CN107429039A - Epoxy molding compounds, preparation method and use - Google Patents
Epoxy molding compounds, preparation method and use Download PDFInfo
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- CN107429039A CN107429039A CN201580077931.4A CN201580077931A CN107429039A CN 107429039 A CN107429039 A CN 107429039A CN 201580077931 A CN201580077931 A CN 201580077931A CN 107429039 A CN107429039 A CN 107429039A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
Abstract
The present invention provides a kind of epoxy molding compounds, preparation method and use.The epoxy molding compounds include epoxy resin, phenolic resin, curing accelerator, the crystalline silica optionally combined with specific preparing spherical SiO 2 and one or more and are selected from following additive：Fire retardant, wax, coupling agent, pigment, ion trap agent and stress absorption agent.The epoxy molding compounds have high-termal conductivity and low line skew, while keep other desirable propertieses required by full molding module.
Description
Technical field
The present invention relates to a kind of epoxy molding compounds, and it includes the crystalline silica with specific size distribution, appoints
Selection of land combines with the preparing spherical SiO 2 with specific particle diameter, and the epoxy molding compounds have high-termal conductivity and low line
Skew.The invention further relates to a kind of method for preparing epoxy molding compounds and epoxy molding compounds to be used for full molding module
Purposes.
Background technology
Epoxy molding compounds (" EMC ") are widely used in various encapsulation fields, such as semiconductor device, integrated circuit, disappear
Power-consuming son, vehicles etc..EMC has a very important effect in Electronic Packaging, for example, protection device inside from all
Such as dust, moisture, radiation or the influence of mechanical shock simultaneously promote to radiate.
With the development of microelectronics packing technique, EMC, as main microelectronics packaging material, it is also fast-developing and
Occupy the market share of the microelectronics packaging material more than 90%.
Molded epoxy naval stores is prepared by epoxy molding compounds.Typical epoxy molding compounds include a kind of or more
Kind epoxy resin, one or more curing agent (curing agent), one or more curing accelerators (catalyst), one or more are filled out
The one or more additives expected and be optionally present.Kept for the regular hour at elevated temperature in a mold, can incited somebody to action
Epoxy molding compounds mould and are cured as the article of solid forms.Then, after the article of the demoulding is usual at elevated temperatures
Solidify to complete curing reaction and obtain the resin article with desirable properties.
US8362115B2 discloses a kind of composition epoxy resin, and it includes specific epoxy resin, phenolic resin, consolidated
Change accelerator and inorganic filler.Wherein disclosed composition epoxy resin has preferable reliability and preferable warpage property.
But US8362115B2 does not refer to thermal conductivity and line skew property.
Module is advanced hybrid integrated semiconductor, such as integrated circuit and power device.Traditional module is half encapsulation
, this makes it possible to realize high power density and quick heat radiating, and requires simple method for packing.However, such half encapsulates
Deficiency be low antijamming capability, lower security coefficient, the low resistance for high pressure and high humidity.Full molding module represents all
Semiconductor is all encapsulated in EMC without exposed fin, and this improves the electric property and stability of module.Full molding module
It is the development trend of module.
In full molding module, there is high requirement for EMC thermal conductivity and mobility.High-termal conductivity always means
The high load of high thermal conductivity filler, the traditional high-termal conductivity EMC that thus be accordingly used in full molding TO applications always require high viscosity, but
This may cause the reduction of the mobility of full molding module and the increase of line skew, because being integrated with many work(in a module
Can unit.
Therefore, a kind of epoxy molding compounds are still needed badly, it can balance high-termal conductivity and high fluidity, and still
Keep other desirable propertieses required in full molding module.
The content of the invention
On the one hand, the present invention provides a kind of epoxy molding compounds, and it has high-termal conductivity and low line skew while protected
Stay other properties required by full molding module.
