CN115521746B - Epoxy resin composition, preparation method thereof and packaging adhesive for microelectronic components - Google Patents
Epoxy resin composition, preparation method thereof and packaging adhesive for microelectronic components Download PDFInfo
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- CN115521746B CN115521746B CN202211242269.1A CN202211242269A CN115521746B CN 115521746 B CN115521746 B CN 115521746B CN 202211242269 A CN202211242269 A CN 202211242269A CN 115521746 B CN115521746 B CN 115521746B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The application relates to an epoxy resin composition, a preparation method thereof and packaging adhesive for microelectronic components, which comprises the following raw materials in percentage by weight: polybutadiene rubber modified epoxy resin: 25-35%; polyurethane modified epoxy resin: 5-10%; a diluent: 5-15%; inorganic filler: 45-55%; and (3) auxiliary agents: 0.5-2%; the microelectronic device packaging adhesive comprises an epoxy resin composition and a curing agent composition. According to the application, through the compounding of the polyurethane modified epoxy resin and the polybutadiene rubber modified epoxy resin, the adhesive property, the high-temperature and high-humidity resistance, the thermal shock resistance and the heat conduction property of the packaging adhesive can be effectively improved.
Description
Technical Field
The application relates to the field of high polymer materials, in particular to an epoxy resin composition, a preparation method thereof and packaging adhesive for microelectronic components.
Background
The microelectronic element packaging adhesive is electronic glue or adhesive which can seal, encapsulate or encapsulate some elements (such as a resistor-capacitor circuit board and the like), and can play roles of water proofing, moisture proofing, shock proofing, dust proofing, heat dissipation, confidentiality and the like after encapsulation. The common packaging glue mainly comprises epoxy resin packaging glue, organic silicon packaging glue, polyurethane packaging glue, ultraviolet light curing packaging glue and the like. The color of the packaging adhesive can be transparent and colorless, and almost any color can be made according to the needs.
The epoxy resin packaging adhesive commonly used at present is generally rigid and hard, the majority of the epoxy resin packaging adhesive is used after the two components are blended, and the minority of the epoxy resin packaging adhesive is heated and solidified. Because the electronic components can generate a large amount of heat in the use process, the epoxy resin packaging adhesive can be subjected to long-time cold and hot alternate impact, the ageing resistance of the epoxy resin packaging adhesive is poor, the adhesiveness to the surface of the electronic components can be reduced after continuous high-low temperature circulation, and in some packaging environments with high requirements on the adhesiveness, the phenomena such as degumming and the like easily occur to cause the failure of the electronic products, so that the service life of the electronic components is influenced.
Disclosure of Invention
In order to improve the ageing resistance of the packaging adhesive and improve the bonding performance of the packaging adhesive after continuous high-low temperature circulation, the application provides an epoxy resin composition, a preparation method thereof and the packaging adhesive for microelectronic components.
In a first aspect, the present application provides an epoxy resin composition, which adopts the following technical scheme:
an epoxy resin composition comprises the following raw materials in percentage by weight:
polybutadiene rubber modified epoxy resin: 25-35%;
polyurethane modified epoxy resin: 5-10%;
a diluent: 5-15%;
inorganic filler: 45-55%; and
auxiliary agent: 0.5 to 2 percent.
By adopting the technical scheme, the polybutadiene rubber modified epoxy resin is used as main resin, the polyurethane modified epoxy resin, the diluent, the inorganic filler and the auxiliary agent are added to prepare the epoxy resin composition, the polyurethane modified epoxy resin has the characteristics of excellent low temperature resistance, elasticity, high gloss, strong adhesive force, low shrinkage, good stability and the like, and after the polyurethane modified epoxy resin is added, the linear expansion coefficient of the epoxy resin composition after solidification can be effectively reduced, and meanwhile, the adhesive force of the packaging adhesive to components and parts of different materials and shells is increased, and particularly, the adhesive force of the packaging adhesive on the surfaces of the components and parts of different materials, particularly for some plastics, metals and materials containing coatings, can be obviously improved. The polyurethane modified epoxy resin material has good weather resistance and ageing resistance, can keep excellent bonding effect after continuous temperature change, can improve the ageing resistance of the epoxy resin packaging adhesive through being matched with polybutadiene modified epoxy resin, still keeps high bonding performance after long-time high and low temperature environment, and improves the service lives of the epoxy resin packaging adhesive and electronic components.
