CN115491172B - Modified epoxy die-bonding adhesive for LEDs and preparation method of modified epoxy resin - Google Patents
Modified epoxy die-bonding adhesive for LEDs and preparation method of modified epoxy resin Download PDFInfo
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- CN115491172B CN115491172B CN202211181917.7A CN202211181917A CN115491172B CN 115491172 B CN115491172 B CN 115491172B CN 202211181917 A CN202211181917 A CN 202211181917A CN 115491172 B CN115491172 B CN 115491172B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 92
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 92
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000004593 Epoxy Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002329 infrared spectrum Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 238000001514 detection method Methods 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 229910018557 Si O Chemical group 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 229920001558 organosilicon polymer Polymers 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000002464 physical blending Methods 0.000 description 4
- -1 polysiloxane Polymers 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920002160 Celluloid Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
The invention discloses a modified epoxy die-bonding adhesive for an LED, which is characterized in that: comprising the following steps: 40-100 parts of modified epoxy resin A, 10-30 parts of epoxy resin B, 40-120 parts of curing agent, 3-10 parts of accelerator, 1-8 parts of antioxidant and 0.1-5 parts of thixotropic agent. Comprises a preparation method, wherein the preparation method comprises the steps of mixing modified epoxy resin A and epoxy resin B uniformly at 60 ℃; adding thixotropic agent, mixing, and cooling; adding a curing agent and stirring; adding antioxidant and promoter, mixing, filtering, and defoaming. The phenyl and Si-O chain segments are introduced into the epoxy resin structure, so that the epoxy resin structure can endow the epoxy resin with excellent high temperature resistance; the special trapezoid double-chain section structure has excellent toughness, elasticity and stability, so that the internal stress of the cured epoxy resin can be effectively reduced, and the cold and hot impact resistance and the tearing resistance of the cured material are improved.
Description
Technical Field
The invention belongs to the technical field of epoxy die bond adhesives, and particularly relates to a modified epoxy die bond adhesive for an LED and a preparation method of modified epoxy resin.
Background
Epoxy resins have many advantages such as corrosion resistance, electrical insulation, excellent adhesion, and good processability. However, since the epoxy resin is a three-dimensional network structure thermosetting resin with high crosslinking degree, the internal stress of a cured product is large, the cracking stress is low, the brittleness of the material is large, the peeling strength and the impact strength are low, and the application of the epoxy resin in the field of high-end LED packaging is greatly limited.
Along with the continuous upgrading and innovation of the whole LED packaging industry, the requirements of the market on products are more and more embodied and high-quality, particularly in the field of small-size chip packaging, the requirement on the commonly used epoxy die bonding adhesive is higher and higher, and the original adhesive is changed into the adhesive which is not only adhesive but also light efficiency maintenance rate is high, and the performance is stable. In order to meet urgent requirements of market application ends on the performance of the epoxy die-bonding adhesive, the epoxy resin is subjected to organosilicon modification treatment, so that the epoxy resin becomes one of effective ways for improving the epoxy die-bonding adhesive. The organic silicon modified epoxy resin can generate a three-dimensional network structure similar to inorganic silicate, so that the heat resistance of the epoxy resin can be improved, the toughness of the material can be improved, and the internal stress of the cured epoxy resin can be improved. Modification of epoxy resins by silicones can be categorized into physical blending and chemical copolymerization. The physical blending modification refers to a blend obtained by mixing organic silicon and epoxy resin according to a certain stoichiometric ratio, and the organic silicon and the epoxy resin do not generate chemical reaction, and only the physical blending method is adopted. Because of the poor compatibility of the silicone phase and the epoxy resin phase, phase separation easily occurs between the two phases, and the dispersed phase is distributed in the middle of the continuous phase, forming a heterogeneous system also called "islands-in-the-sea" structure. The chemical modification is to make the organosilicon and the epoxy resin take part in chemical reaction to finally generate a block copolymer or a graft copolymer, and the chemical modification can be used for connecting Si-O bonds with high bond energy into the structure of the epoxy resin, thereby improving the comprehensive performance of the epoxy resin and avoiding the compatibility problem of the epoxy resin and the organosilicon caused by physical blending.
