CN115521746A - 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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- CN115521746A CN115521746A CN202211242269.1A CN202211242269A CN115521746A CN 115521746 A CN115521746 A CN 115521746A CN 202211242269 A CN202211242269 A CN 202211242269A CN 115521746 A CN115521746 A CN 115521746A
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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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- 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 a packaging adhesive for microelectronic components, which comprises the following raw materials in percentage by weight: polybutadiene rubber-modified epoxy resin: 25 to 35 percent; polyurethane modified epoxy resin: 5 to 10 percent; diluent agent: 5 to 15 percent; inorganic filler: 45 to 55 percent; and an auxiliary agent: 0.5 to 2 percent; the microelectronic component packaging glue comprises an epoxy resin composition and a curing agent composition. According to the application, the adhesive property, the high-temperature and high-humidity resistance, the cold and hot shock resistance and the heat conductivity of the packaging adhesive can be effectively improved by compounding the polyurethane modified epoxy resin and the polybutadiene rubber modified epoxy resin.
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 an encapsulation adhesive for microelectronic components.
Background
The microelectronic component packaging glue is electronic glue or adhesive which can seal, encapsulate or encapsulate some components (such as a resistor-capacitor normal circuit board and the like), and can play roles of water resistance, moisture resistance, shock resistance, dust prevention, heat dissipation, confidentiality and the like after encapsulation. Common packaging adhesives mainly include epoxy resin packaging adhesives, silicone packaging adhesives, polyurethane packaging adhesives, ultraviolet light curing packaging adhesives, and the like. The color of the packaging adhesive can be transparent and colorless, and can also be made into almost any color according to the requirement.
The currently common epoxy resin packaging adhesive is generally rigid and hard, most of the epoxy resin packaging adhesive is two components and needs to be used after blending, and the rest of the epoxy resin packaging adhesive is single component and needs to be cured by heating. Because electronic components can produce a large amount of heat in the use, consequently epoxy resin encapsulation glue can stand long-time cold and hot impact in turn, and epoxy resin encapsulation glue its ageing resistance is relatively poor, can reduce to the adhesion nature on electronic components surface after continuous high low temperature circulation, in some encapsulation environment to the higher requirement of adhesion property, the phenomenon such as coming unstuck appears easily and leads to the electronic product to break down, influences electronic components's life.
Disclosure of Invention
In order to improve the aging resistance of the packaging adhesive and improve the bonding performance of the packaging adhesive after continuous high-temperature and 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 to 35 percent;
polyurethane modified epoxy resin: 5 to 10 percent;
diluent agent: 5 to 15 percent;
inorganic filler: 45 to 55 percent; and
auxiliary agent: 0.5 to 2 percent.
By adopting the technical scheme, the polybutadiene rubber modified epoxy resin is used as main resin, and the polyurethane modified epoxy resin, the diluent, the inorganic filler and the auxiliary agent are added to prepare the epoxy resin composition, wherein the polyurethane modified epoxy resin has the characteristics of excellent low temperature resistance, elasticity, high gloss, strong bonding force, low shrinkage rate, good stability and the like. The polyurethane modified epoxy resin material has good weather resistance and aging resistance, can still keep excellent bonding effect after the temperature is continuously changed, can improve the aging resistance of epoxy resin packaging adhesive by being matched with polybutadiene modified epoxy resin, still keeps very high bonding performance after long-time high and low temperature environment, and prolongs the service life 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 performance, heat generated by electronic components can be quickly conducted away, the influence on the packaging adhesive is reduced, and the aging resistance and the practical life of the packaging adhesive are further improved. Meanwhile, the epoxy resin composition can be further filled with the inorganic filler, and a more compact structure is formed after the packaging adhesive is cured, so that internal cavities are reduced.
Optionally, the polybutadiene rubber modified epoxy resin is prepared from the following raw materials in percentage by weight: 10 to 30 percent of polybutadiene rubber, 68 to 88 percent of epoxy resin and 0.2 to 2 percent of catalyst.
