CN102206398A - Liquid epoxy underfill, preparation method and application thereof - Google Patents
Liquid epoxy underfill, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a liquid epoxy underfill, its preparation method and application. The underfill comprises, by weight, 0-100 parts of two types of liquid epoxy resin, 50-150 parts of a curing agent, 0.05-5.0 parts of a curing accelerator, 0-20 parts of a flexibilizer, 0.05-5.0 parts of silane coupling agent, 100-1000 parts of an inorganic filler, and 0.01-5.0 parts of dye. The liquid epoxy underfill provided in the invention still maintains a low viscosity when the additive amount of the inorganic filler reaches 60-70% (a viscosity less than 6000mPa.s at 25 DEG C). A resin cured product formed by resin curing with proper technology has a flame retardation grade of UL94-V0 and good mechanical performance (an achievable bending strength of 150MPa). Thus, the liquid underfill of the invention can satisfy the requirements of high density microelectronic packaging devices like ball grid array (BGA) packaging devices or chip size packaging devices.
Description
Technical field
The present invention relates to filler and preparation method thereof and application at the bottom of the liquid epoxy.
Background technology
Along with microelectronic packaging technology develops to little, light, thin direction, the advanced packing forms of ball type array (BGA), wafer-level package high-density such as (CSP) has become a kind of main flow trend on the market.Filler at the bottom of the liquid epoxy (Underfill) is the critical material that ensures BGA, CSP package reliability; it is filled in the slit that is formed by miniature soldered ball between upside-down mounting welding core and the organic substrate; its main purpose is the strength of joint that strengthens chip and substrate; protect miniature soldered ball to avoid external pollution; reduce the stress of packaging, improve the work-ing life of device.Consider from reliability and processing performance angle, require liquid epoxy at the bottom of filler have characteristics such as low viscosity, good mechanical property and anti-cracking performance.
U.S. Pat 6,117,953, among Chinese invention patent ZL 00123621.0 and the ZL 03157937.X at the bottom of the disclosed liquid epoxy among the preparation method of filler, all adopt the combination of low viscous alicyclic epoxy and liquid acid anhydride curing agents, had the favorable manufacturability energy.But alicyclic epoxy exists flame retardant properties poor, the problem that fragility is big, the also flame retardant properties of not mentioned material in the above-mentioned patent.Disclose naphthalene nucleus type epoxy and amine curing agent among the U.S. Pat 20090020779A1 and be combined in the application in the filler at the bottom of the epoxy, naphthalene nucleus type epoxy is being contributed aspect material mechanical performance and the raising flame retardant resistance to some extent guaranteeing.
Summary of the invention
The purpose of this invention is to provide filler and preparation method thereof and application at the bottom of a kind of liquid epoxy.
Filler at the bottom of the liquid epoxy provided by the invention comprises Resins, epoxy, solidifying agent, curing catalyst, toughner, surface treatment agent, mineral filler and dyestuff;
Described Resins, epoxy is selected from least a among Resins, epoxy A and the Resins, epoxy B; Wherein, described Resins, epoxy A means and is the cycloaliphatic epoxy resin of liquid under the normal temperature, is selected from shown in the formula I 3,4-epoxycyclohexyl methyl-3 ', and shown in 4 '-epoxycyclohexyl manthanoate and the formula II 1, at least a in the 6-naphthyl diglycidylether; Described Resins, epoxy B is selected from 2,2-two (2,3-epoxy third oxygen support phenyl) methane (also being Bisphenol F type diglycidyl ether epoxy resin) and 2, at least a in 2-two (2,3-epoxy third oxygen supports phenyl) propane (also being the bisphenol A-type diglycidyl ether epoxy resin); Described 2,2-two (2,3-epoxy third oxygen support phenyl) methane and 2, the number-average molecular weight of 2-two (2,3-epoxy third oxygen support phenyl) propane is 400-2000 gram/mole, preferably 400-1000 gram/mole, more preferably 400-800 gram/mole; Above-mentioned two kinds of resins all can be bought by open commercial sources and obtain.
