CN111303382B - Rigid-flexible integrated epoxy resin and reworkable underfill - Google Patents
Rigid-flexible integrated epoxy resin and reworkable underfill Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract
The invention provides a rigid-flexible integrated epoxy resin and a repairable underfill, wherein the rigid-flexible integrated epoxy resin has a structural formula shown in formula (1), a binaphthalene structure is taken as a rigid core to provide rigidity of the epoxy resin and ensure high bonding strength, high modulus and low thermal expansion coefficient of an underfill, polyethylene glycol chain segments at four ends of the binaphthalene are made of flexible components to provide flexibility of the underfill prepared from the epoxy resin and improve the drop reliability of a glue filled chip, and four epoxy groups provide high crosslinking density and improve the high-low temperature cycle resistance effect of the underfill chip. Therefore, the underfill has good underfill effect, low thermal expansion coefficient and good toughness. The flexible chain segment of the polyethylene glycol contained in the epoxy resin can be softened at a certain temperature of 230-250 ℃, so that the underfill has a good repairing effect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to rigid-flexible integrated epoxy resin and a repairable underfill, and particularly relates to rigid-flexible integrated epoxy resin with high crosslinking density and a repairable underfill.
Background
Along with smart mobile phone's development, integrated more and more chips on the mobile phone motherboard, the quantity of chip becomes many, the area grow, the pin quantity grow gradually of chip, this kind of chip mainly be through flip-chip welded mode realize with mainboard circuit between be connected. However, the thermal expansion coefficients of the chip, the substrate and the solder are different, and stress is easily generated during a cold and hot cycle test and a drop test, so that the welding failure is caused. In order to improve the thermal shock reliability and the drop mechanical reliability of the chip, the failure caused by the mismatch of the thermal expansion coefficients is generally reduced by adding the underfill, and the drop reliability is improved.
However, as the integration of chips on the motherboard is higher and higher, for example, more than 20 chips are on the motherboard of the iphone, after the chips with large number are assembled, underfill is dispensed around the chips, so that the glue flows into the bottoms of the chips and is fully filled, and after curing, the difference between the thermal expansion coefficients of the chips and the motherboard can be improved, and the drop reliability between the chips and the motherboard can be improved. Meanwhile, due to the fact that certain defects exist during chip assembly or a certain chip fails in the use process of the mobile phone, the mobile phone needs to be repaired, and at the moment, if a PCB (printed circuit board) is replaced, the cost is very high. Therefore, only the failed chip is required to be taken out for repair, so that the underfill is required to have good repair performance, namely, the adhesive becomes soft when heated, the structural strength becomes low, and the chip is disassembled. Currently, there are three main problems with reworkable underfill materials developed in the industry, the first problem is that the structural strength of the substrate is affected due to the high rework temperature; the second problem is that the Tg point of the reworkable glue is too low and the cross-linking density is low, resulting in a large CTE/CTE of the glue and failure to reduce the CTE between the chip and the PCB substrate. The third problem is that the toughness of the glue is not good enough, which causes the poor falling reliability of the chip. High drop reliability of electronic products cannot be achieved.
Patent 201010212801.6 discloses a single-component underfill with good reworkability, which is composed of liquid epoxy resin, epoxidized polybutadiene, polyurethane modified epoxy resin, alicyclic epoxy resin, epoxy diluent, latent curing agent, accelerator, spherical silica powder and pigment, and has low viscosity, good bonding reliability and curing property during thermal cycle treatment, and improved reworkability, and can be rapidly cured at 150 ℃ for 40 seconds, and has high bonding force, good heat and impact resistance, simple manufacturing process, and wide application in flip chip packaging technology field. According to the patent 201310719026.7, the underfill prepared from epoxy resin, a diluent, a dispersant, an accelerant, a coupling agent and a curing agent has a melting point of more than 60 ℃ through a test value, has the characteristic of easy reworkability, can use lower temperature during heating and glue removal, and reduces heat damage to a mainboard and components; the underfill is easy to fall off from the mainboard and the components when heated, thereby having the advantages of excellent reworkable effect and low reworking rejection rate, but the underfill has larger thermal expansion coefficient. The reworkable filling adhesive disclosed in patent 201811287786.4 is composed of epoxy resin, polyether modified epoxy resin, bismaleimide modified toughened resin, reactive diluent, bismaleimide modified toughened resin and furan alkyl glycidyl ether prepolymer, curing agent, curing accelerator, coupling agent, spherical silica powder and pigment, and has the advantages of fast curing, high glass transition temperature (Tg), low expansion coefficient and good reworkability, and is mainly used for flip chip bottom filling to increase connection reliability.