The polybutadiene rubber is preferably one or more 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 more preferably a mixture of at least one of hydroxyl-terminated polybutadiene rubber, carboxyl-terminated polybutadiene rubber, hydroxyl-terminated polybutadiene rubber acrylonitrile and carboxyl-terminated polybutadiene rubber acrylonitrile with epoxidized hydroxyl-terminated polybutadiene rubber.
The polybutadiene rubber is most preferably epoxidized hydroxyl-terminated polybutadiene rubber.
By adopting the technical scheme, the polybutadiene rubber and the epoxy resin are mixed and modified under the catalytic action 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 viscosity of the prepared epoxy resin composition is too high, the flowability is poor, the encapsulation of electronic components is not facilitated, the epoxy resin composition is not easy to flow into gaps of the electronic components, internal glue shortage and cavities are easily caused, and the heat-conducting property and the voltage breakdown resistance of a glue layer after encapsulation are reduced.
Optionally, the epoxy resin is one or a combination of bisphenol a epoxy resin, bisphenol F epoxy resin and novolac epoxy resin.
Further, the epoxy resin is preferably one or more of liquid bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin; 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, so that encapsulation filling of the encapsulation adhesive is facilitated, the bisphenol F epoxy resin has better viscosity and fluidity, and the epoxy resin composition can be ensured to have 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 ℃, keeping the temperature 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 phenomenon that the local heat release of the mixture is too concentrated to cause uneven reaction of raw materials or change of product properties can be avoided.
Optionally, the polyurethane modified epoxy resin is modified by isocyanate-terminated polyurethane.
Further, the isocyanate-terminated polyurethane is preferably a polyurethane synthesized from toluene-2, 4-diisocyanate and glycols as raw materials.
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 organic tin 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 contains a flexible C-C chain and a C-O-C chain and also contains active amide groups, has good compatibility with other epoxy resin components, can provide good weather resistance and bonding force for the prepared epoxy resin composition by matching with the polybutadiene rubber modified epoxy resin, and has good stability.
Optionally, the inorganic filler includes one or more of silicon micropowder, aluminum oxide, aluminum nitride, silicon nitride, boron nitride, and silicon carbide.
The inorganic filler is preferably a powdery inorganic filler having an amorphous, quasi-spherical or spherical shape.
The inorganic filler is preferably an inorganic filler subjected to surface treatment by 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 to 35 weight percent.
By adopting the technical scheme, the inorganic filler has better dispersibility among resin molecules after being subjected to surface modification treatment by the silane coupling agent. The inorganic filler is preferably powder fillers with two different particle size grade ranges, and the inorganic fillers with two particle size distributions are matched, so that the good fluidity of a mixture can be met, the cured packaging adhesive with a high filler filling ratio has a high heat conductivity coefficient, and gaps among 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 low viscosity long chain difunctional glycol diglycidyl ether.
The diluent is further preferably one or a combination of 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, and 1,4 cyclohexanedimethanol diglycidyl ether.
Optionally, the auxiliary agent includes at least one of an anti-settling agent, a defoaming 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 defoaming agent, 3-10 wt% of dispersing agent, 3-10 wt% of coupling agent and 3-10 wt% of antioxidant, wherein the sum of the components is 100%.
Optionally, the anti-settling agent comprises one or more of fumed silica, barium sulfate, and organic bentonite.
More preferably, the anti-settling agent comprises 10% of fumed silica, 70% of barium sulfate and 20% of organic bentonite, and 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 optimal component proportion can ensure that the filler is not settled and agglomerated on the premise of not increasing viscosity and reducing fluidity after being dispersed at high speed.
Optionally, the defoaming agent is at least one of an oily system silicone defoaming agent and an oily system non-silicone defoaming agent.
Further, the defoaming agent is preferably an oily system silicone defoaming agent.
By adopting the technical scheme, the organic silicon defoaming agent has the characteristics of small addition amount, good defoaming performance and strong foam inhibition performance, and the non-silicon defoaming agent has the advantage of not influencing the bonding force between the casting body and the shell while defoaming.
Optionally, the coupling agent is preferably an epoxy silane coupling agent.