(formula I)
(formula II)
Described solidifying agent is selected from least a in methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride phthalic anhydride and the methyl carbic anhydride;
Described curing catalyst is selected from imidazoles, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3,5-triethyl-six hydrogen-S-triazine, 1,3, at least a in 5-trimethylammonium-six hydrogen-S-triazine, triethylamine, triphenylphosphine, triethyl phosphine, acetylacetone cobalt, ferric acetyl acetonade, acetylacetonate nickel, methyl ethyl diketone neodymium and the aluminium acetylacetonate;
Described toughner is to contain 9 shown in the formula III, the 10-dihydro-9-oxy is assorted-and the silicone compounds of 10-phospho hetero phenanthrene-10-oxide compound (DOPO) group;
(formula III)
The preparation method of the toughner of structure shown in the above-mentioned formula III sees the Chinese patent that publication number is CN101445520A for details.In the described formula III, R
1, R
2, R
3And R
4All be selected from least a in methyl, ethyl, methoxyl group, oxyethyl group, phenyl and the phenoxy group, n is the integer of 1-10, the integer of preferred 1-4, R
5Be methylene radical or ethylidene, R
6Be methylene radical or ethylidene.The preferred DOPO-1 of described toughner, 3-diethylidene-1,1,3,3-tetramethyl disiloxane, DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide or DOPO-1,3-dipropylene-1,1,3,3-tetramethyl disiloxane;
Described surface treatment agent means the interfacial interaction that can increase between mineral filler and the Resins, epoxy, improve the organic compound and composition thereof of both consistencies, be selected from γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (this compound can join silication worker company limited available from Nanjing), γ-An Jibingjisanyiyangjiguiwan (this compound can join silication worker company limited available from Nanjing), γ-mercaptan aminopropyl trimethoxysilane (this compound can join silication worker company limited available from Nanjing), at least a in anilinomethyl Ethoxysilane (this compound can join silication worker company limited available from Nanjing) and β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (this compound can join silication worker company limited available from Nanjing);
Described mineral filler is selected from least a in fused preparing spherical SiO 2, amorphous silica, crystalline silicon-dioxide and the synthetic silicon-dioxide; The median size of described mineral filler is the 0.1-10 micron; Described dyestuff is selected from least a in carbon black and the Graphite Powder 99.
Filler can only be made up of said components at the bottom of the aforesaid liquid epoxy provided by the invention; Preferably, filler is any one among the filler a-c at the bottom of the liquid epoxy of following portions by weight at the bottom of the described liquid epoxy;
Filler a is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is above-mentioned Resins, epoxy A, and the parts by weight of described Resins, epoxy A are 0-100, preferred 20-100, more preferably 50-100; The parts by weight of described solidifying agent are 50-150, specifically can be 60-80,60-100,60-120,80-100,80-120,100-120,100-150 or 120-150, preferred 60-150, more preferably 80-150; The parts by weight of described curing catalyst are 0.05-5, specifically can be 0.5-2 or 0.05-2, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described toughner are 0-20, specifically can be 8-20,10-20,12-20,8-12,8-10,10-12,5-8,5-10 or 2-5, preferred 2-20, more preferably 5-20; The parts by weight of described surface treatment agent are 0.05-5.0, specifically can be 0.05-0.5,0.05-3,0.05-4,0.5-4,0.5-3,3-4 or 4-5, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, specifically can be 300-400,300-350,400-500 or 350-400, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, specifically can be 0.5-5,0.01-0.5,0.01-0.02,0.01-0.05,0.02-0.05 or 0.05-0.5, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy A and toughner is not 0;
Filler b is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is Resins, epoxy B, and the parts by weight of described Resins, epoxy B are 100-0, preferred 100-20, more preferably 100-50; The parts by weight of described solidifying agent are 50-150, specifically can be 60-80,60-100,60-120,80-100,80-120,100-120,100-150 or 120-150, preferred 60-150, more preferably 80-150; The parts by weight of described curing catalyst are 0.05-5, specifically can be 0.5-2 or 0.05-2, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described toughner are 0-20, specifically can be 8-20,10-20,12-20,8-12,8-10,10-12,5-8,5-10 or 2-5, preferred 2-20, more preferably 5-20; The parts by weight of described surface treatment agent are 0.05-5.0, specifically can be 0.05-0.5,0.05-3,0.05-4,0.5-4,0.5-3,3-4 or 4-5, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, specifically can be 300-400,300-350,400-500 or 350-400, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, specifically can be 0.5-5,0.01-0.5,0.01-0.02,0.01-0.05,0.02-0.05 or 0.05-0.5, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy B and toughner is not 0;
