CN109111689A - Encapsulation plastics composite and its application - Google Patents
Encapsulation plastics composite and its application Download PDFInfo
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- CN109111689A CN109111689A CN201710493178.8A CN201710493178A CN109111689A CN 109111689 A CN109111689 A CN 109111689A CN 201710493178 A CN201710493178 A CN 201710493178A CN 109111689 A CN109111689 A CN 109111689A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to encapsulating material fields, disclose encapsulation plastics composite and its application.The plastics composite contains epoxy resin, curing agent, silicon powder, imidazoles curing accelerator, release agent, silane coupling agent and the toughener of particular types and proportion, wherein, the epoxy resin includes liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde epoxy resin and biphenyl type epoxy resin, and the curing agent is cyanurotriamide modified linear phenol-aldehyde resin.The invention also discloses above-mentioned compositions to prepare the application in integrated antenna package plastics.The present invention is by that can obtain the encapsulation plastics with better performance, can be used for the encapsulation of large scale integrated circuit, and relatively environmentally protective with the use of specific epoxy resin, curing agent, filler and auxiliary agent etc..
Description
Technical field
The present invention relates to encapsulating material fields, and in particular to encapsulation plastics composite and its application.
Background technique
With the progress of chip technology, integrated circuit just develops towards highly integrated and surface mounting technique direction, with this phase
The Electronic Packaging of adaptation and the developing trend of baseplate material are that material is made to have the property such as low thermal expansion, high thermoconductivity and high heat resistance
It can feature.Epoxy-plastic packaging material is integrated circuit (IC) one of the main raw material(s) that road encapsulates afterwards, its development is immediately following integrated electricity
The development on road and encapsulation technology.Electronic product is to high-performance, multi-functional, miniaturization, portability, not only to integrated
The performance requirement of circuit is constantly being promoted, and is having higher requirement to Electronic Packaging density.Epoxy-plastic packaging material is also required to not
It improves and improves disconnectedly.In order to meet high-power discrete device, high fever metering device, particularly total incapsulation discrete device to scattered
The requirement of heat, has now been developed using the highly thermally conductive filler such as crystalline sillica, aluminium oxide, aluminium nitride and boron nitride (such as
CN106336620A), highly thermally conductive type epoxy-plastic packaging material is prepared using high filling technique, but water imbibition and heat resistance do not reach
To desirable.
Regulation will limit in discarded electrically or electronically equipment in two decrees of WEEE and RoHS of the publication of European Union in 2003
Phase is forbidden to use six kinds of deleterious materials, the i.e. objects such as lead, Cr VI, cadmium, Polychlorinated biphenyls, halogenated fire-retardants, radioactive substance, asbestos
Matter.Simultaneously the Ministry of Information Industry of China also issued and implemented " electronics and IT products pollution control management method ", electronic product it is green
Colour circle guaranteed request has become a kind of irreversible trend.In order to abide by the decree of two instructions of European Union and China, IC is sealed
Package material must be changed or improve and adapt to environmental requirement.Therefore exploitation Halogen is needed, without antimony, without phosphorus environmental type
High-performance epoxy-plastic packaging material.
Summary of the invention
The purpose of the invention is to overcome performance of the existing technology poor (especially water imbibition and heat resistance)
Problem provides encapsulation plastics composite and its application.
To achieve the goals above, one aspect of the present invention provides a kind of encapsulation plastics composite, the plastics composite
Contain:
Wherein, the epoxy resin includes liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde asphalt mixtures modified by epoxy resin
Rouge and biphenyl type epoxy resin, and liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde epoxy resin and biphenyl
Weight ratio between type epoxy resin is (8-22): (3-15): (8-25): (4.5-12.5);The curing agent is melamine
Modified linear phenol-aldehyde resin.
Second aspect of the present invention provides above-mentioned plastics composite and is preparing the application in integrated antenna package plastics.
Third aspect present invention provides the method using above-mentioned plastics composite preparation encapsulation plastics, this method packet
It includes: filler being surface-treated, melting mixing, cooling and crushing.
The present invention, can be in lower cost by being used cooperatively specific epoxy resin, curing agent, filler and auxiliary agent etc.
