CN115895551A - Underfill with high reliability and preparation method thereof - Google Patents
Underfill with high reliability and preparation method thereof Download PDFInfo
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- CN115895551A CN115895551A CN202211431592.3A CN202211431592A CN115895551A CN 115895551 A CN115895551 A CN 115895551A CN 202211431592 A CN202211431592 A CN 202211431592A CN 115895551 A CN115895551 A CN 115895551A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- underfill
- diglycidyl ether
- poss
- isosorbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003921 oil Substances 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- POPVULPQMGGUMJ-UHFFFAOYSA-N octasilsesquioxane cage Chemical compound O1[SiH](O[SiH](O2)O[SiH](O3)O4)O[SiH]4O[SiH]4O[SiH]1O[SiH]2O[SiH]3O4 POPVULPQMGGUMJ-UHFFFAOYSA-N 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 claims 1
- 229920003986 novolac Polymers 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 18
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 17
- 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
- 238000001723 curing Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- -1 phenolic aldehyde Chemical class 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004088 simulation 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
Abstract
The invention provides a high-reliability underfill adhesive, and a preparation method and application thereof. The cross-linking point in the system is increased by preparing the epoxy resin containing the POSS and the isosorbide chain segment, the fluidity and the bonding strength are improved, and meanwhile, the bottom filling adhesive 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 bottom filling agent is improved, and the bottom filling agent is used for the field of electronic device packaging materials.
Description
Technical Field
The invention belongs to the technical field of filling adhesives, and particularly relates to a bottom filling adhesive with high reliability and a preparation method thereof.
Background
With the development of scientific technology, the integration level of electronic components in portable intelligent electronic products and vehicle-mounted electronic equipment is higher and higher, the chip area is enlarged continuously, the pin count of integrated circuits is increased continuously, the chip packaging size is required to be further miniaturized and miniaturized, and the integrated circuits are developed towards lighter, thinner and smaller directions, so that a plurality of new packaging technologies and packaging forms appear. Flip chip (flip chip) interconnection technology, which connects an IC chip and a printed wiring substrate by small and thin solder bumps, is one of the most prominent packaging technologies. However, since the thermal expansion coefficients of the chip, the printed wiring board, and the solder are different, thermal stress is likely to occur during the cold-heat shock test. Particularly, local thermal stress is easily concentrated on the solder bump far from the center of the chip, so that the solder ball is easily cracked, and the performance reliability of the circuit is greatly reduced. Therefore, in order to alleviate the thermal stress, an underfill is formed by the liquid thermosetting resin composition, which can function to protect the chip return surface and the solder balls.
The underfill is a material suitable for the flip chip underfill technology, and generally permeates into a gap between a chip and a substrate by utilizing a capillary action principle, is gradually solidified and filled in the gap between the chip and the substrate through thermal curing, and protects high-density welding salient points and the chip between the chip and the substrate. However, the adhesion between the underfill material formed by curing the conventional underfill and the chip, substrate and solder bump 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, substrate and/or solder bump, and the chip is not protected and damaged.
Therefore, in view of the above problems, it is desirable to find an underfill adhesive with good adhesive strength, high glass transition temperature and low coefficient of linear thermal expansion, which has high reliability, to meet the requirement of protecting chips.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide an underfill with high reliability and a preparation method thereof, which aims to solve the technical problem of low reliability of the existing underfill.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the highly reliable underfill adhesive 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 to 5 percent of accelerant.
The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic aldehyde epoxy resin, alicyclic epoxy resin and dicyclopentadiene phenol epoxy resin.
The particle size of the silicon dioxide is 30-50 mu m.
The curing agent is selected from one or more of dicyandiamide, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone and derivatives of diaminodiphenyl sulfone.
The accelerator is at least one selected from imidazole latent accelerators and amine latent accelerators.
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 POSS modified epoxy resin is obtained by reacting amino-terminated POSS and isosorbide diglycidyl ether in a solvent. The mol ratio of the amino-terminated POSS to the isosorbide diglycidyl ether is 1.
The amino-terminated POSS is amino-terminated octasilsesquioxane or amino-terminated decasilsesquioxane.
The isosorbide diglycidyl ether is obtained by reacting isosorbide with epichlorohydrin. The molar ratio of the isosorbide to the epoxy chloropropane is 1:2.
further, the POSS modified epoxy resin is prepared by the following steps:
reacting amino-terminated POSS and isosorbide diglycidyl ether in a toluene solution at 80-90 ℃ for 10-15h, and then removing the toluene solvent in vacuum at 100-110 ℃ to obtain the POSS modified epoxy resin.
The isosorbide diglycidyl ether is prepared by the following steps:
heating isosorbide and epoxy chloropropane in a container to react for 5-8h at 60-70 ℃, distilling under reduced pressure, separating out a reaction product, adding the reaction product into a saturated aqueous solution of NaOH, 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 purpose of the invention is to provide a preparation method of underfill with high reliability, which comprises the following steps:
s1, weighing raw materials of each component according to a formula;
s2, putting the epoxy resin, the POSS modified epoxy resin and the diluent in a formula ratio 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 materials are added;
and S4, adding a curing agent and an accelerant into the reaction kettle in the step S3, and stirring for 60-120 minutes at the rotating speed of 300-1000 r/min, the temperature of 15-20 ℃ and the vacuum degree of 0.05-0.08MPa to obtain a finished product.