The underfill disclosed above still needs further improvement in the properties of thermal expansion coefficient, modulus, toughness, etc.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a rigid-flexible integrated epoxy resin and a reworkable underfill,
in contrast, the technical scheme adopted by the invention is as follows:
a rigid-flexible integrated epoxy resin has a structural formula shown as the following formula (1):
wherein n is more than or equal to 50 and less than or equal to 200.
The invention also discloses a preparation method of the rigid-flexible integrated epoxy resin, which comprises the following steps:
step S1, preparing to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol;
step S2, adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol obtained in the step S1 into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 80-120 ℃ and reacting for 2-6 hours to obtain flexible long-arm binaphthalene with a binaphthalene structure in the middle and polyethylene glycol flexible chain segments at four ends; the reaction formula is as follows:
wherein n is 50 to 200.
And S3, adding the flexible long-arm binaphthyl obtained in the step S2 into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting at the temperature of 80-100 ℃ for 2-6 hours to obtain the rigid-flexible integrated epoxy resin with high crosslinking density. The reaction formula is as follows:
wherein n is 50 to 200.
As a further improvement of the present invention, step S1 includes: adding 2, 7-dihydroxynaphthalene into a solvent A, adding a catalyst A, and reacting at the temperature of 50-120 ℃ for 2-6 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol. Further, the catalyst A is ferric chloride hexahydrate; the reaction formula is shown as follows:
as a further improvement of the invention, the mass ratio of the 2, 7-dihydroxynaphthalene to the solvent A to the catalyst A is 1: 10-50: 0.01-0.1.
In a further improvement of the invention, in step S2, the mass ratio of [1,1' -binaphthalene ] -2,2',7,7' -tetraol, solvent A, ethylene oxide and catalyst B is 1: 10-50: 5-20: 0.01-0.1.
In a further improvement of the invention, in step S3, the mass ratio of the flexible long-arm binaphthalene, the solvent A, the ethylene oxide and the catalyst C is 1: 10-60: 20-40: 0.01-0.2.
As a further improvement of the invention, the solvent A is one or a mixture of several of formamide, N-methyl pyrrolidone, dimethyl sulfoxide, cyclohexanone, tetramethylethylenediamine and dioxane;
the catalyst B is one or a mixture of more of triethylamine, ammonium carbonate, sodium carbonate, potassium carbonate and sodium hydroxide;
the catalyst C is one or a mixture of sodium hydroxide, potassium hydroxide and sodium bicarbonate.
The invention also discloses a reworkable underfill which comprises the following components: the rigid-flexible integrated epoxy resin, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent,
wherein the rigid-flexible integrated epoxy resin, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent are in a mass ratio of 1: 0-1: 0.1-0.5: 0.002-0.005: 0.2-0.6: 0-0.002.
Wherein the second epoxy resin is different from a rigid-flex integrated epoxy resin.
The preparation method of the reworkable underfill comprises the following steps: and mixing and reacting the rigid-flexible integrated epoxy resin, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent to obtain the reworkable underfill.
