CN116970260A - Epoxy plastic package material and preparation method and application thereof - Google Patents

Epoxy plastic package material and preparation method and application thereof Download PDF

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Publication number
CN116970260A
CN116970260A CN202311229835.XA CN202311229835A CN116970260A CN 116970260 A CN116970260 A CN 116970260A CN 202311229835 A CN202311229835 A CN 202311229835A CN 116970260 A CN116970260 A CN 116970260A
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epoxy
resin
epoxy resin
molding compound
parts
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CN116970260B (en
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付可欣
朱朋莉
宁一
毛竹
刘明强
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Shenzhen Institute of Advanced Electronic Materials
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses an epoxy plastic package material, which comprises the following components: an epoxy resin (A), an epoxy compound (B), a phenolic resin (C), an inorganic filler (D), a curing accelerator (E) and a silane coupling agent (F); wherein the epoxy compound (B) is an epoxy compound having a dicyclopentadiene alicyclic structure, a triazine ring structure or a sulfone group. The invention introduces the epoxy compound containing dicyclopentadiene alicyclic structure, triazine ring structure and/or sulfonyl structure into the epoxy molding compound to improveT g Simultaneously reducing dielectric constant and dielectric loss. In addition, the epoxy plastic packaging material provided by the invention also has good continuous formability and mechanical properties, and meets the use requirements.

Description

Epoxy plastic package material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electronic packaging materials, in particular to an epoxy plastic packaging material and a preparation method and application thereof.
Background
SiC, gaN elements are characterized by high pressure resistance and high operating temperature compared to conventional Si elements, and thus the encapsulation material is also required to have a high glass transition temperature (T g ) In addition, from the aspect of dielectric performance, most of epoxy plastic packaging materials currently have high dielectric constants, so that leakage current of the whole component is increased and a capacitance effect is generated. The performance of the existing epoxy plastic packaging material can not meet the high-speed development of the packaging technology. Therefore, there is an urgent need to develop a high T-value g And the epoxy plastic package material has low dielectric property, good reliability and continuous formability, so as to meet application requirements.
Disclosure of Invention
The present invention provides a glass transition temperature (T) g ) Epoxy plastic package material with low dielectric constant, and preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides an epoxy molding compound, comprising: an epoxy resin (A), an epoxy compound (B), a phenolic resin (C), an inorganic filler (D), a curing accelerator (E) and a silane coupling agent (F);
wherein the epoxy compound (B) is an epoxy compound having a dicyclopentadiene alicyclic structure, a triazine ring structure or a sulfone group.
As a preferred embodiment, the epoxy compound (B) is selected from at least one of compounds having a structure represented by formula (1) to formula (3):
（1）
（2）
（3）。
as a preferred embodiment, the epoxy resin (a) is selected from at least one of phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, alkyl substituted or unsubstituted diglycidyl ether type epoxy resin, 1, 2-stilbene type epoxy resin, sulfone group-containing epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, epoxy resin obtained by co-condensing dicyclopentadiene with phenols and/or naphthols, naphthalene ring-containing epoxy resin, trimethylolpropane type epoxy resin, alicyclic epoxy resin, and phenyl aralkyl type epoxy resin;
and/or the phenolic resin (C) is selected from at least one of phenol novolac resin, biphenyl aralkyl novolac resin, cresol novolac epoxy resin, biphenyl novolac resin, triphenylmethane novolac resin, naphthol novolac resin and aralkyl novolac resin;
and/or the inorganic filler (D) is selected from at least one of silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and barium titanate; preferably, the average particle diameter of the inorganic filler is 0.1-45 μm;
and/or the curing accelerator (E) is selected from at least one of 1, 8-diaza-bicyclo [5.4.0] undecene-7, 1, 5-diaza-bicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo [5.4.0] undecene-7, 2-methylimidazoline, 2-phenylimidazoline, 2-phenyl-4-methylimidazoline, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine;
and/or the silane coupling agent (F) is selected from at least one of silane coupling agents shown as a formula (4):
（4）；
in the formula (4), b is an integer between 1 and 3; a is an integer of 0 to 3;
R 5 selected from the group consisting of、/>、H 2 N-、/>、/>、HS-and->Any one of them; (X) j Any one selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms;
R 6 and R is 7 Each independently selected from methyl or ethyl.
In some specific embodiments, the silane coupling agent represented by formula (4) may be exemplified by gamma- (2, 3-glycidoxypropoxy) propyltrimethoxysilane, trimethyloxyphenyl silane, 3-aminopropyltriethoxy silane, 3- (methacryloyloxy) propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl) triethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyl trimethoxysilane, gamma-anilinopropyl triethoxysilane, gamma-anilinopropyl methyldimethoxysilane, gamma-anilinopropyl methyldiethoxysilane, gamma-anilinopropyl ethyldiethoxysilane, gamma-anilinopropyl ethyldimethoxysilane, gamma-anilinomethyl trimethoxysilane, gamma-anilinomethyl triethoxysilane, gamma-anilinomethyl dimethoxysilane, gamma-anilinomethyl diethoxysilane, gamma-anilinomethyl dimethoxysilane, and the like, and any of these coupling agents may be used alone or in combination.