In the case of obtain have high-hydroscopicity, high-fire resistance, low viscosity, low-expansion coefficient and high-termal conductivity encapsulation plastics, can use
In the encapsulation of large scale integrated circuit.Moreover, the present invention can not use the raw material containing elements such as halogen, antimony and phosphorus, can also expire
Sufficient UL-94V-0 grades of flame-retardant standard, simultaneously, moreover it is possible to ensure the mobility, operability and reliability of encapsulation plastics, therefore accord with
Close environmentally protective growth requirement.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Encapsulation plastics composite provided by the invention contains:
Wherein, the epoxy resin includes liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde asphalt mixtures modified by epoxy resin
Rouge and biphenyl type epoxy resin, and liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde epoxy resin and biphenyl
Weight ratio between type epoxy resin is (8-22): (3-15): (8-25): (4.5-12.5);The curing agent is melamine
Modified linear phenol-aldehyde resin.
According to the present invention, the epoxy resin includes at least above-mentioned four kinds of epoxy resin.In preferred implementation side of the invention
In formula, the content of epoxy resin is 30-47 parts by weight.In further preferred embodiment, relative to filling out for 100 parts by weight
Material, the content of epoxy resin are 16.9-34.3 parts by weight.
In the present invention, the liquid crystal epoxy resin (different from the liquid crystal epoxy resin of biphenyl type epoxy resin) is particularly advantageous
In improving melt viscosity, processing forming, thermal expansion coefficient, water absorption rate, moisture resistance, glass transition temperature, resistance to immersed solder and Reflow Soldering, tough
Property and reduce silicon powder content.In preferred embodiment of the invention, relative to the filler of 100 parts by weight, liquid crystalline epoxy
The content of resin is 6.1-8.9 parts by weight.The liquid crystal epoxy resin can for aryl nitrone, biphenyl class, α-methylstyrene class,
Methylene amine, and can be backbone chain type, or side chain type, but be thermotropic liquid crystal, liquid-crystal phase-transition temperature is usually in 95-
In 150 DEG C.Under preferable case, the liquid crystal epoxy resin is JEC-832 or the Japan of rivers and mountains Jiang Huanhua Industrial Co., Ltd
The HP-4032D of DIC Corporation.
In the present invention, the glycidyl amine type epoxy resin is particularly conducive to improve resistance to ag(e)ing, acid resistance and reduction
Water absorption rate.In preferred embodiment of the invention, relative to the filler of 100 parts by weight, glycidyl amine type epoxy resin
Content be 1.7-10 parts by weight.The glycidyl amine type epoxy resin can be the conventional selection of this field, for example, can be with
For four glycidyl amine of diaminodiphenylmethane, diglycidyl para-aminophenol, triglycidyl group para-aminophenol
(TGPAP) and at least one of N, N, N', N'- four glycidyl group -4,4'- diaminodiphenylmethane (TGDDM) etc..It shrinks
The basic structure of glyceramine type epoxy resin is preferably shown below:
In the present invention, o-cresol formaldehyde epoxy resin is particularly conducive to increase crosslink density, improves the heat resistance of composition, together
When reduce cost.In preferred embodiment of the invention, relative to the filler of 100 parts by weight, o-cresol formaldehyde epoxy resin
Content be 6.1-9.5 parts by weight.The o-cresol formaldehyde epoxy resin can be conventional selection, usually by o-cresol-formaldehyde resin
(O-CN) it is obtained with epoxychloropropane (ECH) reaction, basic structure can be shown in formula I:
In Formulas I, m is preferably the arbitrary integer between 10-100.The o-cresol formaldehyde epoxy resin that the present invention uses can lead to
Cross commercially available, such as N-665 of Japan DIC Corporation.
In the present invention, biphenyl type epoxy resin is particularly conducive to the heat resistance and water resistance of encapsulation plastics.In the present invention
In preferred embodiment, relative to the filler of 100 parts by weight, the content of biphenyl type epoxy resin is 3-5.9 parts by weight.Connection
Benzene-type epoxy resin can be conventional selection, and basic structure can be as shown in Formula II:
In Formula II, k is preferably the arbitrary integer between 10-100.The biphenyl type epoxy resin that the present invention uses can pass through
It is commercially available, such as the JPPN-603 of rivers and mountains Jiang Huanhua Industrial Co., Ltd, the high molecular BRG-557 of Showa, Japanese chemical drug
The H-1 of NC-3000 series, bright sum.