At present, the research on the modification of the organosilicon of the epoxy resin is reported to be mainly based on the chemical copolymerization of a single-chain organosilicon polymer and the epoxy resin. Cao Xinyu and the like disclose a siloxane bridge ladder polysiloxane and a preparation method thereof (CN 104045831A), wherein the main chain of the ladder-shaped organosilicon polymer is double-chain organosilicon polymer, and compared with common single-chain organosilicon polymer macromolecules, the polysiloxane bridge ladder-shaped polysiloxane has more excellent high temperature resistance (the temperature resistance grade can reach more than 300 ℃), radiation resistance, high strength, high air tightness, higher adhesiveness and the like. The modified epoxy resin with the special trapezoid organosilicon chain segments is obtained by modifying the epoxy resin with the trapezoid organosilicon polymer, and the crystal-fixing glue prepared by taking the modified epoxy resin as the raw material can improve the high-temperature yellowing resistance of the epoxy resin and endow the material with excellent tear resistance and mechanical properties on the premise of maintaining the bonding performance of the epoxy resin to the maximum extent.
Disclosure of Invention
The invention aims to provide a modified epoxy die-bonding adhesive for an LED and a preparation method of modified epoxy resin, which are used for solving the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the modified epoxy die bond adhesive for the LED is an organic silicon modified epoxy resin insulation composite material, and consists of the following substances in parts by weight:
the invention adopts epoxy resin and phenyl trapezoid polysilsesquioxane as raw materials, and utilizes the dehydration condensation reaction of hydroxyl groups of organic silicon and secondary hydroxyl groups in the epoxy resin to form stable silicon-oxygen-alkyl bonds, thereby obtaining modified epoxy resin A.
The epoxy resin is E44 epoxy resin, wherein m is more than or equal to 1 and less than or equal to 8, and the structure is shown as (1):
the phenyl trapezoid polysilsesquioxane is characterized in that n is more than or equal to 2 and less than or equal to 6, and the structure of the phenyl trapezoid polysilsesquioxane is shown as (2):
the preparation method of the modified epoxy resin A specifically comprises the following steps:
(1) Weighing a proper amount of epoxy resin and dimethylbenzene, adding the epoxy resin and dimethylbenzene into a flask provided with a stirring device and a reflux condenser, introducing condensed water, stirring and changing the temperature to 50-100 ℃ at the same time, completely melting the epoxy resin, adding a catalyst tetrabutyl orthotitanate, and continuously stirring to form a uniform solution;
(2) Weighing a proper amount of phenyl trapezoid polysilsesquioxane and dimethylbenzene, adding the phenyl trapezoid polysilsesquioxane and the dimethylbenzene into a beaker, stirring and diluting to obtain a uniform solution, adding a catalyst tetrabutyl orthotitanate, and continuously stirring to obtain the uniform solution;
(3) Heating the solution in the step (1) to 100-200 ℃ while stirring, preserving heat, and then dropwise adding the solution in the step (2) into the solution in the step (1) at a constant speed while stirring for reaction;
(4) When the consumption of the solution in the step (2) reaches a certain amount, reducing the dropping speed, detecting by infrared spectrum until the vibration peak of-OH in the silicon hydroxyl in the reaction solution gradually disappears, stopping dropping, and then continuing stirring and preserving heat for 30-120 min;
(5) After the reaction, the excess solvent in the solution was removed by distillation under reduced pressure to obtain a modified epoxy resin A.
The beneficial effect of adopting the scheme of the last step is: the main body of the modified epoxy resin A is epoxy resin, so that the bonding performance of the die bond adhesive can be ensured; the introduction of the phenyl organosilicon chain segment can improve the high-temperature yellowing resistance of the epoxy resin; the ladder-shaped organosilicon polymer is characterized in that the core of the ladder-shaped organosilicon polymer is a ladder-shaped structure formed by silicon oxide double chains side by side, and the special structure can endow the material with excellent cold and hot impact resistance and tearing resistance.
