Classifications

• • 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
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/226—Mixtures of di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/14—Macromolecular materials
• • 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
  • C08G59/20—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 epoxy compounds used
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
  • C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
• • 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
• • 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
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins

Definitions

• the present invention relates to an epoxy resin composition. Background technique
• UL-94V-0 grade flame retardant quality standard In the prior art, the main method to achieve this quality standard is to add a certain amount of flame retardant. At present, there are many kinds of flame retardants used, and the traditional (non-environmental) mainly uses bromine-based flame retardants and antimony-like resistors. Burning agent. However, as global environmental awareness has increased, countries have drawn up environmental protection laws to limit the use of bromide-containing flame retardants and hazardous substances such as lead in electronic products. As early as the early 1990s, countries such as the United States, Europe, and Japan realized the rapid development of the electronics industry, and the waste of industrial products, especially the lead in the large amount of lead-tin materials used every year, must be taken seriously.
• the traditional bromine-based flame retardants and antimony-based flame retardants will be replaced by environmentally-friendly flame retardants, but the flame retardant effect of the environmentally friendly flame retardants currently used is far less than that of Br/Sb flame retardants. It needs to be added in larger amounts to meet the flame retardant requirements. However, the use of a large amount of flame retardant will seriously affect the flow properties, moldability and reliability of the epoxy resin composition.
• the epoxy molding compound must also have a low coefficient of thermal expansion to match the thermal expansion coefficient of the semiconductor package material such as the chip/base island/frame, thereby reducing the package warpage caused by the thermal expansion coefficient mismatch. . Therefore, in the QFN package, the epoxy molding compound must have high reliability and low warpage, thereby reducing or avoiding undesirable phenomena such as delamination and external warpage of the semiconductor package. Summary of the invention
• the technical problem to be solved by the present invention is to overcome the addition of a bromine-based flame retardant or an antimony-based flame retardant to a conventional epoxy resin composition, and the existing epoxy resin composition is added with a large amount of environmentally-friendly flame retardant. It is difficult to meet the defects of lead-free reflow conditions, thereby providing a green epoxy resin composition with high reliability and low warpage performance that can satisfy the lead-free high-temperature reflow process.
• the epoxy resin composition of the present invention comprises an epoxy resin, a phenol resin, a curing accelerator and an inorganic filler; and the epoxy resin comprises: (1) an epoxy resin represented by Formula I; (2) Formula II An epoxy resin as shown; and (3) an epoxy resin of the formula III and/or formula IV;
• n in the formula I is an integer of 0-50.
• the content of the epoxy resin of the formula I is 20-50%, Preferably, the content of the epoxy resin of the formula II is 10-40%, preferably 15-25%; and the content of the epoxy resin of the formula III is 0-30%, preferably 15-25%; the content of the epoxy resin of the formula IV is 0-40%, preferably 20-30%; the formula III and the formula IV cannot simultaneously be 0%; the percentage of the content is relative to the ring The percentage of the total mass of the oxy-resin mixture.
• the epoxy resin mixture is preferably present in an amount of from 3 to 8% by mass of the epoxy resin composition.
• the epoxy resin of the invention reacts with the phenolic resin to form a self-extinguishing network structure of the epoxy resin composition, that is, when the epoxy resin composition is burned, a foam layer (flame retardant barrier) is formed, and oxygen is blocked, The heat transfer is blocked to achieve the self-extinguishing effect, and the network containing the polyaromatic group formed by the resin compound in the main chain and having thermal decomposition resistance plays a very important role in the stability of the foam layer.
• This composition has excellent heat resistance and reliability, low water absorption and low stress, and can meet the high temperature reliability requirements of the lead-free tantalum process, while having low warpage properties.
• the phenol resin of the present invention is mainly used as a curing agent, and a phenol resin conventionally used in the art can be used, preferably a low water absorbing phenol resin and a biphenyl phenol resin.
• the ratio of the number of phenolic hydroxyl groups in the phenolic resin to the number of epoxy groups in the epoxy resin mixture is from 0.8 to 1.3, preferably from 0.9 to 1.1.
• the curing accelerator according to the present invention is an imidazole compound.
• the imidazole compound means imidazole or a compound containing an imidazole group, preferably dimethylimidazole; and the curing accelerator is preferably contained in an amount of less than or equal to 1% by mass based on the mass of the epoxy resin composition.
• the inorganic filler of the present invention can further reduce the water absorption of the epoxy resin composition, thereby improving reliability.
• the inorganic filler is preferably a composite inorganic filler.
• the composite inorganic filler is preferably silica; the particle size distribution of the composite inorganic filler is preferably: 18-24% less than 3 ⁇ , 20-30% greater than or equal to 3 ⁇ and less than 12 ⁇ , greater than Or equal to 12 and less than 48 ⁇ m, 45-57%, greater than or equal to 48 ⁇ and less than 75 ⁇ , 5-17%; percentage as a percentage of the total mass of the composite inorganic filler.
• the composite inorganic filler preferably has a median diameter d50 of 14-20 ⁇ m, and an average particle diameter of 18-24 ⁇ m ; the composite inorganic filler is contained.