The inorganic filler with good heat conduction characteristic is added into the epoxy resin composition, so that the epoxy resin packaging adhesive has good heat conduction property, heat generated by electronic components can be quickly conducted away, the influence on the packaging adhesive is reduced, and the ageing resistance and the practical service life of the packaging adhesive are further improved. Meanwhile, the inorganic filler can further fill the epoxy resin composition, and after the packaging adhesive is cured, a more compact structure is formed, so that internal cavities are reduced.
Optionally, the polybutadiene rubber modified epoxy resin is made from raw materials comprising the following weight percentages: 10-30% of polybutadiene rubber, 68-88% of epoxy resin and 0.2-2% of catalyst.
The polybutadiene rubber is preferably one or a combination of a plurality of hydroxyl-terminated polybutadiene rubber, carboxyl-terminated polybutadiene rubber, hydroxyl-terminated polybutadiene rubber acrylonitrile, carboxyl-terminated polybutadiene rubber acrylonitrile and epoxidized hydroxyl-terminated polybutadiene rubber.
The polybutadiene rubber is further preferably a mixture of epoxidized hydroxyl-terminated polybutadiene rubber and at least one of hydroxyl-terminated polybutadiene rubber, carboxyl-terminated polybutadiene rubber, hydroxyl-terminated polybutadiene rubber acrylonitrile, and carboxyl-terminated polybutadiene rubber acrylonitrile.
The polybutadiene rubber is most preferably an epoxidized hydroxyl terminated polybutadiene rubber.
By adopting the technical scheme, the polybutadiene rubber and the epoxy resin are mixed and modified through the catalysis of the catalyst, the addition amount of the polybutadiene rubber is preferably 10-30%, and when the addition amount of the polybutadiene rubber is less than 10%, the modified epoxy resin has insufficient toughness and poor low temperature resistance; when the polybutadiene rubber content exceeds 30%, the prepared epoxy resin composition is too high in viscosity and poor in fluidity, is not beneficial to encapsulation of electronic components, is not easy to flow into gaps of the electronic components, is easy to cause internal glue shortage and holes, and reduces the heat conduction property and voltage breakdown resistance of a glue layer after encapsulation.
Optionally, the epoxy resin is one or a combination of bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin.
Further, the epoxy resin is preferably a liquid bisphenol a epoxy resin, bisphenol F epoxy resin, a combination of one or more of novolac epoxy resins; the epoxy value of the epoxy resin is preferably 0.35 to 7.
The epoxy resin is most preferably a liquid bisphenol F epoxy resin.
By adopting the technical scheme, the liquid epoxy resin can enable the modified epoxy resin composition to have lower viscosity and fluidity, is more beneficial to filling and sealing of packaging glue, has better viscosity and fluidity, and can ensure that the epoxy resin composition has lower viscosity on the premise of not changing polybutadiene rubber.
Optionally, the catalyst is one or a combination of two of a quaternary ammonium salt catalyst and a quaternary phosphonium salt catalyst.
Optionally, the polybutadiene rubber modified epoxy resin is prepared by the following method:
mixing polybutadiene rubber and epoxy resin, heating to 100-120 ℃ under continuous stirring, slowly adding a catalyst, heating to 150-160 ℃, preserving heat for 1-2 h, cooling to 70-80 ℃, and discharging to obtain the polybutadiene rubber modified epoxy resin.
By adopting the technical scheme, after the polybutadiene rubber and the epoxy resin are mixed, the catalyst is added at the temperature of 100-120 ℃ for catalytic modification, the catalyst is preferably added in a dropwise manner, the adding time is preferably 30-60 min, and the mixture is continuously stirred in the heating process, so that the uneven reaction of raw materials or the change of the properties of products caused by the excessive concentrated local heat release of the mixture can be avoided.