Further, the epoxy resin B is a cycloaliphatic epoxy resin with a viscosity of 100-500mPas, such as, for example, celluloid CEL2021P;
the beneficial effect of the last step is adopted: the low-viscosity epoxy resin B can effectively adjust the viscosity of the product and improve the application operability of the product;
further, the curing agent is methyl hexahydrophthalic anhydride;
further, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30);
the beneficial effect of the last step is adopted: DMP-30 is taken as an accelerator, so that ring-opening polymerization reaction of epoxy groups of the modified epoxy resin A and the epoxy resin B and methyl hexahydrophthalic anhydride can be effectively promoted, and the crosslinking density of the die bond adhesive is improved;
further, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite;
the beneficial effect of the last step is adopted: the yellowing resistance of the die bond adhesive is improved;
further, the accelerator is white carbon DM30.
The preparation method of the modified epoxy die bond adhesive for the LED comprises the following steps:
the modified epoxy resin A and the epoxy resin B are uniformly mixed at 60 ℃; then adding thixotropic agent, mixing uniformly, and cooling to room temperature; adding a curing agent and uniformly stirring; and finally adding the modified epoxy crystal-fixing adhesive and the accelerator, uniformly mixing, and filtering and defoaming to obtain the modified epoxy crystal-fixing adhesive.
The invention has the technical effects and advantages that: the phenyl and Si-O chain segments are introduced into the epoxy resin structure, so that the epoxy resin structure can endow the epoxy resin with excellent high temperature resistance; meanwhile, the special trapezoid double-chain section structure has excellent toughness, elasticity and stability, so that the internal stress of the cured epoxy resin can be effectively reduced, and the cold and hot impact resistance and the tearing resistance of the cured material are improved.
Drawings
FIG. 1 is a graph showing baking of a die bond adhesive prepared according to various embodiments of the present invention in an oven at 200deg.C for 12 hours.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides a preparation method of modified epoxy resin A, which comprises the following steps:
(1) 100g of E44 epoxy resin and 50g of dimethylbenzene are weighed and added into a flask provided with a stirring device and a reflux condenser, condensed water is firstly introduced, the temperature is raised to 70 ℃ while stirring, the epoxy resin is completely melted, and then 1.0g of tetrabutyl orthotitanate is added and continuously stirred into a uniform solution;
(2) Weighing 30g of phenyl trapezoid polysilsesquioxane and 10g of dimethylbenzene, adding into a beaker, stirring and diluting to obtain a uniform solution, adding 0.3g of tetrabutyl orthotitanate, and continuously stirring to obtain the uniform solution;
(3) Heating the solution in the step (1) to 160 ℃ while stirring, preserving heat, and then dropwise adding the solution in the step (2) into the solution in the step (1) at a uniform speed while stirring for reaction;
(4) When the consumption of the solution in the step (2) reaches 75%, reducing the dropping speed, detecting by infrared spectrum until the vibration peak of-OH in the silicon hydroxyl in the reaction solution gradually disappears, stopping dropping, and then continuing stirring and preserving heat for 1h;
(5) After the reaction, the excess solvent in the solution was removed by distillation under reduced pressure to obtain a modified epoxy resin A.
Example 2
The embodiment provides a preparation method of a modified epoxy die-bonding adhesive for an LED, which comprises the following steps:
weighing 80 parts by weight of the modified epoxy resin A and 20 parts by weight of the epoxy resin B prepared in the example 1, and uniformly mixing at 60 ℃; adding 303 parts of thixotropic agent gas phase white carbon black DM, uniformly mixing, and cooling to room temperature; then 85 parts of methyl hexahydrophthalic anhydride as a curing agent is added and stirred uniformly; and finally adding 3 parts of antioxidant tris (2, 4-di-tert-butylphenyl) phosphite ester and 5 parts of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), uniformly mixing, and carrying out post-treatment such as filtration and defoaming to obtain the modified epoxy crystal-fixing adhesive.
Comparative example 1
The modified epoxy die-bonding glue sold in the market is MTS-200Y, and the main epoxy resin material used in the product is chemically modified by phenyl hydroxyl silicone oil.