The obtained rigid-flexible integrated epoxy resin with high crosslinking density is used as base resin to prepare the reworkable high-performance underfill adhesive, can be used on the mainboard of electronic products such as smart phones and smart automobiles, is used for underfilling chips, and can improve the environmental reliability and mechanical reliability of the chips.
As a further improvement of the invention, the second epoxy resin is one or a mixture of more of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin and alicyclic epoxy resin. Further, the molecular weight of the second epoxy resin is 1000-30000. Further, the halogen content is below 200ppm, and the metal ion content is below 5 ppm.
As a further improvement of the invention, the diluent is one or a mixture of more than two of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycidyl methacrylate, C12-C14 alkyl glycidyl ether and 1, 2-cyclohexanediol diglycidyl ether.
As a further improvement of the invention, the curing agent is one or a mixture of more than two of pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropane tri (3-mercaptopropionate).
AsA further improvement of the invention, the catalyst is one orA mixture of two or more of 2MZ, C11Z, C17Z, 2E4MZ, 2PZ-PW, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 1,2DMZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, 2MZ-A, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2PHZ, 2P4MHZ, PN-23 of Japanese gourmet company, PN-40, PN-H, MY-24 and PN-50 which are made in four countries in Japan.
As a further improvement of the invention, the filler is one or a mixture of more of spherical silica, calcium carbonate, talcum powder and magnesium oxide. Furthermore, the particle size of the filler is 200-800 nm.
As a further improvement of the invention, the defoaming agent is one or a mixture of more than two of BYK-051, BYK-052, BYK-053, BYK-054, BYK-056, BYK-057, BYK-065, BYK-066N, BYK-067A, BYK-070, BYK-077, BYK-085, BYK-088 and BYK-141. The above antifoam types are all available from BYK, Germany.
Compared with the prior art, the invention has the beneficial effects that:
according to the high-crosslinking-density rigid-flexible integrated epoxy resin disclosed by the technical scheme of the invention, the binaphthalene structure is a rigid core, the rigidity of the epoxy resin is provided, the high bonding strength, the high modulus and the low thermal expansion coefficient of an underfill are ensured, the polyethylene glycol chain segments at four ends of the binaphthalene are flexible, the flexibility of the underfill prepared from the epoxy resin is provided, the falling reliability of a glue filled chip is improved, the high crosslinking density is provided by four epoxy groups, the high and low temperature circulation resistant effect of the underfill chip is improved, and therefore the underfill has a good underfill effect, a low thermal expansion coefficient and good toughness. The flexible chain segment of the polyethylene glycol contained in the epoxy resin can be softened at a certain temperature of 230-250 ℃, so that the underfill has a good repairing effect.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
A reworkable underfill prepared by the steps of:
(1) synthesis of rigid-flexible integrated epoxy resin
(a) Adding 2, 7-dihydroxynaphthalene (CAS No.:582-17-2) into a solvent A, adding a catalyst A, raising the temperature to 50 ℃ and reacting for 2 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol, wherein the mass ratio of the 2, 7-dihydroxynaphthalene to the solvent A to the catalyst A is 1:10: 0.01.
(b) Adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol in the step (a) into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 80 ℃ and reacting for 2 hours to obtain the flexible long-arm binaphthalene of which the middle is a binaphthalene structure and four ends are polyethylene glycol flexible chain segments. Wherein the mass ratio of the [1,1' -binaphthalene ] -2,2',7,7' -tetraol, the solvent A, the ethylene oxide and the catalyst B is 1:10:5: 0.01.
(c) And (C) adding the flexible long-arm binaphthalene substance obtained in the step (b) into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting for 2 hours at the elevated temperature of 80 ℃ to obtain the rigid-flexible integrated epoxy resin with high crosslinking density. Wherein the mass ratio of the flexible long-arm binaphthalene, the solvent A, the ethylene oxide and the catalyst C is 1:10:20: 0.01.
Wherein the solvent A is formamide, the catalyst A is ferric trichloride hexahydrate, the catalyst B is triethylamine, and the catalyst C is sodium hydroxide.