Optionally, the polyurethane modified epoxy resin is modified epoxy resin modified by isocyanate-terminated polyurethane.
Further, the isocyanate-terminated polyurethane is preferably polyurethane synthesized from toluene-2, 4-diisocyanate and diols.
Further, the polyurethane modified epoxy resin is prepared by the following method: mixing toluene-2, 4-diisocyanate and polyethylene glycol, heating to 100-120 ℃, adding epoxy resin and a catalyst, stirring for reacting for 2-3 h, cooling to 70-80 ℃, and discharging to obtain the polyurethane modified epoxy resin. The catalyst is an organotin catalyst.
By adopting the technical scheme, the modified epoxy resin modified by the isocyanate-terminated polyurethane prepolymer synthesized by taking toluene-2, 4-diisocyanate and diols as raw materials has the structure of not only containing flexible C-C chains and C-O-C chains, but also having active amide groups, has good compatibility with other epoxy resin components, and can provide good weather resistance and adhesive force for the prepared epoxy resin composition by matching with the polybutadiene rubber modified epoxy resin.
Optionally, the inorganic filler comprises one or more of silica micropowder, alumina, aluminum nitride, silicon nitride, boron nitride, and silicon carbide.
The inorganic filler is preferably a powder inorganic filler having an amorphous, quasi-spherical or spherical shape.
The inorganic filler is preferably an inorganic filler subjected to surface treatment of a silane coupling agent; the silane coupling agent is preferably an epoxy silane coupling agent.
The particle size distribution of the inorganic filler is 40-60 mu m: 65-85 wt%, 10-30 μm: 15-35 wt%.
By adopting the technical scheme, the inorganic filler has better dispersibility among resin molecules after being subjected to surface modification treatment of the silane coupling agent. The inorganic filler is preferably powder filler with two different particle size grade ranges, and the inorganic filler with two particle size distributions is matched, so that the good fluidity of the mixture can be met, the high heat conductivity coefficient of the cured packaging adhesive with high filler filling ratio can be met, and gaps between large particle size powder can be filled with small particle size powder to form a compact structure.
Optionally, the diluent is a reactive diluent; preferably a long chain difunctional glycol diglycidyl ether of low viscosity.
The diluent is further preferably one or more of ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dipropylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether.
Optionally, the auxiliary agent comprises at least one of an anti-settling agent, an antifoaming agent, a dispersing agent, a coupling agent and an antioxidant.
Optionally, the auxiliary agent comprises: 75-85 wt% of anti-settling agent, 3-10 wt% of defoamer, 3-10 wt% of dispersant, 3-10 wt% of coupling agent, 3-10 wt% of antioxidant, and the sum of the components is 100%.
Optionally, the anti-settling agent comprises one or more of fumed silica, barium sulfate, and organic bentonite.
Further preferably, the anti-settling agent comprises 10% of fumed silica, 70% of barium sulfate and 20% of organic bentonite, wherein the sum of the components is 100%; the barium sulfate is preferably 8000 mesh precipitated barium sulfate.
By adopting the technical scheme, the anti-settling agent with the preferable component proportion can ensure that the filler does not settle and agglomerate on the premise of not increasing viscosity and reducing fluidity after being dispersed at high speed.
Optionally, the defoamer is at least one of an oily system silicone defoamer and an oily system non-silicone defoamer.
Further, the defoamer is preferably an oily system silicone defoamer.
By adopting the technical scheme, the organic silicon defoamer has the characteristics of small addition amount, good defoaming performance and strong foam inhibition performance, and the non-silicon defoamer has the advantage of not influencing the adhesive force between the pouring body and the shell while defoaming.
Alternatively, the coupling agent is preferably an epoxy silane coupling agent.
Optionally, the antioxidant comprises a main antioxidant and an auxiliary antioxidant; the main antioxidant is preferably a phenolic antioxidant or an amine antioxidant, and the auxiliary antioxidant is preferably a thioether antioxidant or a phosphorus antioxidant.