Comparative example 2
The model of the epoxy die bond adhesive is DX-20 in certain Germany.
Comparative example 3
The model of the organosilicon die-bonding adhesive of a certain daily brand on the market is LPS-8445S-1.
The die bond adhesives prepared in example 2 and comparative examples 1, 2 and 3 were subjected to performance test, test 1: thrust test of thermal shock test, 5×8mil of die bond adhesive prepared by this example and comparative example 2 The silicon wafer is bonded to 2835 support, and is placed in a blast oven to be cured for 3 hours at 160 ℃, and the cured support is subjected to cold and hot impact test (i.e. heat preservation at-40 ℃ for 15min and then rapidThe silicon wafer was left at 120℃for 15 minutes and reciprocated 500 times, and then the push force values of the silicon wafer, which was reciprocated 0 and 500 times by cold and hot impact, were measured using a bonding shear force tester (MFM 1200), and the test results are shown in Table 1 below; test 2: 2.0g of the die bond adhesive is weighed, placed in a metal cup bowl with the diameter of 2cm, leveled, placed in a blast oven for curing at 160 ℃, then heated to 200 ℃ and baked for 12 hours for a rapid high-temperature aging test, and the test result is shown in figure 1.
Table 1 different die attach adhesives cold and hot impact test thrust test
As can be seen from the thrust data of the cold and hot impact test in Table 1, the silicone gum is often used in 7X 14mil since the silicone resin has a low hardness after curing, so that the thrust of comparative example 3 is at least 72g, but the thermal shock resistance is excellent 2 The above large-size chip packaging field. As can be seen from the experimental results of the example 2, the comparative example 1 and the comparative example 2, the modified epoxy resin die-bonding adhesive has a small decrease in thrust force compared with the pure epoxy resin and still meets the production line manufacturing process requirement, but the example 2 has a small decrease in thrust force compared with the comparative example 1, and meanwhile, the thermal shock resistance of the example 2 is obviously improved compared with the modified epoxy resin die-bonding adhesive of the comparative example 1, the thermal shock thrust force maintenance rate of the example 2 reaches 88.5%, which is better than 78.2% of that of the comparative example 1.
As can be seen from fig. 1, the various die attach adhesive cakes were subjected to a rapid high temperature aging test at 200 c for 12 hours, the silicone adhesive cake of comparative example 3 was substantially intact without yellowing, the epoxy adhesive cake of comparative example 2 had turned black brown, the modified epoxy adhesive cake of example 2 had slightly yellow, and the modified epoxy adhesive cake of comparative example 1 had exhibited orange-yellow. The high temperature yellowing resistance of the modified epoxy resin die bond adhesives of example 2 and comparative example 1 is better than that of comparative example 2, while the high temperature yellowing resistance of the modified epoxy resin die bond adhesive of example 2 is better than that of comparative example 1, closest to that of the silicone resin die bond adhesive.
The description not related to the specific embodiments of the present invention belongs to the technology known in the art, and may be implemented with reference to the known technology.
The invention is verified by repeated experiments, and satisfactory trial effect is obtained.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (6)
1. The utility model provides a LED is with modified epoxy die bond adhesive which characterized in that: the weight portions of the components are as follows:
40-100 parts of modified epoxy resin A, 10-30 parts of epoxy resin B, 40-120 parts of curing agent, 3-10 parts of accelerator, 1-8 parts of antioxidant and 0.1-5 parts of thixotropic agent;
wherein, the process of obtaining the modified epoxy resin A adopts epoxy resin and phenyl trapezoid polysilsesquioxane as raw materials, and utilizes the dehydration condensation reaction of hydroxyl groups of organic silicon and secondary hydroxyl groups in the epoxy resin to form stable silicon-oxygen-alkyl bonds, thereby obtaining the modified epoxy resin A; wherein, the epoxy resin adopts bisphenol A type epoxy resin E44, and the structural formula is as follows:
wherein m is more than or equal to 1 and less than or equal to 8;
the phenyl trapezoid polysilsesquioxane has the following structural formula:
wherein n is more than or equal to 2 and less than or equal to 6;
the curing agent is methyl hexahydrophthalic anhydride.
