mixing for 30-60 minutes after the addition is finished;
s4, adding the curing agent and the accelerator into the reaction kettle in the step S3, and stirring for 60-120 minutes at the rotating speed of 300-1000 r/min and the temperature of 15-20 ℃ and the vacuum degree of 0.05-0.08MPa to obtain the underfill with high reliability.
8. Use of the high reliability underfill of any one of claims 1-6 in electronic packaging devices.
9. Use of the high reliability underfill according to any one of claims 1-6 as a flip chip packaging material.
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