The epoxy molding compounds of the present invention include：
(a) epoxy resin,
(b) phenolic resin,
(c) curing accelerator,
(d) crystalline silica, it is optionally combined with preparing spherical SiO 2, and
(e) it is one or more to be selected from following additive：Fire retardant, wax, coupling agent, pigment, ion trap agent and stress
Absorbent；
The particle diameter distribution of wherein described crystalline silica is 5-50 weight %, preferably 5-45 weight % crystalline silica
Silicon is less than 10 μm, and 50-95 weight %, preferably 55-95 weight % crystalline silica is more than 10 μm but less than 75 μm；
The particle diameter of the preparing spherical SiO 2 is 0.1-30 μm, preferably 0.1-20 μm, more preferably 0.1-10 μm of model
In enclosing；
Based on the gross weight of the composition, the crystalline silica and the preparing spherical SiO 2 (if present)
Total amount is about 40-90 weight %, preferably 50-88 weight %；
Weight ratio between the crystalline silica and the preparing spherical SiO 2 (if present) is 5:1-35:1st, it is excellent
Select 10:1-30:1st, more preferably 12:1-28:In the range of 1；And
The mol ratio of hydroxyl and the epoxide group in the epoxy resin in the phenolic resin is 0.5-2, preferably
In the range of 0.8-1.7, more preferably 0.9-1.5.
Another aspect of the present invention provides a kind of method for the epoxy molding compounds for preparing the present invention, and it includes following step
Suddenly：
(1) all components are weighed and mix it to obtain pre-mix powder in super mixer；With
(2) pre-mix powder is extruded to obtain extruded product by extruder, then crushed the extruded product
Into powder.
Extruder can be double screw extruder.Extrusion can be carried out preferably at elevated temperatures, such as 60 DEG C -110
Temperature in the range of DEG C.
Another aspect of the present invention is related to purposes of the epoxy molding compounds for full molding module of the present invention.
Embodiment
It hereafter will be described in detail the present invention.What material, method and embodiment herein was merely exemplary, and remove
Non- otherwise indicated, it is restricted to be not intended to figure.It is and described herein although suitable method described herein and material
Similar or equivalent method and material can be used for implementing or test the present invention.All disclosures described herein and other ginsengs
Examining document, all clearly overall quote adds herein.
Unless otherwise defined, all terms used in disclosure herein, including technology and scientific terminology, there is the present invention
The implication that one of ordinary skill in the art are generally understood that.When conflict, including in being defined on, it is defined by this specification.
Except as otherwise noted, all percentage, part, ratio etc. are by weight.
When herein cited number range, except as otherwise noted, the scope is intended to include the institute in its end points and scope
There are integer and fraction.
"one", " one kind " be used for describe the present invention element and component.This is used for the purpose of convenient and provides the present invention
Usual implication.Such description should be understood to include one or at least one, and unless substantially have contrary, its
Also include plural form.
Term "comprising" and " comprising " used herein and " containing " are synonymous, and are covered or open, and
It is not excluded for member, element or method and step extra, do not point out.
Except in the embodiment of operation, or otherwise indicated, represent composition herein, reaction condition or define composition
All numerical value of parameter should be understood to be limited by term " about " in all cases.
Term " room temperature (RT) " used herein refers to about 25 DEG C.
It hereafter will be described in detail every kind of component in the epoxy molding compounds of the present invention.
Epoxy resin (a)
As used herein, term " epoxy resin " represents the polymerization that usual per molecule includes two or more epoxide groups
Thing.
In the epoxy molding compounds of the present invention, epoxy resin is had no particular limits, and any commonly employed ring
Oxygen tree fat is suitable.The example of available epoxy resin includes in the present invention：Bisphenol resin, such as bisphenol A epoxide resin and double
Phenol F epoxy resin；Biphenyl epoxy resin, such as biphenyl epoxy resin and tetramethyl biphenyl epoxy resin；Novolac epoxy resin, such as benzene
Phenol novolak epoxy, cresol novolak epoxy, bisphenol-A phenolic epoxy resin, the aromatic aldehyde of phenol and phenolic hydroxy group group
Condensation product epoxide, and biphenyl novolac epoxy resin；Triphenyl methane epoxy resin；Tetraphenyl ethane epoxy tree
Fat；Dicyclopentadiene phenol epoxy resin；Phenol aralkyl epoxy resin；Epoxy resin, it each has in its molecular structure
There is naphthalene skeleton, such as naphthol novolac epoxy resin, naphthols aralkyl base epoxy, naphthols-phenol cocondensation novolac epoxy resin, naphthalene
Phenol-cresols cocondensation phenolic aldehyde (movolac) epoxy resin, diglycidyl epoxide naphthalene；With double (the 2,7- 2-glycidyls of 1,1-
Base Oxy-1-naphthyl)-alkane.These any materials being applied in combination individually or with two or more.