• the amount is preferably 85-89% of the total mass of the epoxy resin composition.
• the above composite inorganic filler is a high filling technique, and the epoxy resin composition of the present invention can still have good fluidity at a filling ratio of 85-89%.
• the epoxy resin composition further contains a flame retardant.
• the flame retardant is an environmentally-friendly flame retardant conventionally used in the art, and is preferably one or more of a nitrogen-containing, boron-containing, and metal hydroxide-based flame retardant.
• the flame retardant content is preferably less than or equal to 5% by mass of the epoxy resin composition.
• the epoxy resin composition of the present invention may further contain other additives such as a mold release agent, a coupling agent, a colorant, a stress absorber, an adhesion promoter, and an ion trapping agent, etc., depending on the needs of practical use. kind or more.
• the epoxy resin of the present invention further contains a release agent, a coupling agent, a colorant, a stress absorber, an adhesion promoter, and an ion scavenger.
• the kind and content of various additional adjuvants can be selected with reference to conventional techniques in the art.
• the coupling agent is used to increase the adhesion of the epoxy resin composition, preventing moisture from penetrating into the chip from the interface of the plastic and the frame; and the ion trapping agent is for reducing the free ion content of the epoxy resin composition.
• the invention also provides a preparation method of the epoxy resin composition: the components of the epoxy resin composition of the invention are extruded and kneaded at 100 ⁇ 110 ° C on a twin-screw extruder, and then cooled and pulverized. .
• composite inorganic is preferred by using a high filling technique
• the filler makes the epoxy resin composition of the invention have good fluidity at a filling rate of 85 to 89%, and also has low water absorption and low stress, and can better meet the high temperature reliability of the lead-free tantalum process. Sexual requirements, while having low warpage performance.
• Figure 1 is a schematic view of a frame for testing adhesion in an effect embodiment. detailed description
• the phenolic resin used in the examples is a biphenyl type phenolic resin, see Formula V, wherein 1 ⁇ is 0-15
• the epoxy resin composition (1000g) is formulated as follows:
• the silica has a median diameter of 20 ⁇ m and an average particle diameter of 24 ⁇ m.
• the epoxy resin composition (1000g) is formulated as follows:
• the epoxy resin composition (1000g) is formulated as follows:
• the epoxy resin composition (1000g) is formulated as follows:
• the silicon has a particle diameter of less than 3 ⁇ m of 18%, greater than or equal to 3 ⁇ m and less than 12 ⁇ m of 20%, greater than or equal to 12 and less than 48 ⁇ m of 57%, and greater than or equal to 48 ⁇ m and less than 75 ⁇ m of 5%.
• the silica had a median diameter of 18 ⁇ m and an average particle diameter of 22 ⁇ m.
• the epoxy resin composition (1000g) is formulated as follows:
• the silica has a median diameter of 16 ⁇ m, an average particle diameter of 20 ⁇ m , a coloring agent: carbon black of 3 g, a release agent: carnauba wax 5 g; a coupling agent: epoxy bismuth 6 g; a flame retardant : Zinc borate l lg.
• the epoxy resin composition (1000g) is formulated as follows:
• the silica has a median diameter of 16 ⁇ m, an average particle diameter of 20 ⁇ m , a coloring agent: carbon black of 3 g, a release agent: carnauba wax 5 g; a coupling agent: epoxy bismuth 6 g; a flame retardant : 50 g of aluminum hydroxide.
• a coloring agent carbon black of 3 g
• a release agent carnauba wax 5 g
• a coupling agent epoxy bismuth 6 g
• a flame retardant 50 g of aluminum hydroxide.
• the silica has a median diameter of 16 ⁇ m, an average particle diameter of 20 ⁇ m , a coloring agent: carbon black of 3 g, a release agent: carnauba wax 5 g; a coupling agent: epoxy bismuth 6 g; a flame retardant : melamine 30g; stress absorber: silicone siloxane oil 2g; adhesion promoter: bismuth silicon germanium 2g; ion trapping agent: 2g.
• the epoxy resin composition (1000g) is formulated as follows:
• Novolac resin 40 g; imidazole curing accelerator (dimethylimidazole): 2 g; composite inorganic filler: 890 g of silica, 22% of particle size distribution less than 3 ⁇ , greater than or equal to 3 ⁇ and less than 12 ⁇ 18%, greater than or equal to 12 and less than 48 ⁇ 48%, greater than or equal to 48 ⁇ and less than 75 ⁇ 12%; silica has a median diameter d50 of 18 ⁇ , average particle size of 22 ⁇ ; colorant: Carbon black 3g; release agent: carnauba wax 5g; coupling agent: epoxy bismuth 6g; flame retardant: melamine 3g; stress absorber: silicone siloxane oil 2g; adhesion promoter: Mercapto silicon
• the epoxy resin composition (1000g) is formulated as follows:
• Novolac resin 40 g; imidazole curing accelerator (dimethylimidazole): 2 g; composite inorganic filler (same as in Example 8): 890 g; coloring agent: carbon black 3 g; release agent: carnauba wax 5 g; coupling agent: epoxy bismuth 6 g; flame retardant: melamine 3 g; stress absorber: polysiloxane siloxane oil 2 g; adhesion promoter: fluorenyl silicon germanium 2 g; ion trapping agent: 2 g.
• the epoxy resin composition in the effect embodiment was obtained according to Examples 8 to 11.
• the epoxy resin composition was encapsulated on a frame as designed in Fig. 1, wherein the contact area of the epoxy resin composition with the frame was 0.784 sq.in. and in an oven at 175 °C. After curing for 6 hours, it was hygroscopically treated by JEDEC MSL3 (30 ° C / 60% / 168 h), then the treated sample was reflowed 3 times at 260 ° C, and finally tested by a tensile tester. The adhesion of the resin composition to the metal frame.
• Hierarchical reliability The samples were packaged on QFN 7x7mm Cu/Ag and Ni/Pa/Au (PPF) frames, and the packaged samples were post-cured at 175 °C for 6 hours to make JEDEC MSL1 (85/ 85/100%) /260 °C 3 times of reflow pretreatment, then through the C-sam scanning internal stratification of the QFN package.
• Example 9 passed the first level assessment on the PPF
• Example 10 passed the first level assessment on the Cu/Ag.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2009
  • 2009-04-01 CN CN200910048710A patent/CN101851386B/zh active Active
• 2010
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