By adopting the technical scheme, the heat stability of the packaging adhesive can be obviously improved through the cooperation of the main antioxidant and the auxiliary antioxidant, and the service life of the packaging adhesive can be greatly prolonged especially when the packaging adhesive is applied to electrical components such as a temperature sensor, a capacitor and the like.
Optionally, pigments are added to the epoxy resin mixture, wherein the pigments account for 0.1-1% of the total weight of the epoxy resin composition.
By adopting the technical scheme, the packaging adhesive can be prepared into various colors by adding the pigment into the epoxy resin mixture so as to meet the use requirements; the pigment may be selected as carbon black.
In a second aspect, the application provides a method for preparing an epoxy resin composition, which adopts the following technical scheme:
a method of preparing an epoxy resin composition comprising the steps of: sequentially adding polybutadiene rubber modified epoxy resin, polyurethane modified epoxy resin, diluent, auxiliary agent and inorganic filler into a reaction kettle, vacuumizing, and carrying out high-speed dispersion and mixing on the mixture for 60-120 min to obtain the epoxy resin composition.
Optionally, the vacuum degree of the vacuumizing treatment is-0.08-0.1 MPa.
Alternatively, the rotational speed of the high speed dispersion process is 1000 to 2000rpm.
In a third aspect, the present application provides a packaging adhesive for microelectronic components, which adopts the following technical scheme:
the packaging adhesive for the microelectronic element comprises the epoxy resin composition and the curing agent composition, wherein the mass ratio of the epoxy resin composition to the curing agent composition is 100: (18-25).
Optionally, the curing agent composition comprises the following raw materials in percentage by weight:
80-90% of polyether amine;
alicyclic amine: 5-10%;
alkylphenol ethoxylates: 1 to 5 percent; and
hydrolysis inhibitor: 1 to 5 percent.
By adopting the technical scheme, the polyether amine molecular structure contains ether bonds, belongs to a flexible curing agent, has low reaction heat release temperature, long operation time after mixing, has the advantages of colorless transparency, high gloss, good toughness, thermal shock resistance and the like, enhances the flexibility of the product through a polyether main chain with high molecular weight, improves the tearing strength, thereby adjusting the curing product with slightly lower relative hardness, the operation time, the hardness and the flexibility, and can improve the hardness, the modulus and the shock resistance of the cured packaging adhesive by adding a small amount of alicyclic amine. The alkylphenol ethoxylates can increase the flexibility of the cured product, improve the moisture absorption of alicyclic amine, and greatly accelerate the curing speed at high temperature under the condition of not shortening the pot life at normal temperature when being added in a small amount.
Optionally, the polyetheramine is any one of amino-terminated polyoxypropylene ether or amino-terminated polyoxyethylene ether. The molecular weight of the polyether amine is preferably 220-5000, and the active hydrogen equivalent is preferably 50-1000.
Optionally, the alicyclic amine comprises one or more combinations of menthanediamine, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, 4, -diaminodicyclohexylmethane, and derivatives thereof.
Optionally, the alkylphenol ethoxylates comprise one or more of nonylphenol ethoxylates, octylphenol ethoxylates and dodecylphenol ethoxylates; further preferred is dodecylphenol polyoxyethylene ether.
Optionally, the anti-hydrolysis agent is a mixture prepared by melting carbodiimide into diisopropylnaphthalene; the mixing ratio of the polycarbodiimide to the diisopropylnaphthalene is 1 (1-20).
Alternatively, the curative composition is prepared by the following method: sequentially adding polyether amine, alicyclic amine, alkylphenol ethoxylate and an anti-hydrolysis agent into a reaction kettle, controlling the temperature to be 25-60 ℃, and stirring at a low speed of 30-90 rpm for 30-90 min under the protection of nitrogen until the glue solution is uniform and has no floccules and no bubbles, thus obtaining the curing agent composition.