Preferably, the epoxy resin used in the present invention can be selected from following one or more：Orthoresol epoxy novolac
Resin (EOCN), dicyclopentadiene phenol epoxy resin (DCPD), biphenyl epoxy resin (BP), bisphenol-A phenolic epoxy resin
(Bis-AN), triphenyl methane epoxy resin, there is the epoxy resin of naphthalene skeleton, multi-aromatic ring oxygen tree fat (MAR) and multifunctional
Epoxy resin (MFN).
Gross weight based on composition, the amount of composition epoxy resin of the invention can advantageously be 1-25 weights
Measure %, most preferably more preferably 5-20 weight %, 5-15 weight %.
Phenolic resin (b)
The phenolic resin of the present invention is mainly used as curing agent (curing agent).Contained hydroxyl and epoxy resin in phenolic group group
Epoxide group is reacted to form network structure.
Phenolic resin used has no particular limits in the composition of the present invention, as long as conventional use of phenol in EMC
Urea formaldehyde and the desired effects do not damaged in composition of the invention.The example bag for the phenolic resin that can be used in the present invention
Include phenolic resin, dicyclopentadiene phenol add-on type that phenol novolacs, cresol novolac resin, aromatic hydrocarbon formaldehyde resin are modified
Resin, phenol aralkyl resin (Xylok resins), naphthols aralkyl resin, Pehanorm resin, four hydroxy phenyl ethanes
(tetraphenylolethane) resin, naphthol novolac resin, naphthols-phenol cocondensation phenolic resin, naphthols-cresols cocondensation
Close phenolic resin, the naphthol resin that the phenolic resin (having the phenol core coupled by dimethylene) that biphenyl is modified, biphenyl are modified
The phenolic resin that (with the naphthols core connected by dimethylene), amino triazine are modified is (with passing through melamine or benzene generation
The phenol core of melamine connection), the phenolic resin that is modified of aromatic rings containing alkoxy (has by the phenol core of formaldehyde connection and contains
The aromatic rings of alkoxy).Above-mentioned phenolic resin can be individually or with composition of the combination of two or more for the application
In.
Wherein, phenolic resin used in composition of the invention may be preferred that selected from following one or more：Benzene
Phenol phenolic resin, Xylok resins, how fragrant phenolic resin and multifunctional phenolic resin.
Gross weight based on composition, the amount of phenolic resin can be preferably 1-20 weight % in composition of the invention,
More preferably 2-15 weight %, most preferably 2-10 weight %.
Curing accelerator (c)
As used herein, term " curing accelerator " has " catalyst " identical implication, and it is catalyzed or accelerates asphalt mixtures modified by epoxy resin
Curing reaction between fat and curing agent.
Various compounds, such as the compound of organophosphor, amine, amidine compound, imidazolium compounds, metal salts of organic acids, road
Lewis acid, amine complex salt etc. can be used as curing accelerator to be included in epoxy molding compounds.
Preferably, curing accelerator used in the composition of the application is selected from following one or more：Organophosphor
Compound, imidazolium compounds, amine and amidine compound.It is highly preferred that the tool of curing accelerator used in the composition of the application
Body example includes triphenylphosphine (TPP), 1,8- diazabicyclos (5,4,0) hendecene -7 (DBU), [the 2 '-first of 2,4- diaminourea -6
Base imidazole radicals-(1 ')] ethyl-s-triazine (2MZ), 2- phenyl -4-methylimidazole (2P4MZ), N, N- dimethyl benzyl amines and three
Ethamine.Above-mentioned specific curing accelerator can be individually or with the combination of two or more in the composition of the application.