(2) Preparation of reworkable underfill
And mixing the rigid-flexible integrated epoxy resin with a second epoxy resin, a diluent, a curing agent, a catalyst, a filler and an antifoaming agent, wherein the mass ratio of the rigid-flexible integrated epoxy resin to the second epoxy resin to the diluent to the curing agent to the catalyst to the filler to the antifoaming agent is 1:0:0.1:0.1:0.002:0.2: 0.
Wherein the second epoxy resin is bisphenol A epoxy resin, the molecular weight is 1000, the halogen content is below 200ppm, and the metal ion content is below 5 ppm; the diluent is ethylene glycol diglycidyl ether; the curing agent is pentaerythritol tetra (3-mercaptopropionate) (CAS NO. 7575-23-7); the catalyst is 2MZ formed by four countries in Japan; the filler is spherical silicon dioxide, and the particle size of the filler is 200 nm; the defoaming agent is BYK-056.
Example 2
A reworkable underfill prepared by the steps of:
(1) synthesis of rigid-flexible integrated epoxy resin
(a) Adding 2, 7-dihydroxynaphthalene (CAS No.:582-17-2) into a solvent A, adding a catalyst A, raising the temperature to 120 ℃ and reacting for 6 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol, wherein the mass ratio of the 2, 7-dihydroxynaphthalene to the solvent A to the catalyst A is 1:50: 0.1.
(b) Adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol in the step (a) into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 120 ℃ and reacting for 6 hours to obtain the flexible long-arm binaphthalene of which the middle is a binaphthalene structure and four ends are polyethylene glycol flexible chain segments. Wherein the mass ratio of the [1,1' -binaphthalene ] -2,2',7,7' -tetraol, the solvent A, the ethylene oxide and the catalyst B is 1:50:20: 0.1.
(c) And (C) adding the flexible long-arm binaphthalene substance in the step (b) into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting for 6 hours at the elevated temperature of 100 ℃ to obtain the rigid-flexible integrated epoxy resin with high crosslinking density. Wherein the mass ratio of the flexible long-arm binaphthalene, the solvent A, the ethylene oxide and the catalyst C is 1:60:40: 0.2.
Wherein, the solvent A is nitrogen methyl pyrrolidone; the catalyst A is ferric trichloride hexahydrate; the catalyst B is sodium hydroxide; the catalyst C is sodium bicarbonate.
(2) Preparation of reworkable underfill
And mixing the rigid-flexible integrated epoxy resin with high crosslinking density, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent, wherein the mass ratio of the rigid-flexible integrated epoxy resin to the second epoxy resin to the diluent to the curing agent to the catalyst to the filler to the defoaming agent is 1:1:1:0.5:0.005:0.6: 0.002.
Wherein the second epoxy resin is bisphenol F epoxy resin, the molecular weight of the second epoxy resin is 30000, the halogen content is below 200ppm, and the metal ion content is below 5 ppm; the diluent is propylene glycol diglycidyl ether; the curing agent is pentaerythritol tetra (3-mercaptopropionate) (CAS NO. 7575-23-7); the catalyst is PN-23 of the Japan gourmet powder company; the filler is calcium carbonate, and the particle size of the filler is 800 nm; the defoaming agent is BYK-052.
Example 3
A reworkable underfill prepared by the steps of:
(1) synthesis of rigid-flexible integrated epoxy resin
(a) Adding 2, 7-dihydroxynaphthalene (CAS No.:582-17-2) into a solvent A, adding a catalyst A, raising the temperature to 110 ℃ and reacting for 4 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol, wherein the mass ratio of the 2, 7-dihydroxynaphthalene, the solvent A and the catalyst A is 1:40: 0.05.