In further preferred embodiment, liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde ring
Weight ratio between oxygen resin and biphenyl type epoxy resin is 1:(0.2-1.3): (1-1.1): (0.5-0.7).Preferably using this
The plastics composite preparation encapsulation plastics of embodiment can further increase the performance of gained encapsulation plastics.
According to the present invention, the curing agent (or cyanurotriamide modified linear phenol-aldehyde resin) has epoxy resin excellent
Curing performance is particularly conducive to improve crosslink density, to improve the heat resistance of encapsulation plastics.It is advantageous using the curing agent
In the heat distortion temperature (can be improved to 260-290 DEG C) for improving encapsulation plastics.In a preferred embodiment of the invention, described
The content of curing agent is 15-22 parts by weight.In further preferred embodiment, relative to the filler of 100 parts by weight, solidification
The content of agent is 11.5-13.4 parts by weight.Cyanurotriamide modified linear phenol-aldehyde resin is that linear phenol-aldehyde resin changes through melamine
Property obtain, can be conventional selection, basic structure usually as shown in formula III, and (unmodified) linear phenol-aldehyde resin usually by
Formaldehyde and phenol (phenyl ring is substituted or unsubstituted) are with (0.75-0.85): 1 molar ratio polymerize to obtain:
In formula III, n is preferably the arbitrary integer between 1-50, and o is preferably the arbitrary integer between 1-50.
According to the present invention, the silicon powder is particularly conducive to improve loading, increases the thermal conductivity of encapsulation plastics, reduces
Linear expansion coefficient.In a preferred embodiment of the invention, the content of the silicon powder is 130-170 parts by weight.The silicon is micro-
Powder can be silicon powder commonly used in the art, and under preferable case, the silicon powder is melting ball-shaped silicon micro powder.Wherein, molten ball
The partial size of shape silicon powder can be 0.1-30 μm, Oxygen potential > 95%, conductivity≤1 μ s/cm, sodium ions content≤1ppm, chlorine
Ion concentration≤3ppm, specific surface area < 40m2/ g, glass rate (noncrystalline degree) > 97%.
According to the present invention, the plastics composite can also contain stress release agent, and the stress release agent is conducive to release
Put the internal stress of moulding compound.In a preferred embodiment of the invention, the content of stress release agent is 0.3-5 parts by weight.?
In further preferred embodiment, relative to the filler of 100 parts by weight, the content of stress release agent is 0.2-3.4 parts by weight.
The stress release agent can be conventional selection, but under preferable case, the stress release agent be silicone oil, acrylonitrile butadiene,
At least one of rubber and polybutene acrylates.
According to the preferred embodiment of the present invention, the content of the imidazoles curing accelerator is 0.4-0.8 parts by weight.?
In further preferred embodiment, relative to the filler of 100 parts by weight, the content of imidazoles curing accelerator is 0.2-0.5
Parts by weight.The imidazoles curing accelerator can be the common various imidazoles substances in this field, under preferable case, the miaow
Azole curing accelerator is 2-methylimidazole (2MZ), 1- 1-cyanoethyl-2-methylimidazole (2MZCN) and 2-ethyl-4-methylimidazole
At least one of (2E4MZ).
According to the preferred embodiment of the present invention, the content of the release agent is 2.5-3 parts by weight.Further preferred
In embodiment, relative to the filler of 100 parts by weight, the content of release agent is 1.6-2.2 parts by weight.The release agent can be
Release agent commonly used in the art, but preferably stearic acid and/or stearate.Wherein, stearate can for odium stearate and/
Or potassium stearate.
According to the preferred embodiment of the present invention, the content of the silane coupling agent is 1.5-2 parts by weight.Further excellent
In the embodiment of choosing, relative to the filler of 100 parts by weight, the content of silane coupling agent is 1-1.4 parts by weight.The silane is even
Join the conventional selection that agent can be this field, for example, can be γ-(2,3- glycidoxy) propyl trimethoxy silicane, γ-
In aminopropyltriethoxywerene werene, gamma-mercaptopropyltriethoxysilane, γ-mercapto propyldimethoxy-silane and azide silane
At least one.