The amount of curing accelerator is more, and curing rate is faster.But excessive curing accelerator may cause that EMC's is short solid
Change time and short spiral flow.Gross weight based on composition, the amount of curing accelerator is preferably 0.01- in composition of the invention
5 weight %, more preferably 0.01-2 weight %, most preferably 0.05-1 weight %.
Crystalline silica and preparing spherical SiO 2 (d)
Silica, as the filler in EMC, account for 60 weight %-90 weight % of composition total weight, therefore titanium dioxide
The very big influence EMC of selection meeting of silicon property.
In EMC, the main function of silica is to improve thermal conductivity, reduce EMC thermal expansion and the coefficient that shrinks with
And improve reliability.In order to realize above-mentioned advantage, the filling rate of silica should be high as much as possible.However, too high filling
The silica of rate may increase viscosity, reduce the mobility of composition and the reliability of layered product and increase line skew.
By widely studying, it was found by the inventors of the present invention that by selecting certain types of silica, silica
With the particular combination of the specific size distribution of silica, compared with the composition of prior art, thermal conductivity, flowing can be improved
Property and reliability, and reduce line skew.
In the embodiment of the present invention, epoxy molding compounds include the crystalline silica with following particle diameter distribution
Silicon：5-50 weight %, preferably 5-45 weight %'s is less than 10 μm, and 50-95 weight %, preferably 55-95 weight % is more than
10 μm but less than 75 μm.
In a preferred embodiment of the invention, epoxy molding compounds include crystalline silica and preparing spherical SiO 2
Combination, wherein the particle diameter distribution of the crystalline silica be 5-50 weight %, preferably 5-45 weight % be less than 10 μm, and
And 50-95 weight %, preferably 55-95 weight % is more than 10 μm but less than 75 μm, the particle diameter of the preparing spherical SiO 2
For 0.1-30 μm, in the range of preferably 0.1-20 μm, more preferably 0.1-10 μm, and the crystalline silica with it is described spherical
The weight ratio of silica is 5:1-35:1, preferably 10:1-30:1, more preferably 12:1-28:In the range of 1.
Gross weight based on composition, the total amount of silica can be 40-90 weight % in composition of the invention, excellent
Select 50-88 weight %, more preferably 60-85 weight %.
Other additives (e)
The epoxy molding compounds of the present invention can also include one or more and be selected from other following additives：It is fire-retardant
Agent, wax, coupling agent, pigment, ion trap agent and stress absorption agent.Additive used is not special in the composition of the present invention
Limitation, as long as its do not damage the present invention composition desired effects.
For fire retardant, any suitable fire retardant can be used.However, for the angle of environmental problem, preferably without
Halogen fire retardant, more preferably inorganic combustion inhibitor.The example of inorganic combustion inhibitor includes metal hydroxides, metal oxide, boronation and closed
Thing, calcium silicates etc..The example of metal hydroxides includes aluminium hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, hydrogen
Barium monoxide, zirconium hydroxide etc..The example of metal oxide includes zinc molybdate, molybdenum trioxide, molybdenum oxide, zinc stannate, tin oxide, oxygen
Change aluminium, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, tungsten oxide, three
Antimony oxide etc..The example of boron compound includes Firebrake ZB, zinc metaborate (zinc metabonate), barium metaborate, boric acid, boron
Sand etc..Inorganic combustion inhibitor being applied in combination individually or with two or more in the composition of the application.If desired,
The organic fire-retardant of such as brominated epoxy resin can be used alone in the present compositions, or with and inorganic combustion inhibitor
Be applied in combination.Gross weight based on composition, the amount of fire retardant can be preferably 0-20 weight % in composition of the invention,
More preferably 3-15 weight %, most preferably 3-10 weight %.
In the present compositions, wax is used as releasing agent, and can use all suitable waxes, as long as not influenceing this
The desired effects of the composition of invention.The example of wax includes native paraffin and synthetic wax.Preferable example includes lignite wax, aliphatic acid
Ester type waxes, fatty acid wax, aliphatic ester type waxes, Tissuemat E, polypropylene wax, alkyl oligomeric wax and amide waxe.Group of the wax in the application
Can being applied in combination individually or with two or more in compound.Gross weight based on composition, in composition of the invention
The amount of wax can be preferably 0-5 weight %, more preferably 0.2-5 weight %, most preferably 0.3-3 weight %.