(b) Adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol in the step (a) into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 90 ℃ and reacting for 5 hours to obtain the flexible long-arm binaphthalene of which the middle is a binaphthalene structure and four ends are polyethylene glycol flexible chain segments. Wherein the mass ratio of the [1,1' -binaphthalene ] -2,2',7,7' -tetraol, the solvent A, the ethylene oxide and the catalyst B is 1:30:10: 0.06.
(c) And (C) adding the flexible long-arm binaphthalene substance in the step (b) into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting for 3 hours at the elevated temperature of 70 ℃ to obtain the rigid-flexible integrated epoxy resin with high crosslinking density. Wherein the mass ratio of the flexible long-arm binaphthalene, the solvent A, the ethylene oxide and the catalyst C is 1:30:30: 0.1.
Wherein the solvent A is dioxane; the catalyst A is ferric chloride hexahydrate; the catalyst B is sodium carbonate; the catalyst C is potassium hydroxide.
(2) Preparation of reworkable underfill
And mixing the rigid-flexible integrated epoxy resin with high crosslinking density, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent, wherein the mass ratio of the rigid-flexible integrated epoxy resin to the second epoxy resin to the diluent to the curing agent to the catalyst to the filler to the defoaming agent is 1:0.2:0.5:0.3:0.003:0.4: 0.0015.
The second epoxy resin is novolac epoxy resin, the molecular weight of the second epoxy resin is 10000, the halogen content is below 200ppm, and the metal ion content is below 5 ppm;
the diluent is trimethylolpropane triglycidyl ether; the curing agent is trimethylolpropane tri (3-mercaptopropionate) (CAS NO. 33007-83-9); the catalyst is 2PZCNS-PW formed by four countries in Japan; the filler is talcum powder, and the particle size of the filler is 600 nm; the defoaming agent is BYK-077 of BYK company of Germany.
Example 4
A reworkable underfill prepared by the steps of:
(1) synthesis of rigid-flexible integrated epoxy resin
(a) Adding 2, 7-dihydroxynaphthalene (CAS No.:582-17-2) into a solvent A, adding a catalyst A, raising the temperature to 70 ℃ and reacting for 4.5 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol, wherein the mass ratio of the 2, 7-dihydroxynaphthalene to the solvent A to the catalyst A is 1:35: 0.03.
(b) Adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol in the step (a) into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 110 ℃ and reacting for 4.6 hours to obtain the flexible long-arm binaphthalene with a binaphthalene structure in the middle and polyethylene glycol flexible chain segments at four ends. Wherein the mass ratio of the [1,1' -binaphthalene ] -2,2',7,7' -tetraol, the solvent A, the ethylene oxide and the catalyst B is 1:30:12: 0.06.
(c) And (C) adding the flexible long-arm binaphthalene substance in the step (b) into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting for 5.4 hours at the elevated temperature of 95 ℃ to obtain the rigid-flexible integrated epoxy resin with high crosslinking density. Wherein the mass ratio of the flexible long-arm binaphthalene to the solvent A to the ethylene oxide to the catalyst C is 1:34:34: 0.067.
Wherein the solvent A is cyclohexanone; the catalyst A is ferric chloride hexahydrate; the catalyst B is sodium carbonate; the catalyst C is sodium hydroxide.
(2) Preparation of reworkable underfill
And mixing the rigid-flexible integrated epoxy resin with high crosslinking density, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent, wherein the mass ratio of the rigid-flexible integrated epoxy resin to the second epoxy resin to the diluent to the curing agent to the catalyst to the filler to the defoaming agent is 1:0.3:0.2:0.4:0.004:0.45: 0.0017.
The second epoxy resin is alicyclic epoxy resin, and has a molecular weight of 20000, a halogen content of 200ppm or less, and a metal ion content of 5ppm or less.
The diluent is dodecyl glycidyl ether; the curing agent is pentaerythritol tetra (3-mercaptopropionate) (CAS NO. 7575-23-7); the catalyst is PN-H of the Japanese gourmet powder company; the filler is spherical silicon dioxide, and the particle size of the filler is 500. The defoaming agent is BYK-066N of Germany BYK company.