Filler c is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is made up of described Resins, epoxy A and described Resins, epoxy B, wherein, the parts by weight of described Resins, epoxy A are 0-100, preferred 20-100, more preferably 50-100, the parts by weight of described Resins, epoxy B are 100-0, preferred 100-20, more preferably 100-50; The parts by weight of described solidifying agent are 50-150, specifically can be 60-80,60-100,60-120,80-100,80-120,100-120,100-150 or 120-150, preferred 60-150, more preferably 80-150; The parts by weight of described curing catalyst are 0.05-5, specifically can be 0.5-2 or 0.05-2, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described toughner are 0-20, specifically can be 8-20,10-20,12-20,8-12,8-10,10-12,5-8,5-10 or 2-5, preferred 2-20, more preferably 5-20; The parts by weight of described surface treatment agent are 0.05-5.0, specifically can be 0.05-0.5,0.05-3,0.05-4,0.5-4,0.5-3,3-4 or 4-5, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, specifically can be 300-400,300-350,400-500 or 350-400, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, specifically can be 0.5-5,0.01-0.5,0.01-0.02,0.01-0.05,0.02-0.05 or 0.05-0.5, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy A, Resins, epoxy B and toughner is not 0.
The method for preparing filler at the bottom of the aforesaid liquid epoxy provided by the invention, comprise the steps: described Resins, epoxy, described solidifying agent, described curing catalyst, described toughner, described surface treatment agent, described mineral filler and described dyestuff mixing, obtain filler at the bottom of the described liquid epoxy.
In addition; the application of filler in the preparation micro-electron packaging device at the bottom of the liquid epoxy that the invention described above provides; also belong to protection scope of the present invention, wherein, described micro-electron packaging device is BGA Package (BGA) device or chip size packages (CSP) device.
Filler at the bottom of the liquid epoxy provided by the invention still has lower viscosity (25 ℃ time viscosity less than 6000mPas) when the mineral filler addition reaches 60-70%; The resin cured matter that resin forms after suitably technology is solidified has UL94-V0 level flame retardant rating and excellent mechanical property (flexural strength can reach 150MPa) etc., can satisfy the needs of high-density microelectronics Packaging such as BGA, CSP.
Description of drawings
Fig. 1 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 1 liquid epoxy.
Fig. 2 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 2 liquid epoxies.
Fig. 3 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 3 liquid epoxies.
Fig. 4 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 4 liquid epoxies.
Fig. 5 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 5 liquid epoxies.
Fig. 6 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 6 liquid epoxies.
Fig. 7 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of embodiment 7 liquid epoxies.
Fig. 8 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of comparative example 1 liquid epoxy.
Fig. 9 is filler thermo-mechanical analysis (TMA) collection of illustrative plates at the bottom of comparative example 2 liquid epoxies.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.
All as follows the performance of preparation gained liquid epoxy bed material is measured (described measuring method is ordinary method if no special instructions) among the following embodiment:
1) viscosity: use the selection viscometer of Brookfield DV-II company, the viscosity the when rotation number of use 20rpm is measured 25 ℃.
2) Mechanics Performance Testing (GB/T 9341-2000): secundum legem prepares specimen, uses Instron 3365 universal testing machines.
3) second-order transition temperature (T
g) and linear expansivity (CTE): instrument: pass through to use mould at 175 ℃, 6.9N/mm according to the EMMI standard
2, 120 seconds the molding time compacted under and measure.Instrument: thermomechanical analyzer TMA model Q400, U.S. TA company.Temperature rise rate: 2 ℃/min.
4) flame retardant properties test (ASTM UL94 or GB/T 2408-2008 standard): CZF-3 type horizontal vertical burning determinator.