The coupling agent of the present invention, if it exists, improving the compatibility between epoxy resin and silica, and increase
Add adhesion of the epoxy resin to the particular surface of such as chip.Coupling agent is preferably selected from such compound, and it includes at least one
Individual ethylene oxide group and at least one group that can be interacted with inorganic filler material.It is used in the composition of the present invention
The example of coupling agent include silane coupler, such as epoxy silane, amino silane, hydrosulphonyl silane, ureido silane, vinyl silicon
Alkane, alkyl silane.Coupling agent being applied in combination individually or with two or more in the composition of the application.Based on group
The gross weight of compound, the amount of coupling agent can be preferably 0-5 weight %, more preferably 0.2-5 weight % in composition of the invention,
Most preferably 0.2-3 weight %.
Pigment in the composition of the present invention can be used for the different type of differentiation/identity device and cover encapsulation unit
Design and prevent printing opacity.According to being actually needed, epoxy molding compounds of the invention can include one or more pigment.
The example of pigment includes carbon black.Gross weight based on composition, the amount of pigment can be preferably 0-5 weights in composition of the invention
Measure %, most preferably more preferably 0.2-5 weight %, 0.4-3 weight %.
Using ion trap agent to reduce the content of dissociated ion in epoxy molding compounds in the composition of the present invention.This
The ion trap agent commonly used in field can be used in the composition of the present invention, have no particular limits.The composition of the present invention
In the example of used ion trap agent include magnesium hydroxide aluminium profiles, aluminosilicate, antimony hydroxide type and bismuth hydroxide type.Ion
Capturing agent being applied in combination individually or with two or more in the composition of the application.Gross weight based on composition
Amount, the amount of the composition intermediate ion capturing agent of the application can be preferably 0-5 weight %, more preferably 0.1-3 weight %, most preferably
0.1-1 weight %.
Reduce modulus of elasticity and increase pliability using stress absorption agent in the composition of the present invention and reduce hot swollen
Swollen coefficient.The example of stress absorption agent includes silicone oil, silicone resin, butadiene-type rubber etc..Gross weight based on composition, this
The amount of stress absorption agent can be preferably 0-5 weight %, more preferably 0.1-2 weight %, most preferably 0.1-1 in the composition of invention
Weight %.
Depending on desired property, the relative scale of each component can change in wider limitation.Can on demand by
Additive is formulated into epoxy molding compounds.
Had no particular limits for the preparation method of the epoxy molding compounds of the present invention.In a preferred embodiment
In, epoxy molding compounds are prepared by the method comprised the following steps：
(1) weigh all component (a)-(e), and by its in super mixer with 50~500rpm, preferably 100~
400rpm is mixed to obtain pre-mix powder, and
(2) pre-mix powder is squeezed by double screw extruder with the rotating speed of 60~110 DEG C and 50~250rpm oar
Go out to obtain extrusion product, the extrusion product is then broken into powder.
Embodiment
The present invention is described in further detail with reference to Examples below, but it is not limiting as the model of the present invention
Enclose.All numbers are expressed as parts by weight in embodiment.
Embodiment 1-10 and comparative example 1-2
As shown in table 1, the epoxy molding compounds of each of embodiments of the invention 1-10 and comparative example 1 and 2 are weighed
Raw material.All raw materials are less than 10 DEG C with 250r/min by super mixer and mix 15 minutes to obtain pre-mix powder.
Then pre-mix powder is extruded by double screw extruder with about 100 DEG C and 200rpm of oar rotating speed.Acquisition extruded material simultaneously will
It is broken into powder.
The various properties of the epoxy molding compounds obtained according to following test method test, and result following article table 1
It is shown.
Method of testing
Spiral flow：
In spiral current test, the length and weight that are flowed by measuring path of the resin along helical cavity, to determine epoxy
The flowing property of molding compounds.The sample of spiral current test is the powder sample of epoxy molding compounds.Do not require extra
Prepare.Spiral current test is carried out according to method EMI-1-66.Test condition setting is as follows：175 DEG C of temperature, pressure 70km/cm2With
Hardening time 90s.