As a preferred embodiment, the silane coupling agent (F) is selected from at least one of amino organosilane coupling agents represented by formula (5):
（5）；
in the formula (5), b is an integer between 1 and 3; a is an integer of 0 to 3; (X) j Any one selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms; r is R 6 、R 7 Each independently selected from methyl or ethyl.
As a preferred embodiment, further comprising an additive; the additive comprises any one or more of a release agent (G) and a colorant (H).
As a preferred embodiment, the epoxy molding compound comprises the following components in parts by weight: 0.5 to 25 parts of epoxy resin (A), 1 to 20 parts of epoxy compound (B), 3 to 15 parts of phenolic resin (C), 60 to 92 parts of inorganic filler (D), 0.05 to 2 parts of curing accelerator (E), 0.05 to 5 parts of silane coupling agent (F), 0.005 to 2 parts of release agent (G) and 0.1 to 0.6 part of colorant (H).
In a preferred embodiment, the mass of the epoxy compound (B) is 30% to 91%, preferably 60% to 80%, of the total mass of the epoxy resin (a) and the epoxy compound (B).
In yet another aspect, the invention further provides a preparation method of the epoxy molding compound, which comprises the following steps:
and mixing the components in proportion, and kneading and mixing to obtain the epoxy plastic packaging material.
As a preferred embodiment, the preparation method comprises the steps of:
and mixing the components in proportion, and kneading and mixing at the extrusion temperature of 100-180 ℃ to obtain the epoxy molding compound.
In still another aspect, the invention provides application of the epoxy molding compound in semiconductor packaging.
The technical scheme has the following advantages or beneficial effects:
according to the epoxy plastic packaging material, the polyfunctional epoxy compound containing dicyclopentadiene alicyclic structure, triazine ring structure and/or sulfonyl is added into the epoxy plastic packaging material, so that the glass transition temperature of the epoxy plastic packaging material is improved, and meanwhile, the dielectric constant and dielectric loss are reduced. In addition, the invention also obtains good continuous formability by adjusting the components and the content of the epoxy plastic package material, thereby realizing the high T of the epoxy plastic package material g Low dielectric property, good mechanical property, reliability and continuous forming property.
Detailed Description
The following examples are only some, but not all, of the examples of the invention. Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
In the present invention, all the equipment, raw materials and the like are commercially available or commonly used in the industry unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
The invention provides an epoxy plastic packaging material, which comprises the following raw materials: an epoxy resin (A), an epoxy compound (B), a phenolic resin (C), an inorganic filler (D), a curing accelerator (E) and a silane coupling agent (F).
In some embodiments, the epoxy resin (a) is an encapsulating epoxy resin, and is not particularly limited, and specific examples thereof include: (1) Phenol resins obtained by condensing or co-condensing phenols such as phenol novolac epoxy resins, phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, and/or naphthols such as α -naphthol, β -naphthol, and dihydroxynaphthalene with aldehyde-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde in the presence of an acidic catalyst; (2) Alkyl substituted or unsubstituted diglycidyl ether type epoxy resin; (3) 1, 2-stilbene type epoxy resin; (4) an epoxy resin containing sulfur atoms; (5) hydroquinone type epoxy resin; (6) Glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; (7) Glycidylamine type epoxy resin obtained by reacting polyamine such as diaminodiphenylmethane and isocyanic acid with epichlorohydrin; (8) Epoxide of dicyclopentadiene and phenol and/or naphthol co-condensation resin; (9) naphthalene ring-containing epoxy resin; (10) trimethylolpropane type epoxy resin; (11) an ester-ring-type epoxy resin, etc.; (12) An epoxide of an aralkyl type phenol resin such as a phenol aralkyl resin, a naphthol aralkyl resin, etc.; the epoxy resins listed above may be used alone or in any combination.
In some embodiments, the epoxy compound (B) is an epoxy compound containing a dicyclopentadiene alicyclic structure, a triazine ring structure, or a sulfone group, and preferably is at least one of compounds of the structures represented by the formulas (1) to (3):
（1）
（2）
（3）。
in some embodiments, the phenolic resin (C) is selected from at least one of phenol novolac resins, biphenyl aralkyl novolac resins, cresol novolac epoxy resins, biphenyl novolac resins, triphenylmethane novolac resins, naphthol novolac resins, and aralkyl novolac resins, preferably low hygroscopicity phenolic resins, such as biphenyl aralkyl novolac resins and phenol novolac resins. The phenolic resins listed above may be used alone or in any combination.
In some embodiments, the equivalent ratio of the epoxy resin (a) to the epoxy compound (B), the phenolic resin (C), i.e., the ratio of the sum of the moles of epoxy groups in the epoxy resin (a) and the epoxy compound (B) to the moles of hydroxyl groups in the phenolic resin (C), is not particularly limited. The ratio is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3, for limiting the respective unreacted amounts. In order to obtain an encapsulating epoxy molding compound excellent in moldability and reflow resistance, the ratio is preferably set in the range of 0.8 to 1.0.