Comparative example 1
A conventional reworkable underfill prepared by the steps of: mixing epoxy resin, a diluent, a curing agent, a catalyst, a filler and a defoaming agent, wherein the mass ratio of the rigid-flexible integrated high crosslinking density epoxy resin to the diluent to the curing agent to the catalyst to the filler to the defoaming agent is 1:0.5:0.5:0.005:0.6: 0.002.
Wherein the epoxy resin is bisphenol A epoxy resin, the molecular weight of the epoxy resin is 30000, the halogen content is below 200ppm, and the metal ion content is below 5 ppm; the diluent is ethylene glycol diglycidyl ether; the curing agent is pentaerythritol tetra (3-mercaptopropionate) (CAS NO. 7575-23-7); the catalyst is PN-50 of the Japanese monosodium glutamate company; the filler is spherical silicon dioxide, and the particle size of the filler is 800 nm. The defoaming agent is BYK-085 of Germany BYK company.
The above examples were compared with comparative examples in terms of their properties, and the results are shown in Table 1.
Table 1 adhesive performance comparison table of examples 1 to 4 with comparative example 1
In the above table, method for measuring viscosity: the viscosity values were measured using a Brookfield rotational viscometer at 25 ℃ with spindle # 52 and at 10 rpm.
The test method of the bonding strength comprises the following steps: dispensing 0.5mg of glue on FR-4, then pasting a 2mm silicon chip on the FR-4, standing for 5min at room temperature, curing, and testing thrust by using DAGE3800 after curing to obtain the bonding strength.
Method for testing glass transition temperature Tg: and (3) testing by adopting a DSC method, putting 0.5mg of a sample into equipment, controlling the temperature to be 20-200 ℃ and the temperature rise speed to be 10 ℃/min, and analyzing the obtained curve to obtain Tg data.
Coefficient of expansion CTE test method: referring to a standard JISK7197 method, the detection temperature range is-50 to 600 ℃, the temperature is controlled to be 0.01 to 100min, and the TMA range (sensitivity) is as follows: 5mm 0.02m, style size: 100mm 25 mm. The test instrument references two data of CTE obtained from the curve obtained using TMA 4000SE, one above and one below the Tg point.
Modulus test method: a DMA8000 dynamic thermomechanical analyzer is adopted, a stretching method is adopted, the frequency is set to be 500HZ, the temperature rise speed is 20-200 ℃, and modulus data at 25 ℃ can be obtained through a curve after analysis and test.
Compared with the comparative example without the resin, the high-crosslinking rigid-flexible integrated epoxy resin is added in the technical scheme of the invention, so that the CTE is lower in thermal expansion coefficient, the repair temperature is low, the repair can be carried out, the bonding strength is higher after the chip bottom is filled and is subjected to thermosetting, the good bonding strength can be kept after high temperature and high humidity, long-term water sprinkling, long-term vibration, drop test, cold and hot shock and the like, and the requirement of high reliability of electronic products can be met.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A rigid-flexible integrated epoxy resin is characterized in that the structural formula is shown as the following formula (1):
wherein n is more than or equal to 50 and less than or equal to 200.
2. The method for preparing a rigid-flex epoxy resin according to claim 1, comprising the steps of:
step S1, preparing to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol;
step S2, adding the [1,1' -binaphthalene ] -2,2',7,7' -tetraol obtained in the step S1 into a solvent A, adding ethylene oxide and a catalyst B, raising the temperature to 80-120 ℃ and reacting for 2-6 hours to obtain flexible long-arm binaphthalene with a binaphthalene structure in the middle and polyethylene glycol flexible chain segments at four ends;
and S3, adding the flexible long-arm binaphthyl obtained in the step S2 into a solvent A, adding epoxy chloropropane and a catalyst C, and reacting at the temperature of 80-100 ℃ for 2-6 hours to obtain the rigid-flexible integrated epoxy resin.