According to the present invention, the use of toughener is particularly conducive to improve the impact flexibility of encapsulation plastics, to improve resistance to
Thermal stress-cracking performance avoids the stress cracking in high temperature immersed solder and reflow process.Preferred implementation side according to the present invention
Formula, the content of toughener are 5-6 parts by weight.In further preferred embodiment, relative to the filler of 100 parts by weight, increase
Tough dose of content is 2.9-4.7 parts by weight.The toughener can be the common toughener in this field, but in preferred embodiment party
In formula, the toughener is at least one in carboxyl-terminated liguid nitrile rubber, terminal hydroxy liquid polybutadiene and liquid silastic
Kind.Wherein, liquid silastic not only contributes to improve the impact flexibility of encapsulation plastics, and also contributes to anti-flammability.
The present invention can be effectively improved encapsulation plastics in the case where not using the raw material containing elements such as halogen, antimony and phosphorus
Performance.Therefore, in order to meet environmentally protective growth requirement, in a preferred embodiment of the invention, the plastic composition
Halogen in object, antimony, phosphorus and metal oxide total content in 0.001 weight % hereinafter, it is highly preferred that the plastics composite not
Containing halogen, antimony, phosphorus and metal oxide.
According to the present invention, in order to assign plastics certain color, the plastics composite can also contain colorant.It is described
The content of colorant can be 3-6 parts by weight.In preferred embodiment, relative to the filler of 100 parts by weight, colorant
Content be 1.7-2.4 parts by weight.The colorant can be colorant commonly used in the art, it is preferable that the coloring
Agent is at least one of carbon black, chrome blue, chrome green, chrome yellow and molybdate.
Wish to illustrate, although elaborating the main of each ingredient in plastics composite of the invention respectively above
Effect, it is not intended that it only plays above-mentioned effect in plastics composite, on the contrary, in plastics composite of the invention,
Each ingredient be it is complementary, play a role as the collaboration of organic whole, to realize above-mentioned purpose.According to the present invention
A kind of preferred embodiment, the plastics composite is only made of mentioned component.In addition, resin used in the present invention
To be commercially available, for example, the commercial source that can be recorded for embodiment.
The present invention also provides above-mentioned plastics composites to prepare the application in integrated antenna package plastics.
In addition, it is provided by the invention using above-mentioned plastics composite preparation encapsulation plastics method include: to filler into
Row surface treatment, melting mixing, cooling and crushing.
In order to further improve the performance of encapsulation plastics, in a preferred embodiment of the invention, the method is also wrapped
It includes using the metal impurities in magnetic separation method removal raw material and/or smashed material.More specifically, the Magneto separate can be
After surface treatment, Magneto separate is carried out to remove metal impurities to each ingredient, magnetic point can also be carried out to material after being pulverized
From further to remove metal impurities.Magneto separate can be carried out by magnetic sieve (screen-aperture 1-2mm), and metal is miscellaneous
Matter is adsorbed and stayed on sieve by sieve, and removal is facilitated.
In practical operation, the method may include: after component precise, by filler silane coupling agent mixed
It is handled, is first mixed 3-5 minutes, then stand 3-7 minutes in conjunction machine, carry out repeatedly being surface-treated repeatedly;So
After be proportionally added into other components, detected using metal detector and metal impurities removed by Magneto separate, then mix 3-5 point
Clock, by mixture melting mixing, melting temperature can be 95-135 DEG C, and mixing time can be 3-5 minutes;After product is cooling,
It pulverizes and sieves, pipeline transmission, Magneto separate is stirred, and plays ingot.
The present invention will be described in detail by way of examples below.