Embodiment 1
Weighing 50 gram Resins, epoxy A 1,6-naphthyl diglycidylether, 50 gram Resins, epoxy B Bisphenol F type diglycidyl ether epoxy resin (400≤M
n≤ 500), 150 gram solidifying agent methylhexahydrophthalic anhydrides, 5 gram surface treatment agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 20 gram toughner DOPO-1,3-diethylidene-1,1,3, the 3-tetramethyl disiloxane, 0.1 micron fusion spherical silica of 80 gram mineral filler median sizes, 10 microns fusion preparing spherical SiO 2s of 220 gram median sizes, 2 gram carbon blacks add in the centrifugal mixer and stirred 30 minutes, add 0.5 gram curing catalyst 1-cyanoethyl-2-ethyl-4-methylimidazole and continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Wherein, DOPO-1,3-diethylidene-1,1,3, the 3-tetramethyl disiloxane is to be prepared as follows and to get: with DOPO (108.0g, 0.50mol), 1,1,3,3-tetramethyl--1, the 3-divinyl disiloxane (46.5g, 0.25mol), AIBN (4.1g, 0.025mol) and the mixing solutions of benzene (100mL) add in the 1000mL there-necked flask, 80 ℃ of back flow reaction after 1 hour underpressure distillation go out to desolvate and react in the lower-boiling impurity produced, cool to 60 ℃.Wash 3～5 times with sherwood oil and draw the low polar impurity of producing in the reaction, underpressure distillation obtains faint yellow transparent solid 105.0g, DOPO-1,3-diethylidene-1,1,3,3-tetramethyl disiloxane (productive rate 68%) after removing and desolvating.
Embodiment 2
Weighing 100 gram Resins, epoxy A3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl manthanoate, 80 gram solidifying agent methyl tetrahydrophthalic anhydrides, 0.5 gram surface treatment agent shrink γ-mercaptan aminopropyl trimethoxysilane, 2 gram toughner DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide, 0.2 micron fusion spherical silica of 100 gram median sizes, 4 microns fusion preparing spherical SiO 2s of 400 gram median sizes, 5 gram carbon blacks add in the centrifugal mixer and stirred 30 minutes, add 5 gram curing catalyst ferric acetyl acetonades and continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Wherein, DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide is to be prepared as follows and to get: with DOPO (108.0g, 0.50mol), 1,3-dimethyl-1,3-divinyl-1,3-phenylbenzene sily oxide (77.5g, 0.25mol), AIBN (4.1g, 0.025mol) and the mixing solutions of benzene (100mL) add in the 1000mL there-necked flask, 80 ℃ of back flow reaction after 1 hour underpressure distillation go out to desolvate and react in the lower-boiling impurity produced, cool to 60 ℃.Wash 3～5 times with sherwood oil and draw the low polar impurity of producing in the reaction, underpressure distillation obtains faint yellow transparent solid 129.5g, DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide (productive rate 70%) after removing and desolvating.
Embodiment 3
Weighing 80 gram Resins, epoxy B bisphenol A-type diglycidyl ether epoxy resin (900≤M
n≤ 1000), 20 gram Resins, epoxy B Bisphenol F type diglycidyl ether epoxy resin (400≤M
n≤ 500), 150 gram solidifying agent methylhexahydrophthalic anhydrides, 60 gram solidifying agent methyl carbic anhydrides, 5 gram surface treatment agent γ-An Jibingjisanyiyangjiguiwans, 5 gram toughner DOPO-1,3-diethylidene-1,1,3, the 3-tetramethyl disiloxane, 0.8 micron fusion spherical silica of 50 gram median sizes, 1 micron fusion preparing spherical SiO 2 of 250 gram median sizes, 0.01 gram Graphite Powder 99 adds in the centrifugal mixer and stirred 30 minutes, add 0.05 gram curing catalyst 2-phenyl-4-methylimidazole and continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Embodiment 4
Weighing 20 gram Resins, epoxy A 1,6-naphthyl diglycidyl ether epoxy resin, 30 gram Resins, epoxy A 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl manthanoate, 50 gram Resins, epoxy B Bisphenol F type diglycidyl ether epoxy resin (500≤M
n≤ 600), 80 gram solidifying agent methylhexahydrophthalic anhydrides, 0.05 gram surface treatment agent anilinomethyl Ethoxysilane, 8 gram toughner DOPO-1,3-dipropylene-1,1,3,3-tetramethyl disiloxane, 0.1 micron fusion spherical silica of 50 gram median sizes, 2.5 microns fusion preparing spherical SiO 2s of 300 gram median sizes, 0.5 the gram carbon black adds in the centrifugal mixer and stirred 30 minutes, adds 0.5 gram curing catalyst 2-ethyl-4-methylimidazole, continue to stir 5 minutes, and obtained filler at the bottom of the finely dispersed liquid epoxy.