In the range of EMC acceptable spiral flow length is 15 inches -65 inches, preferably 20 inches -55 inches.
Gel time：
In gel time test, the gel point of epoxy molding compounds is tested.In testing, by heater plate extremely
175℃.The powder sample of epoxy molding compounds is placed in heating plate, places up to making sample gelation, is surveyed with timer
Measure gel time (start timer immediately when sample is placed in heating plate, and stop when gelation is completed).
EMC acceptable gelling time is in the range of -60 seconds 15 seconds, preferably -50 seconds 20 seconds.
Viscosity：
Viscosity number is determined using SHIMADU capillary rheometer CFT-500D, and temperature is 175 DEG C and load is
10Kgf。
Thermal conductivity：
The thermal conductivity value of moulding compound is surveyed using ANTER Corporation thermal conductivity instrument Quickline-10
Fixed, test condition setting is as follows：The thickness of exemplar is 5mm, a diameter of 50mm of exemplar, and test temperature is set as 43 DEG C.
For full molding module, the acceptable thermal conductivity values of EMC are at least 2.0W/MK, and the higher the better.
Water imbibition：
Water imbibition value is according to " PCT 24 " method determines.Exemplar size is set as Φ 50*3mm, and test condition is
121 DEG C/100RH%/2atm/24 hours.Water imbibition value may be calculated exemplar weightening/exemplar weight * after PCT24 hours
100%.
The acceptable water imbibition values of EMC are less than 1.0%, preferably smaller than 0.8%, more preferably less than 0.6%.
Thermal coefficient of expansion (CTE1＆2) and glass transition temperature (Tg)：
CTE1＆2 the and Tg values of moulding compound are determined using TA Instruments thermomechanical analyzer Q-400, and
And test condition setting is as follows：Exemplar size is set as Φ 5 × (5 ± 0.1) mm, and exemplar is added with 10 DEG C/min speed from room temperature
Heat is to 280 DEG C, and it is 0.1N to load.CTE1 is calculated within the temperature range of 50 DEG C -70 DEG C, and CTE2 is at 220 DEG C -240 DEG C
Calculated in temperature range, and Tg is obtained within the temperature range of 100 DEG C -220 DEG C.
In the range of acceptable CTE1 values are 6ppm-45ppm, preferably 10ppm-40ppm.Acceptable CTE2 values are
In the range of 20ppm-90ppm, preferably 25ppm-80ppm.
In the range of the acceptable Tg values of EMC are 90 DEG C -210 DEG C, but it is the higher the better.Preferably, Tg values are higher than 130
DEG C, more preferably higher than 145 DEG C.
Line skew：
Line skew value determines by the following method：The sample of encapsulation is placed in X-ray emitter, circuit is obtained by it
The first solder joint projection and the second solder joint projection；By two spot projection connections to obtain baseline, its projected length is L；Line taking is inclined
The peak of camber line caused by shifting and parallel with baseline at peak do tangent line；Measure the distance A of tangent line and baseline；Pass through
Formula A/L*100% calculates line skew value.
Acceptable line skew value is less than 10%, and the smaller the better.