A third object of the present invention is to provide a highly reliable underfill for use in electronic packaging devices, particularly as a flip-chip packaging material.
Compared with the prior art, the invention has the following advantages:
(1) The invention creatively introduces the glycidyl ether containing the isosorbide chain segment onto the amino-terminated POSS to form the hyperbranched POSS modified epoxy resin, thereby providing more crosslinking sites, further improving the crosslinking degree of the system and further improving the bonding strength of the underfill; on the other hand, the high glass transition temperature, the low linear thermal expansion coefficient and the good flow property of the system are brought.
(2) The inventor creatively discovers that the POSS modified epoxy resin and the epoxy resin generate synergistic action in an underfill system, so that the underfill has high reliability due to the improvement of the bonding strength and the reduction of the linear thermal expansion coefficient.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to 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 provided with a stirrer, a thermometer and a nitrogen introducing device, heating to 45 ℃, slowly dropwise adding 0.2mol of epoxy chloropropane, reacting for 5 hours after the dropwise adding is finished within 30 minutes when the temperature is increased to 65 ℃, carrying out reduced pressure distillation, separating out a reaction product, adding the reaction product into a three-neck flask of NaOH saturated aqueous solution, reacting for 3 hours at 40 ℃, washing with water, separating out an oil layer, and carrying out reduced pressure distillation to obtain isosorbide diglycidyl ether.
(2) Preparing POSS modified epoxy resin:
adding 300g of toluene into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, adding 0.01mol of aminopropyl decasilsesquioxane and 0.1mol of isosorbide diglycidyl ether, heating to 85 ℃, reacting for 10 hours, and removing the toluene solvent in vacuum at 100-110 ℃ to obtain the 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 provided with a stirrer, a thermometer and a nitrogen introducing device, heating to 45 ℃, slowly dropwise adding 0.2mol of epoxy chloropropane, reacting for 5 hours after the dropwise adding is finished within 30 minutes when the temperature is increased to 65 ℃, carrying out reduced pressure distillation, separating out a reaction product, adding the reaction product into a three-neck flask of NaOH saturated aqueous solution, reacting for 3 hours at 40 ℃, washing with water, separating out an oil layer, and carrying out reduced pressure distillation to obtain isosorbide diglycidyl ether.
(2) Preparing POSS modified epoxy resin:
adding 300g of toluene into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, adding 0.01mol of aminopropyl octa polysilsesquioxane and 0.08mol of isosorbide diglycidyl ether into the three-neck flask, heating the mixture to 85 ℃, reacting for 10 hours, and removing a toluene solvent at 100-110 ℃ in vacuum to obtain the 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, putting the bisphenol A epoxy resin DER331, POSS-EP1 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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:
20% of bisphenol A epoxy resin DER 331%;
POSS-EP1 10％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP1 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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% 15%;
POSS-EP1 15％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP1 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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 a curing agent dicyandiamide and an accelerant 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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 DER 331% 25%;
POSS-EP2 5％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP2 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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 material addition is finished;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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:
20% of bisphenol A epoxy resin DER 331;
POSS-EP2 10％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP2 and the diluent 1, 4-butanediol diglycidyl ether into a reaction kettle according to the formula ratio, 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;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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:
DER 331% of bisphenol A epoxy resin;
POSS-EP2 15％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP2 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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 material addition is finished;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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:
30% of bisphenol A epoxy resin DER 331;
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331 and the diluent 1, 4-butanediol diglycidyl ether into a reaction kettle according to the formula ratio, 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;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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 a diluent into a reaction kettle according to the formula ratio, 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 a curing agent dicyandiamide and an accelerant 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, 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:
10% of bisphenol A epoxy resin DER 331;
POSS-EP1 20％；
45% of silicon dioxide;
dicyandiamide 10%
10% of 1, 4-butanediol diglycidyl ether;
2-Ethyl-4-methylimidazole 5%
S2, putting the bisphenol A epoxy resin DER331, POSS-EP1 and 1, 4-butanediol diglycidyl ether serving as a diluent into a reaction kettle according to the formula ratio, 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;
and S4, adding a curing agent dicyandiamide and an accelerator 2-ethyl-4-methylimidazole into the reaction kettle in the step S3, and stirring for 120 minutes at the rotation speed of 500r/min, the temperature of 20 ℃ and the vacuum degree of 0.08MPa to obtain a finished product.
Sample preparation and performance testing:
and (3) testing tensile shear performance: the underfill adhesives of examples 1-6 and comparative examples 1-3 were uniformly applied to two sets of aluminum sheets, the aluminum sheets were 100mm (length)/25 mm (width)/1.5 mm (thickness), each adhered test piece was coated with adhesive over its entire width, the length of the adhesive coating was 12.5mm, and the typical thickness of the adhesive coating was 0.2mm, and the aluminum sheets were bonded two by two to ensure that the two adhered test pieces were aligned precisely and the adhesive layers were as uniform in thickness as possible.