Wherein, DOPO-1,3-dipropylene-1,1,3, the 3-tetramethyl disiloxane is to be prepared as follows and to get: with DOPO (108.0g, 0.50mol), 1,1,3,3-tetramethyl--1,3-diallyl sily oxide (53.5g, 0.25mol), AIBN (4.1g, 0.025mol) and the mixing solutions of benzene (100mL) add in the 1000mL there-necked flask, 80 ℃ of back flow reaction after 1 hour underpressure distillation go out to desolvate and react in the lower-boiling impurity produced, cool to 60 ℃.Wash 3～5 times with sherwood oil and draw the low polar impurity of producing in the reaction, underpressure distillation obtains faint yellow transparent solid 132.5g, DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide (productive rate 69%) after removing and desolvating.
Embodiment 5
Weighing 90 gram Resins, epoxy A 1,6-naphthyl diglycidyl ether epoxy resin, 10 gram Resins, epoxy A3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl manthanoate, 100 gram solidifying agent methylhexahydrophthalic anhydrides, 5 gram surface treatment agent β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 20 parts of toughner DOPO-1,3-diethylidene-1,1,3, the 3-tetramethyl disiloxane, 0.4 micron fusion spherical silica of 400 gram median sizes, 0.05 gram Graphite Powder 99, add in the centrifugal mixer and stirred 30 minutes, add 5 gram curing catalysts 1,3,5-trimethylammonium-six hydrogen-S-triazine, continue to stir 5 minutes, and obtained filler at the bottom of the finely dispersed liquid epoxy.
Embodiment 6
Weighing 100 gram Resins, epoxy B Bisphenol F type diglycidyl ether epoxy resin (400≤Mn≤500), 100 gram solidifying agent methylhexahydrophthalic anhydrides, 3 gram surface treatment agent shrink γ-mercaptan aminopropyl trimethoxysilane, 10 gram toughner DOPO-1,3-diethylidene-1,1,3, the 3-tetramethyl disiloxane, 3.5 microns fusion spherical silicas of 350 gram median sizes, 0.02 gram carbon black, add in the centrifugal mixer and stirred 30 minutes, add 2 gram curing catalyst triphenylphosphines, continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Embodiment 7
Weighing 100 gram Resins, epoxy A 1,6-naphthyl diglycidyl ether epoxy resin, 120 gram solidifying agent methyl tetrahydrophthalic anhydrides, 4 gram surface treatment agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 12 gram toughner DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide, 0.4 micron fusion spherical silica of 200 gram median sizes, 2.5 microns fusion preparing spherical SiO 2s of 200 gram median sizes, 0.2 gram carbon black, add in the centrifugal mixer and stirred 30 minutes, add 5 gram curing catalyst 1-cyanoethyl-2-ethyl-4-methylimidazoles, continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Comparative example 1
Weighing 100 grams 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl manthanoate, 80 gram methyl tetrahydrophthalic anhydrides, 0.5 gram shrink γ-mercaptan aminopropyl trimethoxysilane, 0.2 micron fusion spherical silica of 100 gram median sizes, 4.0 microns fusion preparing spherical SiO 2s of 400 gram median sizes, 0.01 gram Graphite Powder 99 adds in the centrifugal mixer and stirred 30 minutes, add 1 gram ferric acetyl acetonade and continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Comparative example 2
DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide prepares with embodiment 2.