Optionally, the antioxidant comprises a primary antioxidant and a secondary antioxidant; the primary antioxidant is preferably a phenol antioxidant or an amine antioxidant, and the secondary antioxidant is preferably a thioether antioxidant or a phosphorus antioxidant.
By adopting the technical scheme, the thermal stability of the packaging adhesive can be obviously improved through the matching 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, a pigment is further added to the epoxy resin mixture, and the pigment accounts 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 from carbon black.
In a second aspect, the present application provides a method for preparing an epoxy resin composition, which adopts the following technical scheme:
a preparation method of an epoxy resin composition comprises the following steps: sequentially adding polybutadiene rubber modified epoxy resin, polyurethane modified epoxy resin, diluent, auxiliary agent and inorganic filler into a reaction kettle, vacuumizing, and dispersing and mixing the mixture at a high speed for 60-120 min to obtain the epoxy resin composition.
Optionally, the vacuum degree of the vacuum pumping treatment is-0.08-0.1 MPa.
Optionally, the rotating speed in the high-speed dispersing process is 1000-2000 rpm.
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 component comprises the epoxy resin composition and a curing agent composition, wherein the mass ratio of the epoxy resin composition to the curing agent composition is 100: (18 to 25).
Optionally, the curing agent composition comprises the following raw materials in percentage by weight:
80-90% of polyether amine;
alicyclic amine: 5 to 10 percent;
alkylphenol ethoxylates: 1 to 5 percent; and
hydrolysis resistance agent: 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 and long operation time after mixing, and the product has the advantages of colorless transparency, high gloss, good toughness, cold and heat shock resistance and the like. The alkylphenol ethoxylates can increase the flexibility of the cured product and improve the moisture absorption of the alicyclic amine, and when the alkylphenol ethoxylates is added in a small amount, the curing speed at high temperature can be greatly accelerated under the condition that the working life at normal temperature is not shortened.
Optionally, the polyether amine is any one of amino-terminated polyoxypropylene ether or amino-terminated polyoxyethylene ether. The molecular weight of the polyether amine is preferably 220 to 5000, and the active hydrogen equivalent weight is preferably 50 to 1000.
Optionally, the alicyclic amine comprises a combination of one or more of menthane diamine, isophorone diamine, 1, 3-bis (aminomethyl) cyclohexane, 4, -diaminodicycloethyl methane, and derivatives thereof.
Optionally, the alkylphenol ethoxylates comprises one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and dodecylphenol polyoxyethylene ether; more preferably, dodecylphenol polyoxyethylene ether.
Optionally, the hydrolysis resistant agent is a mixture prepared by melting carbodiimide in diisopropylnaphthalene; the mixing ratio of the polycarbodiimide to the diisopropyl naphthalene is 1 (1-20).
Optionally, the curing agent composition is prepared by the following method: sequentially adding polyether amine, alicyclic amine, alkylphenol polyoxyethylene ether 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 glue liquid is uniform and has no floccules and no bubbles to obtain the curing agent composition.
By adopting the technical scheme, the reaction is carried out under the protection of nitrogen, and the phenomenon that the composition contains alkylphenol ethoxylates to generate yellow edges can be avoided through the protection of nitrogen.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the epoxy resin composition provided by the technical scheme of the application takes polybutadiene rubber modified epoxy resin as main resin, polyurethane modified epoxy resin, anti-diluent, inorganic filler and 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 bonding force, low shrinkage rate, good stability and the like, after the polyurethane modified epoxy resin is added, the linear expansion coefficient of the cured epoxy resin composition can be effectively reduced, meanwhile, the adhesive force of the packaging adhesive to components and parts made of different materials and shells is increased, and particularly, the adhesive force of the packaging adhesive on the surface of the packaging adhesive can be obviously improved for some plastics, metals and materials containing coatings.
2. The epoxy resin composition that this application technical scheme provided adds the inorganic filler that has good heat conduction characteristic in the epoxy resin composition, can make epoxy resin encapsulation glue possess good heat conductivility, also can carry out further packing to the epoxy resin composition simultaneously, forms more compact structure after the encapsulation glue solidification, reduces inside cavity.