2. The modified epoxy die attach adhesive for an LED of claim 1, wherein: the epoxy resin B is an alicyclic epoxy resin with the viscosity of 100-500 mPas.
3. The modified epoxy die attach adhesive for an LED of claim 1, wherein: the accelerator
Is 2,4, 6-tris (dimethylaminomethyl) phenol.
4. The modified epoxy die attach adhesive for an LED of claim 1, wherein: the antioxidant
Is tris (2, 4-di-tert-butylphenyl) phosphite.
5. The modified epoxy die attach adhesive for an LED of claim 1, wherein: modified epoxy resin
The preparation method of A comprises the following steps:
s1: firstly, weighing a proper amount of epoxy resin and dimethylbenzene, adding the epoxy resin and dimethylbenzene into a flask provided with a stirring device and a reflux condenser, firstly introducing condensed water, heating to 50-100 ℃ while stirring to enable the epoxy resin to be completely melted, adding a catalyst tetrabutyl orthotitanate, and continuously stirring to form a uniform solution;
s2: weighing a proper amount of phenyl trapezoid polysilsesquioxane and dimethylbenzene, adding the mixture into a beaker for dilution, stirring the mixture uniformly, and adding
Adding catalyst tetrabutyl orthotitanate, and continuously and uniformly stirring;
s3: then heating the melted epoxy resin solution to 100-200 ℃ while stirring, preserving heat, and dripping the diluted phenyl trapezoid polysilsesquioxane solution into the epoxy resin solution at a constant speed while stirring for reaction;
s4: when the consumption of the phenyl trapezoid polysilsesquioxane solution reaches a certain amount, the dropping speed is reduced, the detection is carried out through infrared spectrum until the vibration peak of-OH in the silicon hydroxyl in the reaction solution gradually disappears, the dropping is stopped, and the stirring is continued for keeping
The temperature is 30min-120min;
s5: finally, the solution after the reaction is distilled under reduced pressure, and redundant solvent in the solution is removed to obtain
A modified epoxy resin A;
wherein the epoxy resin is E44 epoxy resin, and the structural formula is as follows:
wherein m is more than or equal to 1 and less than or equal to 8;
the phenyl trapezoid polysilsesquioxane has the following structural formula:
wherein n is more than or equal to 2 and less than or equal to 6.
6. A method for preparing the modified epoxy die-bonding adhesive for the LED according to claim 1, which is characterized in that: the method comprises the following steps:
the modified epoxy resin A and the epoxy resin B are uniformly mixed at 60 ℃; then adding thixotropic agent, mixing uniformly, and cooling to room temperature; adding a curing agent and uniformly stirring; and finally adding an antioxidant and an accelerator, uniformly mixing, and filtering and defoaming to obtain the modified epoxy crystal-fixing adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211181917.7A CN115491172B (en) | 2022-09-27 | 2022-09-27 | Modified epoxy die-bonding adhesive for LEDs and preparation method of modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211181917.7A CN115491172B (en) | 2022-09-27 | 2022-09-27 | Modified epoxy die-bonding adhesive for LEDs and preparation method of modified epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115491172A CN115491172A (en) | 2022-12-20 |
| CN115491172B true CN115491172B (en) | 2024-03-22 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106753138A (en) * | 2017-01-06 | 2017-05-31 | 上海汉司实业有限公司 | A kind of LED single-component epoxy insulation crystal-bonding adhesive and preparation method |
| CN107400239A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes of end-blocking and its preparation method and application certainly |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400239A (en) * | 2016-05-19 | 2017-11-28 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes of end-blocking and its preparation method and application certainly |
| CN106753138A (en) * | 2017-01-06 | 2017-05-31 | 上海汉司实业有限公司 | A kind of LED single-component epoxy insulation crystal-bonding adhesive and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Viscoelastic and Mechanical Properties of Epoxy/Multifunctional Polyhedral Oligomeric Silsesquioxane Nanocomposites and Epoxy/Ladderlike Polyphenylsilsesquioxane Blends;Li GZ 等;Macromolecules;8686-8693 * |
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