In following embodiment, the source of each ingredient is as follows:
Polyfunctional epoxy resin: TGDDM, JEPN-838, rivers and mountains Jiang Huanhua Industrial Co., Ltd;
Liquid crystal epoxy resin: JEC-832, rivers and mountains Jiang Huanhua Industrial Co., Ltd;
O-cresol formaldehyde epoxy resin: JECN-804, rivers and mountains Jiang Huanhua Industrial Co., Ltd;
Biphenyl type epoxy resin: JPPN-603, rivers and mountains Jiang Huanhua Industrial Co., Ltd;
Phenol-formaldehyde resin modified: JECN-803S, rivers and mountains Jiang Huanhua Industrial Co., Ltd;
Colorant: carbon black, Beijing Reagent Company;
Stearic acid (release agent): chemical pure, Beijing Reagent Company;
Imidazoles curing accelerator: 2MZ (embodiment 1) or 2MZCN (embodiment 2 and 3), the limited public affairs of Guangzhou Chkawai electronic material
Department;
Silicon powder: QG75, Nonmetallic Minerals in Yunnan Province produce research institute;
Toughener: carboxyl-terminated liguid nitrile rubber, A-658, the complete works of Science and Technology Ltd. of Shenzhen gold;
Silane coupling agent: γ-(2,3- glycidoxy) propyl trimethoxy silicane, KH-560, military big organosilicon green wood
Expect limited liability company.
Embodiment 1
The method of preparation encapsulation plastics include: according to shown in table 1 by after component precise (g), by filler silane
Coupling agent is handled in mixing machine, is first mixed 5 minutes, then stand 3 minutes, is carried out 5 times and is carried out at surface repeatedly
Reason;Then other components are proportionally added into, detected using metal detector and metal impurities are removed by Magneto separate, are then mixed
3 minutes, by mixture melting mixing, melting temperature was 100 DEG C, and mixing time is 4 minutes;After product is cooling, pulverizes and sieves and (take
The screenings of 100 meshes), pipeline transmission, Magneto separate is stirred, plays ingot and be tested for the property.Performance test methods are such as
Under:
Thermal coefficient is examined with thermal conductivity measuring apparatus (Tianjin English Bell's development in science and technology Co., Ltd, imDRY3001- II)
It surveys;
Melt viscosity: measured using the heightization Flow Meter of Japanese Shimadzu Corporation, test condition: mouth mold is 0.5 × 1mm, is carried
Lotus is 10kg, and temperature is 175 DEG C;
Water imbibition: determinand is 4 hours dry at 120 DEG C, 20g, which is weighed, as sample to be tested (is denoted as w1), it will be to test sample
Product are impregnated 30 minutes with 50g deionized water, and after filtering, solid phase is drained 5 minutes, then weigh the weight (note of the solid phase drained
For w2), water absorption rate is calculated with following formula:
Glass transition temperature (Tg): the glass transition of the composition is measured using thermomechanical analyzer (U.S. TA, TMA)
Diameter 3mm, the sample block of high 6mm, then in 175 DEG C/6h is made in moulding material sample by temperature under the conditions of 175 DEG C/25MPa
Under conditions of solidified after, tested using TMA, test condition are as follows: temperature be 20-300 DEG C, heating rate be 10 DEG C/min;
Thermal expansion coefficient (α 1, α 2) utilize thermomechanical analyzer (TMA) measurement: using thermo-mechanical analysis device (TMA100,
セ イ コ ー electronics industry Co. Ltd. system), apply the loading of 50mN, is surveyed under conditions of heating rate is 10 DEG C/min
It is fixed, find out 100-150 DEG C of average value;
Bending strength and bending elastic modulus, are tested using universal testing machine;
Anti-flammability: flame retardant test is carried out according to GB4609-84 by vertical combustion.
The performance test results are also as shown in table 1.
Comparative example 1
Encapsulation plastics, but liquid crystal epoxy resin, o-cresol formaldehyde epoxy resin, modification are prepared according to the method for embodiment 1
Phenolic resin is different (being shown in Table 1) with the content of the epoxy resin containing biphenyl, and the performance test results are also as shown in table 1.
Comparative example 2
Encapsulation plastics, but imidazoles curing accelerator, silane coupling agent and toughener are prepared according to the method for embodiment 1
Content it is different (being shown in Table 1), the performance test results are also as shown in table 1.