Weighing 80 gram bisphenol A-type diglycidyl ether epoxy resin (600≤M
n≤ 700), 20 gram Bisphenol F type diglycidyl ether epoxy resin (700≤M
n≤ 800), 60 gram methylhexahydrophthalic anhydrides, 60 gram methyl carbic anhydrides, 5 gram γ-An Jibingjisanyiyangjiguiwans, 5 gram DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide, 0.8 micron fusion spherical silica of 50 gram median sizes, 1.0 microns fusion preparing spherical SiO 2s of 250 gram median sizes, 0.3 gram Graphite Powder 99, add in the centrifugal mixer and stirred 30 minutes, add 2-phenyl-4-methylimidazole and continue to stir 5 minutes, obtain filler at the bottom of the finely dispersed liquid epoxy.
Shown in Fig. 1-9, its physicals is all listed in table 1 to thermo-mechanical analysis (TMA) collection of illustrative plates that the foregoing description prepares filler at the bottom of the gained liquid epoxy respectively.
The performance of filler and resin cured matter thereof at the bottom of table 1, the liquid epoxy
By above-mentioned Fig. 1-9 and table 1 as can be known, filler has good mechanical performance, high glass-transition temperature (T at the bottom of the liquid epoxy that makes among the embodiment
g), low linear expansion rate (CTE) and good flame retardant property etc.
Claims (7)
1. filler at the bottom of the liquid epoxy comprises Resins, epoxy, solidifying agent, curing catalyst, toughner, surface treatment agent, mineral filler and dyestuff;
Described Resins, epoxy is selected from least a among Resins, epoxy A and the Resins, epoxy B; Wherein, described Resins, epoxy A is selected from 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl manthanoate and 1, at least a in the 6-naphthyl diglycidylether; Described Resins, epoxy B is selected from 2,2-two (2,3-epoxy third oxygen support phenyl) methane and 2, at least a in 2-two (2,3-epoxy third oxygen support phenyl) propane;
Described solidifying agent is selected from least a in methylhexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride phthalic anhydride and the methyl carbic anhydride;
Described curing catalyst is selected from imidazoles, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3,5-triethyl-six hydrogen-S-triazine, 1,3, at least a in 5-trimethylammonium-six hydrogen-S-triazine, triethylamine, triphenylphosphine, triethyl phosphine, acetylacetone cobalt, ferric acetyl acetonade, acetylacetonate nickel, methyl ethyl diketone neodymium and the aluminium acetylacetonate;
Described toughner is phosphorous silicone compounds shown in the formula III;
(formula III)
In the described formula III, R
1, R
2, R
3And R
4All be selected from least a in methyl, ethyl, methoxyl group, oxyethyl group, phenyl and the phenoxy group, n is the integer of 1-10, R
5Be methylene radical or ethylidene, R
6Be methylene radical or ethylidene;
Described surface treatment agent is selected from γ-(2,3-epoxy third oxygen) at least a in propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-mercaptan aminopropyl trimethoxysilane, anilinomethyl Ethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane;
Described mineral filler is selected from least a in fused preparing spherical SiO 2, amorphous silica, crystalline silicon-dioxide and the synthetic silicon-dioxide;
Described dyestuff is selected from least a in carbon black and the Graphite Powder 99.
2. filler at the bottom of the liquid epoxy according to claim 1 is characterized in that: filler is made up of described Resins, epoxy, described solidifying agent, described curing catalysts, described toughner, described surface treatment agent, described mineral filler and described dyestuff at the bottom of the described liquid epoxy.