By adopting the technical scheme, the reaction is carried out under the protection of nitrogen, and the composition can be prevented from generating yellow edges due to the inclusion of alkylphenol ethoxylates through the protection of nitrogen.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the epoxy resin composition provided by the technical scheme of the application, the polybutadiene rubber modified epoxy resin is used as main resin, the polyurethane modified epoxy resin, the anti-diluent, the inorganic filler and the auxiliary agent are added to prepare the epoxy resin composition, the polyurethane modified epoxy resin has the characteristics of excellent low temperature resistance, elasticity, high gloss, strong adhesive force, low shrinkage, good stability and the like, and after the polyurethane modified epoxy resin is added, the linear expansion coefficient of the epoxy resin composition after curing can be effectively reduced, and meanwhile, the adhesive force of the packaging adhesive to components and shells of different materials is increased, and especially, the adhesive force of the packaging adhesive on the surfaces of the components and shells can be obviously improved for some plastics, metals and materials containing coating layers.
2. According to the epoxy resin composition provided by the technical scheme of the application, the inorganic filler with good heat conduction property is added into the epoxy resin composition, so that the epoxy resin packaging adhesive has good heat conduction property, meanwhile, the epoxy resin composition can be further filled, a more compact structure is formed after the packaging adhesive is cured, and the internal cavity is reduced.
3. According to the epoxy resin composition provided by the technical scheme of the application, the modified epoxy resin modified by the isocyanate-terminated polyurethane prepolymer synthesized by using toluene-2, 4-diisocyanate and diols as raw materials has the structure of not only containing flexible C-C chains and C-O-C chains, but also having active amide groups, has good compatibility with other epoxy resin components, and can provide good weather resistance and adhesive force for the prepared epoxy resin composition by matching with polybutadiene rubber modified epoxy resin.
Detailed Description
The present application will be described in further detail with reference to specific examples.
Preparation example of polybutadiene rubber modified epoxy resin
Preparation examples 1 to 5
The polybutadiene rubber modified epoxy resin provided in preparation examples 1 to 5 has the following specific preparation methods with reference to Table 1: and sequentially feeding polybutadiene rubber and epoxy resin into a reaction kettle, continuously stirring and heating to 120 ℃, slowly dropwise adding a catalyst, finishing dropwise adding within 30min, heating to 150 ℃, preserving heat for 2h, and then cooling to 80 ℃ for discharging to obtain the polybutadiene rubber modified epoxy resin.
Wherein the polybutadiene rubber is hydroxyl-terminated polybutadiene rubber (HTPB); the epoxy resin is bisphenol A epoxy resin, and the epoxy value is 0.5; the catalyst was benzyl triethylammonium chloride (TEBA).
Table 1: preparation examples 1 to 5 component proportions (mass percent)
| Polybutadiene rubber | Epoxy resin | Catalyst | |
| Preparation example 1 | 10％ | 88％ | 2％ |
| Preparation example 2 | 30％ | 68％ | 2％ |
| Preparation example 3 | 20％ | 79％ | 1％ |
| Preparation example 4 | 5％ | 93％ | 2％ |
| Preparation example 5 | 35％ | 63％ | 2％ |
Preparation example 6
The difference between this preparation and preparation 3 is that the polybutadiene rubber is a combination of epoxidized hydroxyl-terminated polybutadiene rubber (EHTPB) and hydroxyl-terminated polybutadiene rubber (HTPB) in a mass ratio of 1:1, and the remainder is the same as in preparation 3.
Preparation example 7
The present preparation differs from preparation 3 in that the polybutadiene rubber is an epoxidized hydroxyl terminated polybutadiene rubber (EHTPB); the remainder remained the same as in preparation example 3.
Preparation example 8
The difference between this preparation and preparation 7 is that the epoxy resin is a liquid bisphenol F epoxy resin, and the epoxy value is 0.54; the remainder remained the same as in preparation example 3.