And (3) placing the aluminum sheet coated with the adhesive in an oven at the temperature of 120 ℃ for 2h for curing and forming, and testing the shear strength according to GB/T7124-2008.
And (3) testing the flow property: adhering four corners of a square glass sheet with the width of 20mm and the thickness of 0.5mm to four corners of the glass sheet by using a double-sided adhesive with the thickness of 50um (a simulation packaging chip), then placing the glass sheet on an electric heating plate with the temperature of 90 ℃, preheating for 3min, transversely coating the underfill to be tested along one side of the square glass sheet by using a thin steel needle, starting timing at the same time, allowing the underfill to flow at the bottom of the glass sheet under the action of capillary force, and recording the time for the underfill to flow to the half (10 mm) of the side length of the glass sheet.
Coefficient of thermal expansion test (CTE). The coefficient of thermal expansion test (CTE) was carried out according to ASTM D696 using thermomechanical analysis (TMA) with a temperature rise rate of 10 ℃/min in ppm/DEG C.
Glass transition temperature (Tg) after curing the underfill at 120 ℃ for 30min, the temperature rise rate was 5 ℃/min by thermomechanical analysis (TMA), and the glass transition temperature in units of ℃ during heating from 30 to 300 ℃ was confirmed.
The properties are shown in Table 1.
TABLE 1
Comparing examples 1-6 and comparative examples 1-2 in Table 1, it can be seen that the epoxy resin and the POSS modified epoxy resin have a synergistic effect, and the combination of the two improves the adhesive property, flow property and reliability of the underfill, which is reflected by the improvement of tensile shear strength and glass transition temperature, and the reduction of flow time and thermal expansion coefficient.
Comparing examples 1-3,4-6 and comparative examples 1-3 in Table 1, it can be seen that as the POSS modified epoxy resin content in the underfill increases, the properties of the underfill tend to increase, and the best results are obtained when the POSS modified epoxy resin content is 10%, indicating that the introduction of POSS segments and isosorbide segments into the underfill results in improved overall properties.
Comparing examples 1-3 and 4-6 in table 1, it can be seen that the more sites connecting isosorbide glycidyl ether in the POSS modified epoxy resin, the stronger the segment rotation ability, the more obvious the nano effect brought by POSS, and the higher the adhesive strength of the underfill, which is reflected by the improvement of the tensile shear strength.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting the same, and although the embodiments of the present invention are described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention, and these modifications or equivalent substitutions cannot make the modified technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
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 to 5 percent of accelerant.
2. The highly reliable underfill according to claim 1 wherein said epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, dicyclopentadiene phenol type epoxy resin;
the curing agent is selected from one or more of dicyandiamide, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone and derivatives of 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 selected from at least one of imidazole latency accelerators and amine latency accelerators.
3. The highly reliable underfill according to claim 1, wherein the silica has a particle size of 30-50 μm.
4. The highly reliable underfill according to claim 1, wherein said POSS modified epoxy resin is obtained by reacting amino-terminated POSS with isosorbide diglycidyl ether in a solvent; the isosorbide diglycidyl ether is obtained by reacting isosorbide with epichlorohydrin.
5. The underfill of claim 4, wherein the molar ratio of isosorbide to epichlorohydrin is 1:2, the mol ratio of the amino-terminated POSS to the isosorbide diglycidyl ether is 1.
6. The high reliability underfill of claim 4 wherein said amino-terminated POSS are amino-terminated octasilsesquioxane and amino-terminated decasilsesquioxane.
7. The highly reliable underfill according to claim 4, wherein the POSS modified epoxy resin is prepared by the following steps: reacting amino-terminated POSS and isosorbide diglycidyl ether in a toluene solution at 80-90 ℃ for 10-15h, and then removing the toluene solvent in vacuum at 100-110 ℃ to obtain POSS modified epoxy resin;
the isosorbide diglycidyl ether is prepared by the following steps: heating isosorbide and epoxy chloropropane in a container to react for 5-8h at 60-70 ℃, distilling under reduced pressure, separating out a reaction product, adding the reaction product into a saturated aqueous solution of NaOH, 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.
8. A method for preparing the underfill with high reliability performance as set forth in any one of claims 1 to 7, comprising the steps of:
s1, weighing raw materials of each component according to the formula of claim 1;
s2, putting the epoxy resin, the POSS modified epoxy resin and the diluent in a formula ratio 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 materials are added;
and S4, adding a curing agent and an accelerant into the reaction kettle in the step S3, and stirring for 60-120 minutes at the rotating speed of 300-1000 r/min, the temperature of 15-20 ℃ and the vacuum degree of 0.05-0.08MPa to obtain the high-reliability underfill adhesive.
9. Use of a high reliability underfill according to any one of claims 1-7 in an electronic packaging device.
10. Use of a high reliability underfill according to any one of claims 1-7 as a flip chip packaging material.
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