Table 1:(weight %)
Table 1:(continuous -1) (weight %)
Table 1:(continuous -2) (weight %)
Note：
1):Dicyclopentadiene phenol epoxy resin (DCPD), it has following general structure：
2):Study On O-cresol Epoxy Resin (EOCN), it has following general structure：
3):Biphenyl epoxy resin (BP), it has following general structure：
4):Bisphenol-A phenolic epoxy resin (Bis-AN), it has following general structure：
5):Phenol novolacs (PN), it has following general structure：
6):Multifunctional phenolic resin (MFN), it has following general structure：
7):Xylok resins, it has following general structure：
8):Triphenylphosphine (TPP),
9):2- phenyl -4-methylimidazole (2P4MZ),
10):2,4- diaminourea -6 [2 '-methylimidazolyl-(1 ')] ethyl-s-triazines (2MZ),
11):1,8- diazabicyclo (5,4,0) hendecene -7 (DBU),
12):Crystalline silica, its particle diameter distribution be 15-45% in the range of 0.1-10 μm, 55-85% is in 10-75
In the range of μm, and average grain diameter is 20-50 μm,
13):Preparing spherical SiO 2, its particle diameter is in the range of 0.1-30 μm, and average grain diameter is 0.2-25 μm,
14):Firebrake ZB,
15):Aluminium hydroxide,
16):Epoxidation silicone glycidyl resin,
17):Phenyl amino propyl trimethoxy silane,
18):3-mercaptopropyi trimethoxy silane,
19):Aliphatic ester type waxes, it has following general structure：
20):Tissuemat E, it has following general structure：
21):Fatty acid ester wax, it has following general structure：
22):Carbon black,
23):Magaldrate hydrate,
24):Polybutadiene ene-type stress absorption agent,
25):Fused silica, in the range of its particle diameter is 0.1-30 μm, and average grain diameter is 0.2-25 μm.
As seen from Table 1, the thermal conductivity of embodiments of the invention 1-10 all epoxy molding compounds is at least 2.0W/
MK, and the thermal conductivity of comparative example 1-2 epoxy molding compounds is then less than 2.0W/MK.Moreover, embodiments of the invention 1-
10 all epoxy molding compounds have the low line skew less than 7%.Meanwhile embodiments of the invention 1-10 all epoxies
Other properties required by the EMC of molding compounds are also well kept.
Describe the present invention in detail in embodiments.But those skilled in the art can significantly modifications and changes it is real
Apply spirit of the scheme without departing from the present invention.All modifications and change both fall within the scope of the claim appended by the application
It is interior.
Claims (15)
1. a kind of epoxy molding compounds, it is included：
(a) epoxy resin,
(b) phenolic resin,
(c) curing accelerator,
(d) crystalline silica, it is optionally combined with preparing spherical SiO 2, and
(e) it is one or more to be selected from following additive：Fire retardant, wax, coupling agent, pigment, ion trap agent and stress absorption
Agent；
The particle diameter distribution of wherein described crystalline silica is that 5-50 weight %, preferably 5-45 weight % crystalline silica is small
In 10 μm, and 50-95 weight %, preferably 55-95 weight % crystalline silica is more than 10 μm but less than 75 μm,
In the range of the particle diameter of the preparing spherical SiO 2 is 0.1-30 μm, preferably 0.1-20 μm, more preferably 0.1-10 μm,
Based on the gross weight of the composition, the total amount of the crystalline silica and the preparing spherical SiO 2 (if present)
It is about 40-90 weight %, preferably from about 50-88 weight %, more preferably from about 60-85 weight %,
Weight ratio between the crystalline silica and the preparing spherical SiO 2 (if present) is 5:1-35:1st, preferably
10:1-30:1st, more preferably 12:1-28:In the range of 1；And
The mol ratio of hydroxyl and the epoxide group in the epoxy resin in the phenolic resin is 0.5-2.0, preferably 0.8-
1.7th, more preferably in the range of 0.9-1.5.
2. the epoxy molding compounds of claim 1, wherein the epoxy resin is selected from following one or more：Orthoresol
Novolac epoxy resin (EOCN), dicyclopentadiene phenol epoxy resin (DCPD), biphenyl epoxy resin, bisphenol-A phenolic asphalt mixtures modified by epoxy resin
Fat, triphenyl methane epoxy resin, epoxy resin, multi-aromatic ring oxygen tree fat (MAR) and the multi-functional epoxy tree with naphthalene skeleton
Fat (MFN).
3. the epoxy molding compounds of claim 1 or 2, wherein the phenolic resin is selected from following one or more：Benzene
Phenol phenolic resin, Xylok resins, how fragrant phenolic resin and multifunctional phenolic resin.