3. According to the technical scheme, the epoxy resin composition is modified by the isocyanate-terminated polyurethane prepolymer synthesized by taking toluene-2, 4-diisocyanate and glycols as raw materials, has a structure containing a flexible C-C chain and a C-O-C chain, has active amide groups, has good compatibility with other epoxy resin components, can provide good weather resistance and bonding force for the prepared epoxy resin composition by matching with polybutadiene rubber modified epoxy resin, and has good stability.
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 resins provided in preparation examples 1 to 5 had the component ratios shown in Table 1, and the specific preparation methods were as follows: sequentially feeding polybutadiene rubber and epoxy resin into a reaction kettle, continuously stirring and heating to 120 ℃, slowly dripping a catalyst, finishing dripping within 30min, heating to 150 ℃, preserving heat for reaction for 2h, then cooling to 80 ℃, and 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 benzyltriethylammonium chloride (TEBA).
Table 1: preparation examples 1 to 5 component proportions (in mass percent)
| Polybutadiene rubber | Epoxy resin | Catalyst and process for preparing same | |
| 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 preparation example is different from the preparation example 3 in that the polybutadiene rubber is a combination of epoxidized hydroxyl-terminated polybutadiene rubber (EHTPB) and hydroxyl-terminated polybutadiene rubber (HTPB), the mass ratio of the two is 1.
Preparation example 7
This preparation example differs from preparation example 3 in that the polybutadiene rubber is epoxidized hydroxyl-terminated polybutadiene rubber (EHTPB); the remainder was the same as in preparation example 3.
Preparation example 8
The difference between the preparation example and the preparation example 7 is that the epoxy resin is liquid bisphenol F epoxy resin, and the epoxy value is 0.54; the remainder was the same as in preparation example 3.
Preparation example of urethane-modified epoxy resin
Preparation examples 9 to 11
The component ratios of the urethane-modified epoxy resins provided in preparation examples 9 to 11 are shown in Table 2, and the specific preparation methods are 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 h, then cooling to 70-80 ℃, and discharging to obtain the polyurethane modified epoxy resin, wherein the catalyst is an organic tin catalyst dibutyltin dilaurate.
Table 1: preparation examples 1 to 3 component proportions (in percentage by mass)
| Isocyanates | Diols | Catalyst and process for preparing same | |
| Preparation example 9 | 15％ | 84％ | 1％ |
| Preparation example 10 | 25％ | 74％ | 1％ |
| Preparation example 11 | 18％ | 80％ | 2％ |
Preparation example 12
This preparation example differs from preparation example 11 in that the isocyanate is diphenylmethane diisocyanate, and the remainder is identical to preparation example 11.
Example 1
The embodiment provides a packaging adhesive for a microelectronic component, which comprises an epoxy resin composition and a curing agent composition in a mass ratio of 100, wherein the epoxy resin composition and the curing agent composition are in a component ratio as shown in table 1, and the preparation method comprises the following steps:
s1, preparing an epoxy resin composition: sequentially feeding the polybutadiene rubber modified epoxy resin prepared in the preparation example 1, the polyurethane modified epoxy resin prepared in the preparation example 9, a diluent, an auxiliary agent and an inorganic filler into a reaction kettle which is simultaneously provided with two high-speed dispersion discs and a frame type stirring paddle or a reaction kettle which is simultaneously provided with two high-speed dispersion discs and a frame type stirring paddle, vacuumizing to set the vacuum degree to be 0.1MPa after feeding is finished, setting the rotating speed of the high-speed dispersion discs to be 1000 r/min and the rotating speed of the frame type stirring paddle to be 120 r/min, and stirring for 60min in vacuum until glue liquid 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 polyoxyethylene and an anti-hydrolysis agent into a reaction kettle with paddle type stirring, stirring at a low speed under the protection of nitrogen gas, setting the rotating speed to be 300 r/min and the temperature to be 25 ℃, and stirring for 90min until glue liquid is uniform and has no floccules and no bubbles, so as to obtain a curing agent composition.