3. liquid epoxy bed material according to claim 1 and 2 is characterized in that: filler is any one among the filler a-c at the bottom of the liquid epoxy of following portions by weight at the bottom of the described liquid epoxy;
Filler a is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is above-mentioned Resins, epoxy A, and the parts by weight of described Resins, epoxy A are 0-100, preferred 20-100, more preferably 50-100; The parts by weight of described solidifying agent are 50-150, preferred 60-150, more preferably 80-150; The parts by weight of described curing catalyst are 0.05-5, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described toughner are 0-20, preferred 2-20, more preferably 5-20; The parts by weight of described surface treatment agent are 0.05-5.0, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy A and toughner is not 0;
Filler b is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is Resins, epoxy B, and the parts by weight of described Resins, epoxy B are 100-0, preferred 100-20, more preferably 100-50; The parts by weight of described solidifying agent are 50-150, preferred 60-150, more preferably 80-150; The parts by weight of described curing catalyst are 0.05-5, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described toughner are 0-20, preferred 2-20, more preferably 5-20; The parts by weight of described surface treatment agent are 0.05-5.0, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy B and toughner is not 0;
Filler c is made up of each component of following portions by weight at the bottom of the described liquid epoxy: described Resins, epoxy is made up of described Resins, epoxy A and described Resins, epoxy B, wherein, the parts by weight of described Resins, epoxy A are 0-100, preferred 20-100, more preferably 50-100, the parts by weight of described Resins, epoxy B are 100-0, preferred 100-20, more preferably 100-50; The parts by weight of described solidifying agent are 50-150, preferred 60-150, more preferably 80-150, the parts by weight of described curing catalyst are 0.05-5, preferred 0.1-5, more preferably 0.5-5, the parts by weight of described toughner are 0-20, preferred 2-20, more preferably 5-20, the parts by weight of described surface treatment agent are 0.05-5.0, preferred 0.1-5, more preferably 0.5-5; The parts by weight of described mineral filler are 100-1000, preferred 200-500, more preferably 300-500; The parts by weight of described dyestuff are 0.01-5.0, preferred 0.1-5, more preferably 0.1-2; Wherein, the weight part number average of described Resins, epoxy A, Resins, epoxy B and toughner is not 0.
4. according to the arbitrary described liquid epoxy bed material of claim 1-3, it is characterized in that: described 2,2-two (2,3-epoxy third oxygen support phenyl) methane and 2,2-two (2,3-epoxy third oxygen support phenyl) number-average molecular weight of propane is 400-2000 gram/mole, preferred 400-1000 gram/mole, more preferably 400-800 gram/mole; In the described formula III, n is the integer of 1-4; Toughner shown in the described formula III is DOPO-1,3-diethylidene-1,1,3,3-tetramethyl disiloxane, DOPO-1,3-diethylidene-1,3-dimethyl-1,3-phenylbenzene sily oxide or DOPO-1,3-dipropylene-1,1,3,3-tetramethyl disiloxane; The median size of described mineral filler is the 0.1-10 micron.
5. method for preparing filler at the bottom of the arbitrary described liquid epoxy of claim 1-4, comprise the steps: described Resins, epoxy, described solidifying agent, described curing catalysts, described toughner, described surface treatment agent and described mineral filler and described dyestuff mixing, obtain filler at the bottom of the described liquid epoxy.
6. the application of filler in the preparation micro-electron packaging device at the bottom of the arbitrary described liquid epoxy of claim 1-4.
7. application according to claim 6 is characterized in that: described micro-electron packaging device is ball grating array package device or chip size packages device.