Preparation example of polyurethane modified epoxy resin
Preparation examples 9 to 11
The composition ratios of the polyurethane modified epoxy resins provided in preparation examples 9 to 11 are shown in Table 2, and the specific preparation method is as follows: mixing toluene-2, 4-diisocyanate and polyethylene glycol, heating to 100 ℃, adding epoxy resin and a catalyst, stirring for reacting for 2-3 hours, cooling to 70-80 ℃, discharging to obtain polyurethane modified epoxy resin, wherein the catalyst is organotin catalyst dibutyl tin dilaurate.
Table 1: preparation examples 1 to 3 component proportions (mass percent)
| Isocyanate(s) | Diols | Catalyst | |
| Preparation example 9 | 15％ | 84％ | 1％ |
| Preparation example 10 | 25％ | 74％ | 1％ |
| PREPARATION EXAMPLE 11 | 18％ | 80％ | 2％ |
Preparation example 12
The difference between this preparation and preparation 11 is that the isocyanate is diphenylmethane diisocyanate, the remainder remaining the same as preparation 11.
Example 1
The embodiment provides a packaging adhesive for microelectronic components, which comprises an epoxy resin composition and a curing agent composition with a mass ratio of 100:18, wherein the component proportions of the epoxy resin composition and the curing agent composition are as follows with reference to a table 1:
s1, preparing an epoxy resin composition: feeding the polybutadiene rubber modified epoxy resin prepared in preparation example 1, the polyurethane modified epoxy resin prepared in preparation example 9, a diluent, an auxiliary agent and an inorganic filler in sequence in a reaction kettle or a middle reaction kettle with two high-speed dispersing discs and frame stirring paddles at the same time, vacuumizing to set the vacuum degree to 0.1MPa after the feeding is completed, setting the rotating speed of the high-speed dispersing discs to 1000 revolutions per minute, setting the rotating speed of the frame stirring paddles to 120 revolutions per minute, and stirring in vacuum for 60 minutes until the glue solution is uniform, free of particles and free of bubbles to obtain an epoxy resin composition;
s2, preparing a curing agent composition: sequentially feeding polyether amine, alicyclic amine, alkylphenol ethoxylate and an anti-hydrolysis agent into a reaction kettle with blade paddle stirring, stirring at a low speed under the protection of nitrogen, setting the rotating speed to 300 revolutions per minute, setting the temperature to 25 ℃, and stirring for 90min until the glue solution is uniform and has no floccules and no bubbles, wherein the obtained product is the curing agent composition.
S3, preparing packaging adhesive for microelectronic components: and mixing the epoxy resin composition and the curing agent composition according to the proportion, and uniformly stirring to obtain the packaging adhesive for the microelectronic element.
In the step S1, the diluent is ethylene glycol diglycidyl ether; the inorganic filler is alpha alumina with the particle diameter of 40-60 mu m and modified by the surface of the epoxy silane coupling agent; the auxiliary agent comprises an anti-settling agent, a defoaming agent, a dispersing agent, a coupling agent and an antioxidant; 80% of anti-settling agent, 5% of defoamer, 5% of dispersant, 5% of coupling agent and 5% of antioxidant by weight of the total auxiliary agent; the anti-settling agent is fumed silica, the antifoaming agent is an oily system non-silicon antifoaming agent HT833, the coupling agent is an epoxy silane coupling agent KH-560, and the antioxidant is a phenolic antioxidant 1076.
In the step S2, the polyetheramine is polyetheramine D230; alicyclic amine Menthanediamine (MDA); the alkylphenol polyoxyethylene ether is nonylphenol polyoxyethylene ether; the hydrolysis resisting agent is a mixture of polycarbodiimide and diisopropylnaphthalene, the polycarbodiimide is melted in the diisopropylnaphthalene at 80 ℃ to prepare the hydrolysis resisting agent, and the mixing ratio of the polycarbodiimide to the diisopropylnaphthalene is 1:1.
examples 2 to 8
Examples 2 to 8 differ from example 1 in that the sources of the polybutadiene rubber modified epoxy resin and the polyurethane modified epoxy resin are different, and with specific reference to Table 2 below, the remainder remain the same as in example 1.