S3, preparing the packaging adhesive for the microelectronic component: 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 component.
In the step S1, the diluent is ethylene glycol diglycidyl ether; the inorganic filler is alpha alumina with the grain diameter of 40-60 mu m and surface modified by epoxy silane coupling agent; the auxiliary agent comprises an anti-settling agent, a defoaming agent, a dispersing agent, a coupling agent and an antioxidant; based on the total weight of the auxiliary agent, 80% of anti-settling agent, 5% of defoaming agent, 5% of dispersing agent, 5% of coupling agent and 5% of antioxidant; the anti-settling agent is fumed silica, the defoaming agent is an oily system non-silicon defoaming agent HT833, the coupling agent is an epoxy silane coupling agent KH-560, and the antioxidant is a phenol antioxidant 1076.
In the step S2, the polyether amine is polyether amine D230; alicyclic amine Menthane Diamine (MDA); the alkylphenol polyoxyethylene ether is nonylphenol polyoxyethylene ether; the hydrolysis resisting agent is a mixture of dissolved polycarbodiimide and diisopropyl naphthalene, and is prepared by melting polycarbodiimide in diisopropyl naphthalene at 80 ℃, wherein the mixing ratio of polycarbodiimide to diisopropyl naphthalene is 1:1.
examples 2 to 8
Examples 2 to 8 differ from example 1 in the source of the polybutadiene rubber-modified epoxy resin and the polyurethane-modified epoxy resin, as shown in Table 2 below, and remain the same as example 1.
Table 2: examples 2 to 8 sources 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 is different from example 1 in that the urethane-modified epoxy resin was not added to the epoxy resin composition, and the rest was 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, and the remainder was identical to example 1.
Comparative example 3
This comparative example differs from example 1 in that the polybutadiene-modified epoxy resin was derived from preparation example 5, and the remainder was identical to example 1.
Performance detection
Heating and curing the packaging adhesive for the microelectronic components prepared in each embodiment and comparative example at 100 ℃ for 2 hours to prepare an adhesive film, and carrying out performance detection, wherein the detection items are as follows:
tensile strength: testing the tensile strength of the adhesive film according to the GB/T1040.1-2018 standard;
bonding strength: testing the adhesive strength of the adhesive film according to the GB/T7124-2008 standard;
heat conductivity: testing the thermal conductivity coefficient of the packaging adhesive according to the ASTM D5470 standard;
boiling test: and (3) curing the microelectronic element by using the packaging adhesive, boiling for 1000h, and observing whether the adhesive layer has cracking and degumming phenomena in a high-temperature and high-humidity environment.
And (3) testing cold and hot impact: curing the microelectronic element by using the packaging adhesive, placing the cured microelectronic element in a liquid constant-temperature water bath, keeping the microelectronic element at the low temperature of 0-5 ℃ and the high temperature of 95-100 ℃ for 2min at each temperature, continuously circulating the microelectronic element at the high temperature and the low temperature for 10000 times, and observing whether the adhesive layer is cracked and degummed.
The results of the performance measurements are shown in Table 3 below.
Table 3: performance test results of examples 1 to 9 and comparative examples 1 to 3
As can be seen from the data in the table 3, the original packaging adhesive for the microelectronic component prepared by the technical scheme of the application is used by matching the polybutadiene rubber modified epoxy resin and the polyurethane modified epoxy resin, the bonding property of the packaging adhesive is further improved, the packaging adhesive still has a good bonding effect after 1000h boiling and 10000 times of limit cold and hot impact tests, shows good aging resistance, and has good heat conductivity and mechanical strength.
The characteristics of the encapsulating paste for microelectronic components are further investigated below.
Example 10
This example is different from example 1 in that the inorganic filler includes 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, and the rest is identical to example 1.
Example 11
This example is different from example 1 in that the particle size of alpha alumina is 10 to 30 μm, and the rest is the same as example 1.
Example 12
This example is different from example 1 in that the particle size of alpha alumina is 80 to 100 μm, and the rest is the same as example 1.