Comparative example 3
Encapsulation plastics are prepared according to the method for embodiment 1, unlike, o-cresol formaldehyde epoxy resin replaces with " bicyclic
Pentadiene phenol type epoxy resin (HP-7200H is purchased from Japan DIC Corporation) ", the performance test results are also such as 1 institute of table
Show.
Comparative example 4
Encapsulation plastics are prepared according to the method for embodiment 1, unlike, polyfunctional epoxy resin is replaced with into liquid crystal
Epoxy resin, the performance test results are also as shown in table 1.
Table 1
It can be seen that can be used in being made using plastics composite of the present invention by the result of table 1 and there is high-hydroscopicity, height
Heat resistance, low viscosity, low-expansion coefficient and high-termal conductivity encapsulation plastics, be halogen-free, the elements such as antimony and phosphorus, green ring
It protects.In addition, being respectively compared embodiment 1 and comparative example 1-4 can be seen that and only cooperate the epoxy resin of particular types and amount, consolidate
Agent, filler and auxiliary agent etc. can be effectively improved above-mentioned performance (especially water imbibition and heat resistance).
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of encapsulation plastics composite, which is characterized in that the plastics composite contains:
Wherein, the epoxy resin include liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde epoxy resin and
Biphenyl type epoxy resin, and liquid crystal epoxy resin, glycidyl amine type epoxy resin, o-cresol formaldehyde epoxy resin and biphenyl type ring
Weight ratio between oxygen resin is (8-22): (3-15): (8-25): (4.5-12.5);The curing agent is cyanurotriamide modified
Linear phenol-aldehyde resin.
2. plastics composite according to claim 1, wherein the plastics composite contains:
3. plastics composite according to claim 1 or 2, wherein relative to the filler of 100 parts by weight, liquid crystalline epoxy tree
The content of rouge is 6.1-8.9 parts by weight, and the content of glycidyl amine type epoxy resin is 1.7-10 parts by weight, o-cresol formaldehyde epoxy
The content of resin is 6.1-9.5 parts by weight, and the content of biphenyl type epoxy resin is 3-5.9 parts by weight, and the content of curing agent is
11.5-13.4 parts by weight, the content of imidazoles curing accelerator are 0.2-0.5 parts by weight, and the content of release agent is 1.6-2.2 weight
Part is measured, the content of silane coupling agent is 1-1.4 parts by weight, and the content of toughener is 2.9-4.7 parts by weight.
4. plastics composite described in any one of -3 according to claim 1, wherein liquid crystal epoxy resin, glycidyl amine
Weight ratio between type epoxy resin, o-cresol formaldehyde epoxy resin and biphenyl type epoxy resin is 1:(0.2-1.3): (1-1.1):
(0.5-0.7)。
5. plastics composite according to claim 1, wherein the silicon powder is melting ball-shaped silicon micro powder;
And/or the imidazoles curing accelerator is 2-methylimidazole, 1- 1-cyanoethyl-2-methylimidazole and 2- ethyl -4- methyl
At least one of imidazoles;
And/or the release agent is stearic acid and/or stearate;
And/or the silane coupling agent is γ-(2,3- glycidoxy) propyl trimethoxy silicane, three second of gamma-amino propyl
Oxysilane, gamma-mercaptopropyltriethoxysilane, γ-at least one of mercapto propyldimethoxy-silane and azide silane;
And/or the toughener be carboxyl-terminated liguid nitrile rubber, terminal hydroxy liquid polybutadiene and liquid silastic in extremely
Few one kind.
6. plastics composite according to claim 1, wherein coloring of the plastics composite also containing 3-6 parts by weight
Agent.
7. plastics composite according to claim 6, wherein the colorant is carbon black, chrome blue, chrome green, chrome yellow and molybdenum
At least one of hydrochlorate.
8. right will go plastics composite described in any one of 1-7 preparing the application in integrated antenna package plastics.
9. a kind of method that remove the preparation encapsulation plastics of plastics composite described in any one of 1-7 using right, feature
It is, this method comprises: being surface-treated to filler, melting mixing, cooling and crushing.
10. according to the method described in claim 9, wherein, the method also includes using magnetic separation method removal raw material and/or powder
The metal impurities in material after broken.
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