Table 2: EXAMPLES 2 to 8 Source of raw materials
| Polybutadiene rubber modified epoxy resin | Polyurethane modified epoxy resin | |
| Example 2 | Preparation example 2 | Preparation example 9 |
| Example 3 | Preparation example 3 | Preparation example 9 |
| Example 4 | Preparation example 6 | Preparation example 9 |
| Example 5 | Preparation example 7 | Preparation example 9 |
| Example 6 | Preparation example 8 | Preparation example 9 |
| Example 7 | Preparation example 8 | Preparation example 10 |
| Example 8 | Preparation example 8 | PREPARATION EXAMPLE 11 |
| Example 9 | Preparation example 8 | Preparation example 12 |
Comparative example 1
This comparative example differs from example 1 in that the polyurethane-modified epoxy resin was not added to the epoxy resin composition, and the remainder remained the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that the polybutadiene modified epoxy resin was derived from preparation example 4, the remainder remaining in accordance with example 1.
Comparative example 3
This comparative example differs from example 1 in that the polybutadiene modified epoxy resin was derived from preparation 5, the remainder remaining in accordance with example 1.
Performance detection
The packaging adhesive for microelectronic devices prepared in each example and comparative example was cured by heating at 100 ℃ for 2 hours to prepare an adhesive film, and performance test was performed as follows:
tensile strength: testing the tensile strength of the adhesive film according to GB/T1040.1-2018 standard;
adhesive strength: the adhesive strength of the adhesive film is tested according to GB/T7124-2008 standard;
thermal conductivity: testing the thermal conductivity of the encapsulant according to ASTM D5470 standard;
and (3) water boiling test: and (3) curing the packaging adhesive for the microelectronic element, boiling the packaging adhesive for 1000 hours, and observing whether the adhesive layer has cracking and degumming phenomena in a high-temperature and high-humidity environment.
Cold and hot impact test: and (3) curing the packaging adhesive for the microelectronic component, placing the cured packaging adhesive into a liquid constant-temperature water bath, keeping the temperature at the low temperature of 0-5 ℃ and the high temperature of 95-100 ℃ for 2min, continuously circulating the high temperature and the low temperature 10000 times, and observing whether the adhesive layer is cracked or degummed.
The results of the performance tests are shown in Table 3 below.
Table 3: results of Performance measurements of examples 1 to 9 and comparative examples 1 to 3
As can be seen from the data in Table 3, the microelectronic element packaging adhesive prepared by the technical scheme of the application has the advantages that the adhesive property of the packaging adhesive is further improved through the matched use of the polybutadiene rubber modified epoxy resin and the polyurethane modified epoxy resin, the packaging adhesive still has good adhesive effect after 1000h of water boiling and 10000 times of extreme cold and hot impact tests, and has good ageing resistance, good heat conduction property and mechanical strength.
The characteristics of the encapsulation adhesive for microelectronic devices are further investigated below.
Example 10
This example differs from example 1 in that the inorganic filler comprises 70wt% of alpha alumina having a particle size of 40 to 60 μm and 30wt% of alpha alumina having a particle size of 10 to 30 μm, the remainder remaining in accordance with example 1.
Example 11
This example differs from example 1 in that the particle size of the alpha alumina is 10 to 30 μm, and the remainder remains the same as in example 1.
Example 12
This example differs from example 1 in that the particle size of the alpha alumina is 80 to 100 μm, and the remainder remains the same as in example 1.
Example 13
This example differs from example 1 in that the defoamer is an oily system silicone defoamer DF-834, the remainder remaining consistent with example 1.
Example 14
This example differs from example 1 in that the anti-settling agent comprises 10wt% fumed silica, 70wt% 8000 mesh precipitated barium sulfate, 20wt% organobentonite, the remainder remaining in accordance with example 1.
Example 15
This example differs from example 1 in that the polyetheramine is polyetheramine D400, the remainder remaining in accordance with example 1.