4. any one of claim 1-3 epoxy molding compounds, wherein the curing accelerator is selected from following one kind
It is or a variety of：Triphenylphosphine (TPP), 1,8- diazabicyclos (5,4,0) hendecene -7 (DBU), [the 2 '-methyl of 2,4- diaminourea -6
Imidazole radicals-(1 ')] ethyl-s-triazine (2MZ), 2- phenyl -4-methylimidazole (2P4MZ), N, N- dimethyl benzyl amines and three second
Amine.
5. any one of claim 1-4 epoxy molding compounds, wherein the fire retardant is selected from following one kind or more
Kind：Firebrake ZB, aluminium hydroxide, magnesium hydroxide, titanium oxide, calcium silicates, brominated epoxy resin and antimony trioxide.
6. any one of claim 1-5 epoxy molding compounds, wherein the wax is selected from following one or more：It is brown
Coal wax, fatty acid ester wax, fatty acid wax, aliphatic ester type waxes, Tissuemat E, polypropylene wax, alkyl oligomeric wax and amide waxe.
7. any one of claim 1-6 epoxy molding compounds, wherein the coupling agent is selected from following one kind or more
Kind：Epoxy silane, amino silane, hydrosulphonyl silane, ureido silane, vinyl silanes and alkyl silane.
8. any one of claim 1-7 epoxy molding compounds, wherein the ion trap agent is selected from following one kind
It is or a variety of：Magnesium hydroxide aluminium profiles, aluminosilicate, antimony hydroxide type and bismuth hydroxide type.
9. any one of claim 1-8 epoxy molding compounds, wherein the stress absorption agent is selected from following one kind
It is or a variety of：Silicone oil, silicone resin and butadiene-type rubber.
10. any one of claim 1-9 epoxy molding compounds, wherein the gross weight based on the epoxide, institute
Compound is stated to include：
(a) 1-25 weight % epoxy resin,
(b) 1-20 weight % phenolic resin,
(c) 0.01-5 weight % curing accelerator,
(d) 40-90 weight % crystalline silica and preparing spherical SiO 2 (if present), and
(e) 0.1-45 weight % one or more additives.
11. any one of claim 1-9 epoxy molding compounds, wherein the gross weight based on the epoxide, institute
Compound is stated to include：
(a) 5-20 weight % epoxy resin,
(b) 2-15 weight % phenolic resin,
(c) 0.01-2 weight % curing accelerator,
(d) 50-88 weight % crystalline silica and preparing spherical SiO 2 (if present), and
(e) 0.5-40 weight % one or more additives.
12. a kind of method for the epoxy molding compounds for preparing any one of claim 1-11, it comprises the following steps：
(1) all components are weighed and mix it to obtain pre-mix powder in super mixer；With
(2) pre-mix powder is extruded to obtain extruded product by extruder, the extruded product is then broken into powder
End.
13. the method for claim 12, wherein the extruder is double screw extruder.
14. claim 12-13 method, wherein the extrusion is carried out at 60~110 DEG C, rotating speed is 50~250rpm.
15. any one of claim 1-11 epoxy molding compounds are used for the purposes of full molding module.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2015/074575 WO2016145651A1 (en) | 2015-03-19 | 2015-03-19 | Epoxy molding compound, preparation and use thereof |
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| CN110066491A (en) * | 2018-01-22 | 2019-07-30 | 衡所华威电子有限公司 | A kind of composition epoxy resin, preparation method and use |
| CN110128781A (en) * | 2018-02-09 | 2019-08-16 | 衡所华威电子有限公司 | Epoxy molding plastic, preparation method and use |
| CN110128782A (en) * | 2018-02-09 | 2019-08-16 | 衡所华威电子有限公司 | Compatible anticorrosive composition epoxy resin of a kind of copper wire and preparation method thereof |
| CN112980138A (en) * | 2019-12-17 | 2021-06-18 | 衡所华威电子有限公司 | Epoxy resin composition for packaging electronic components and preparation method thereof |
| CN114437512A (en) * | 2022-01-07 | 2022-05-06 | 昆山兴凯半导体材料有限公司 | Epoxy molding compound and preparation method thereof |
| CN114989561A (en) * | 2022-03-28 | 2022-09-02 | 昆山兴凯半导体材料有限公司 | High-strength high-reliability epoxy resin composition and preparation method thereof |
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