Example 13
The difference between the embodiment and the embodiment 1 is that the defoaming agent is an oily system organic silicon defoaming agent DF-834, and the rest is consistent with the embodiment 1.
Example 14
This example is different from example 1 in that the anti-settling agent comprises fumed silica 10wt%, 8000 mesh precipitated barium sulfate 70wt%, and organobentonite 20wt%, and the rest is the same as example 1.
Example 15
This example differs from example 1 in that the polyetheramine is polyetheramine D400, which otherwise remains the same as example 1.
Example 16
This example differs from example 1 in that the alkylphenol ethoxylate is dodecylphenol ethoxylate, which is otherwise identical to example 1.
Example 17
The difference between this example and example 1 is that in the hydrolysis resistant agent, the mixing ratio of polycarbodiimide to diisopropyl naphthalene is 1:20, the remainder being in accordance with example 1.
Example 18
The difference between the embodiment and the embodiment 1 is that in the hydrolysis-resistant agent, the mixing ratio of the polycarbodiimide to the diisopropyl naphthalene is 5:1, the remainder being in accordance with example 1.
The performance of the packaging adhesive for microelectronic devices in examples 10 to 18 was tested, and the test results are shown in table 4 below.
Table 4: results of testing the Performance of examples 10 to 18
The preferred technical solutions in the present application are further verified in embodiments 10 to 18, and it can be seen from the test data that the preferred technical solutions can all obtain better effects, and the performance of the packaging adhesive is further improved.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: equivalent changes in structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. The epoxy resin composition is characterized by comprising the following raw materials in percentage by weight:
polybutadiene rubber-modified epoxy resin: 25 to 35 percent;
polyurethane modified epoxy resin: 5 to 10 percent;
diluent agent: 5 to 15 percent;
inorganic filler: 45 to 55 percent; and
auxiliary agent: 0.5 to 2 percent;
the sum of the above components is 100%.
2. The epoxy resin composition according to claim 1, wherein the urethane-modified epoxy resin is a modified epoxy resin modified with isocyanate-terminated urethane.
3. The epoxy resin composition as claimed in claim 2, wherein the isocyanate-terminated polyurethane is a polyurethane synthesized from toluene-2, 4-diisocyanate and a diol.
4. The epoxy resin composition as claimed in claim 1, wherein the polybutadiene rubber-modified epoxy resin is prepared from raw materials comprising, by weight: 10-30% of polybutadiene rubber, 68-88% of epoxy resin and 0.2-2% of catalyst, wherein the sum of the components is 100%.
5. The epoxy resin composition of claim 4, wherein the polybutadiene rubber is one or more 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.
6. The epoxy resin composition as claimed in claim 1, wherein the inorganic filler has a particle size distribution of 40 to 60 μm:65 to 85wt%,10 to 30 μm:15 to 35wt percent.
7. The method for preparing an epoxy resin composition according to any one of claims 1 to 6, 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 dispersing and mixing the mixture at a high speed for 60 to 120min to obtain the epoxy resin composition.
8. An encapsulation adhesive for a microelectronic component, which is characterized by comprising the epoxy resin composition and the curing agent composition according to any one of claims 1 to 6, wherein the mass ratio of the epoxy resin composition to the curing agent composition is 100: (18 to 25).
9. The packaging adhesive for microelectronic components according to claim 8, wherein the curing agent composition comprises the following raw materials by weight percent:
80-90% of polyether amine;
alicyclic amine: 5 to 10 percent;
alkylphenol ethoxylates: 1 to 5 percent; and
hydrolysis resistance agent: 1 to 5 percent.
10. The packaging adhesive for microelectronic components according to claim 9, wherein the curing agent composition is prepared by the following method: sequentially adding polyether amine, alicyclic amine, alkylphenol polyoxyethylene and an anti-hydrolysis agent into a reaction kettle, controlling the temperature to be 25-60 ℃, and stirring at low speed of 30-90rpm for 30-90min under the protection of nitrogen until the glue solution is uniform and has no floccules and no air bubbles, thereby obtaining the curing agent composition.
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| CN115521746B (en) | 2023-08-29 |
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