3. The method for producing a rigid-flex integrated epoxy resin according to claim 2, characterized in that: step S1 includes: adding 2, 7-dihydroxynaphthalene into a solvent A, adding a catalyst A, and reacting at the temperature of 50-120 ℃ for 2-6 hours to obtain [1,1' -binaphthalene ] -2,2',7,7' -tetraol.
4. The method for producing a rigid-flex epoxy resin according to claim 3, characterized in that: the mass ratio of the 2, 7-dihydroxynaphthalene to the solvent A to the catalyst A is 1: 10-50: 0.01-0.1.
5. The method for producing a rigid-flex epoxy resin according to claim 4, characterized in that: in step S2, the mass ratio of [1,1' -binaphthalene ] -2,2',7,7' -tetraol, the solvent A, the ethylene oxide and the catalyst B is 1: 10-50: 5-20: 0.01-0.1.
6. The method for producing a rigid-flex epoxy resin according to claim 5, characterized in that: in the step S3, the mass ratio of the flexible long-arm binaphthyl, the solvent A, the epichlorohydrin and the catalyst C is 1: 10-60: 20-40: 0.01-0.2.
7. The method for producing a rigid-flex epoxy resin according to claim 6, characterized in that: the solvent A is one or a mixture of more of formamide, N-methyl pyrrolidone, dimethyl sulfoxide, cyclohexanone, tetramethylethylenediamine and dioxane;
the catalyst A is ferric chloride hexahydrate;
the catalyst B is one or a mixture of more of triethylamine, ammonium carbonate, sodium carbonate, potassium carbonate and sodium hydroxide;
the catalyst C is one or a mixture of sodium hydroxide, potassium hydroxide and sodium bicarbonate.
8. A reworkable underfill comprising the components: the rigid-flex epoxy resin, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler, the defoamer according to claim 1,
wherein the rigid-flexible integrated epoxy resin, the second epoxy resin, the diluent, the curing agent, the catalyst, the filler and the defoaming agent are in a mass ratio of 1: 0-1: 0.1-0.5: 0.002-0.005: 0.2-0.6: 0-0.002.
9. The reworkable underfill according to claim 8, wherein: the second epoxy resin is one or a mixture of more of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin and alicyclic epoxy resin, and the molecular weight of the second epoxy resin is 1000-30000.
10. The reworkable underfill according to claim 9, wherein: the diluent is one or a mixture of more of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycidyl methacrylate, C12-14 alkyl glycidyl ether and 1, 2-cyclohexanediol diglycidyl ether;
the curing agent is one or a mixture of pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropane tri (3-mercaptopropionate);
the catalyst is one orA mixture of more of 2MZ, C11Z, C17Z, 2E4MZ, 2PZ-PW, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 1,2DMZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, 2MZ-A, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2PHZ, 2P4MHZ, PN-23, PN-40, PN-H, MY-24 and PN-50;
the filler is one or a mixture of more of spherical silicon dioxide, calcium carbonate, talcum powder and magnesium oxide;
the defoaming agent is one or a mixture of more of BYK-051, BYK-052, BYK-053, BYK-054, BYK-056, BYK-057, BYK-065, BYK-066N, BYK-067A, BYK-070, BYK-077, BYK-085, BYK-088 and BYK-141.
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| CN116063252A (en) * | 2022-12-26 | 2023-05-05 | 北京智芯微电子科技有限公司 | Binaphthyl monomer and preparation method thereof, epoxy resin and preparation method and application thereof |
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| CN1203103C (en) * | 2003-03-17 | 2005-05-25 | 中国科学院广州化学研究所 | Naphthyl type epoxy resin and its preparing method |
| US10047256B2 (en) * | 2013-03-06 | 2018-08-14 | Dic Corporation | Epoxy resin composition, cured product, heat radiating material, and electronic member |
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