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| CN 201110076366 CN102206398A (en) | 2011-03-28 | 2011-03-28 | Liquid epoxy underfill, preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038285A (en) * | 2010-07-29 | 2013-04-10 | 三井化学株式会社 | Composition, composition being for end-face sealing agent for display devices and consisting of the composition, display devices, and process for producing same |
| CN104684955A (en) * | 2012-09-26 | 2015-06-03 | 赫克塞尔合成有限公司 | Resin composition and composite structure containing resin |
| CN106633918A (en) * | 2017-01-13 | 2017-05-10 | 山东船舶技术研究院 | High-strength high-heat-resistance flame-retardant silicone rubber material and preparation method thereof |
| CN106832408A (en) * | 2017-03-02 | 2017-06-13 | 张家港市山牧新材料技术开发有限公司 | A kind of siliceous DOPO derivative flame retardants and preparation method thereof |
| CN106832409A (en) * | 2017-03-02 | 2017-06-13 | 张家港市山牧新材料技术开发有限公司 | A kind of DOPO derivative flame retardants and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117953A (en) * | 1998-01-22 | 2000-09-12 | Shin-Etsu Chemical Co., Ltd. | Liquid epoxy resin composition for ball grid array package |
| CN1590498A (en) * | 2003-09-03 | 2005-03-09 | 中国科学院化学研究所 | Liquid epoxy packaging material and its preparation method and application |
| CN1887892A (en) * | 2006-07-28 | 2007-01-03 | 四川东材企业集团有限公司 | No-halogen fire-proof phosphorus-containing compound with high heat stability and its prepn |
| CN101205349A (en) * | 2007-12-03 | 2008-06-25 | 南京航空航天大学 | High-conductivity epoxy moulding material having heat conducting path and manufacturing method thereof |
| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
-
2011
- 2011-03-28 CN CN 201110076366 patent/CN102206398A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117953A (en) * | 1998-01-22 | 2000-09-12 | Shin-Etsu Chemical Co., Ltd. | Liquid epoxy resin composition for ball grid array package |
| CN1590498A (en) * | 2003-09-03 | 2005-03-09 | 中国科学院化学研究所 | Liquid epoxy packaging material and its preparation method and application |
| CN1887892A (en) * | 2006-07-28 | 2007-01-03 | 四川东材企业集团有限公司 | No-halogen fire-proof phosphorus-containing compound with high heat stability and its prepn |
| CN101445520A (en) * | 2007-11-26 | 2009-06-03 | 中国科学院化学研究所 | Phosphoric organic silicon compound, preparation method and application thereof |
| CN101205349A (en) * | 2007-12-03 | 2008-06-25 | 南京航空航天大学 | High-conductivity epoxy moulding material having heat conducting path and manufacturing method thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038285A (en) * | 2010-07-29 | 2013-04-10 | 三井化学株式会社 | Composition, composition being for end-face sealing agent for display devices and consisting of the composition, display devices, and process for producing same |
| CN103038285B (en) * | 2010-07-29 | 2015-11-25 | 三井化学株式会社 | Composition, the display equipment mechanical seal agent composition, display equipment and the manufacture method thereof that are made up of said composition |
| CN104684955A (en) * | 2012-09-26 | 2015-06-03 | 赫克塞尔合成有限公司 | Resin composition and composite structure containing resin |
| CN106633918A (en) * | 2017-01-13 | 2017-05-10 | 山东船舶技术研究院 | High-strength high-heat-resistance flame-retardant silicone rubber material and preparation method thereof |
| CN106832409B (en) * | 2017-03-02 | 2018-11-02 | 张家港市山牧新材料技术开发有限公司 | A kind of DOPO derivative flame retardants and preparation method thereof |
| CN106832409A (en) * | 2017-03-02 | 2017-06-13 | 张家港市山牧新材料技术开发有限公司 | A kind of DOPO derivative flame retardants and preparation method thereof |
| CN106832408A (en) * | 2017-03-02 | 2017-06-13 | 张家港市山牧新材料技术开发有限公司 | A kind of siliceous DOPO derivative flame retardants and preparation method thereof |
| CN106832408B (en) * | 2017-03-02 | 2019-01-15 | 张家港市山牧新材料技术开发有限公司 | A kind of siliceous DOPO derivative flame retardant and preparation method thereof |
| CN110402265A (en) * | 2017-03-16 | 2019-11-01 | 3M创新有限公司 | Epoxy casting resin preparation |
| CN110402265B (en) * | 2017-03-16 | 2022-05-03 | 3M创新有限公司 | Epoxy casting resin formulation |
| CN113604184A (en) * | 2021-10-09 | 2021-11-05 | 武汉市三选科技有限公司 | Chip packaging material, chip packaging structure and packaging method |
| WO2024055946A1 (en) * | 2022-09-15 | 2024-03-21 | 华为技术有限公司 | Resin composition, method for preparing same, and use thereof |
| CN116640475A (en) * | 2023-04-28 | 2023-08-25 | 广东工业大学 | Chip resistor secondary protection slurry and preparation method and application thereof |
| CN116640475B (en) * | 2023-04-28 | 2024-07-16 | 广东工业大学 | Chip resistor secondary protection slurry and preparation method and application thereof |
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