Example 16
This example differs from example 1 in that alkylphenol ethoxylates are dodecylphenol ethoxylates, the remainder remaining in the same manner as in example 1.
Example 17
This example differs from example 1 in that the mixing ratio of polycarbodiimide to diisopropylnaphthalene in the hydrolysis inhibitor is 1:20, all remaining in accordance with example 1.
Example 18
This example differs from example 1 in that the mixing ratio of polycarbodiimide to diisopropylnaphthalene in the hydrolysis inhibitor is 5:1, the remainder remain the same as in example 1.
The performance of the encapsulation compound for microelectronic devices in examples 10 to 18 was examined, and the examination results are shown in Table 4 below.
Table 4: examples 10 to 18 Performance test results
The preferred technical schemes in the application are further verified in the embodiments 10-18, and test data show that the preferred technical schemes can obtain better effects, and the performance of the packaging adhesive is further improved.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (7)
1. An epoxy resin composition is characterized by comprising the following raw materials in percentage by weight:
polybutadiene rubber modified epoxy resin: 25-35%;
polyurethane modified epoxy resin: 5-10%;
a diluent: 5-15%;
inorganic filler: 45-55%;
auxiliary agent: 0.5-2%;
the sum of the components is 100 percent;
the polybutadiene rubber modified epoxy resin comprises the following raw materials in percentage by weight: 10-30% of polybutadiene rubber, 68-88% of epoxy resin, 0.2-2% of catalyst, and 100% of the sum of the components; the polybutadiene rubber modified epoxy resin is prepared by the following method: mixing polybutadiene rubber and epoxy resin, heating to 100-120 ℃ under continuous stirring, slowly adding a catalyst, then heating to 150-160 ℃ for heat preservation for 1-2 h, cooling to 70-80 ℃, and discharging to obtain the polybutadiene rubber modified epoxy resin; the polyurethane modified epoxy resin is modified epoxy resin modified by isocyanate-terminated polyurethane; the isocyanate-terminated polyurethane is polyurethane synthesized by taking toluene-2, 4-diisocyanate and diols as raw materials.
2. An epoxy resin composition according to claim 1, wherein the polybutadiene rubber is one or more of a hydroxyl-terminated polybutadiene rubber, a carboxyl-terminated polybutadiene rubber, a hydroxyl-terminated polybutadiene rubber acrylonitrile, a carboxyl-terminated polybutadiene rubber acrylonitrile, and an epoxidized hydroxyl-terminated polybutadiene rubber.
3. The epoxy resin composition according to claim 1, wherein the particle size distribution of the inorganic filler is 40-60 μm: 65-85 wt%, 10-30 μm: 15-35 wt%.
4. A method for producing an epoxy resin composition according to any one of claims 1 to 3, comprising the steps of: sequentially adding polybutadiene rubber modified epoxy resin, polyurethane modified epoxy resin, a diluent, an auxiliary agent and an inorganic filler into a reaction kettle, vacuumizing, and carrying out high-speed dispersion and mixing on the mixture for 60-120 min to obtain the epoxy resin composition.
5. An encapsulation adhesive for microelectronic components, comprising the epoxy resin composition according to any one of claims 1 to 3 and a curing agent composition, wherein the mass ratio of the epoxy resin composition to the curing agent composition is 100: (18-25).
6. The packaging adhesive for microelectronic components according to claim 5, wherein the curing agent composition comprises the following raw materials in percentage by weight:
80-90% of polyether amine;
alicyclic amine: 5-10%;
alkylphenol ethoxylates: 1-5%; and
hydrolysis inhibitor: 1-5%.
7. The packaging adhesive for microelectronic components according to claim 6, wherein the curing agent composition is prepared by the following method: and sequentially adding polyether amine, alicyclic amine, alkylphenol ethoxylate and an anti-hydrolysis agent into a reaction kettle, controlling the temperature to be 25-60 ℃, and stirring at a low speed of 30-90 rpm for 30-90 min under the protection of nitrogen until the glue solution is uniform and has no floccules and no bubbles, thereby obtaining the curing agent composition.
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