In some embodiments, the inorganic filler (D) is an inorganic filler conventionally used in the art, and specifically, silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, barium titanate, and the like; wherein the silicon dioxide is crystalline silicon dioxide, fused silicon dioxide and synthetic silicon dioxide; the above-listed inorganic fillers may be used alone or in any combination. The average particle diameter of the inorganic filler is 0.1 to 45. Mu.m, preferably 0.1 to 10. Mu.m, in view of fluidity.
In some embodiments, the present invention further adds a curing accelerator (E) in view of the hardenability of the epoxy molding compound. The curing accelerator used in the invention is a curing accelerator commonly used in epoxy molding compounds, and is not particularly limited; specifically, examples of the organic phosphine include cyclic amidine compounds such as 1, 8-diaza-bicyclo [5.4.0] undecene-7, 1, 5-diaza-bicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo [5.4.0] undecene-7, and the like, and compounds having polar bonds such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, and the like, imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-phenyl-4-methylimidazoline, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and the like, and compounds having polar bonds such as maleic anhydride, the above quinone compounds, phenylazomethane, phenol, and the like are added to these organic phosphine compounds. The above-listed curing accelerators may be used alone or in any combination.
In some embodiments, the silane coupling agent (F) is selected from at least one of silane coupling agents represented by formula (4):
（4）；
in the formula (4), b is an integer between 1 and 3; a is an integer of 0 to 3;
R 5 selected from the group consisting of、/>、H 2 N-、/>、/>、、HS-、/>One of the following; wherein, (X) j One selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms;
R 6 and R is 7 Independently selected from methyl or ethyl, and at R 6 OR 7 In the case where a plurality of the above-mentioned materials are present, they may be the same or different from each other.
Specifically, the silane coupling agent represented by the formula (4) may be exemplified by gamma- (2, 3-glycidoxypropoxy) propyltrimethoxysilane, trimethyloxyphenyl silane, 3-aminopropyltriethoxysilane, 3- (isobutenyloxy) propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl) triethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, gamma-anilinopropyltrimethoxysilane, gamma-anilinopropylmethyldimethoxysilane, gamma-anilinopropylmethyldiethoxysilane, gamma-anilinopropylethyl diethoxysilane, gamma-anilinopropylethyl dimethoxysilane, gamma-anilinomethyl trimethoxysilane, gamma-anilinomethyl triethoxysilane, gamma-anilinomethyl dimethoxysilane, gamma-anilinomethyl diethoxysilane, gamma-anilinomethyl dimethoxysilane, etc. The silane coupling agents listed above may be used alone or in any combination.
From the aspect of fluidity, the silane coupling agent is selected from one or more of amino organosilane coupling agents represented by formula (5):
（5）；
in the formula (5), b is an integer between 1 and 3; a is an integer of 0 to 3; (X) j Any one selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms; r is R 6 、R 7 Each independently selected from methyl or ethyl, and at R 6 、OR 7 In the case where a plurality of the above-mentioned materials are present, they may be the same or different from each other.
Specifically, as the amino organosilane coupling agent represented by the formula (5), there can be mentioned: gamma-anilinopropyl trimethoxysilane, gamma-anilinopropyl triethoxysilane, gamma-anilinopropyl methyl dimethoxysilane, gamma-anilinopropyl methyl diethoxysilane, gamma-anilinopropyl ethyl dimethoxysilane, etc., preferably gamma-anilinopropyl trimethoxysilane.
The amino organosilane coupling agent is mixed into the epoxy resin composition, so that the cohesiveness of the filler and the resin can be improved, and the bulk performance of the filler can be better exerted.
In some embodiments, additives are also included.
In some embodiments, the additive comprises a mold release agent (G). In the technical scheme of the invention, the release agent is at least one selected from linear saturated carboxylic acid and oxidized polyethylene wax; wherein the oxidized polyethylene wax has a number average molecular weight of 550 to 1200, preferably 800 to 1000.
In some embodiments, the additive comprises colorant (H). In the present embodiment, the colorant is a conventional colorant, such as a carbon black colorant.
In some embodiments, the epoxy molding compound comprises, in parts by weight: 0.5 to 25 parts of epoxy resin (A), 1 to 20 parts of epoxy compound (B), 3 to 15 parts of phenolic resin (C), 60 to 92 parts of inorganic filler (D), 0.05 to 2 parts of curing accelerator (E), 0.05 to 5 parts of silane coupling agent (F), 0.005 to 2 parts of release agent (G) and 0.1 to 0.6 part of colorant (H).
In some embodiments, the ratio of the epoxy compound (B) in the total mass of the epoxy resin (a) and the epoxy compound (B) is not particularly limited, and is preferably 30% to 91%, more preferably 60% to 80%.
In some embodiments, too low a content of the inorganic filler (D) may result in too low a viscosity of the epoxy molding compound, voids are easily generated during molding, and the improvement of dielectric constant and thermal expansion coefficient is small; on the contrary, the inorganic filler content is too large, so that the fluidity of the epoxy plastic packaging material is poor, and the defects of incomplete filling and the like are caused.
In some embodiments, the content of the curing accelerator (E) is too low, and the hardenability of the epoxy molding compound tends to be poor in a short time; on the contrary, the hardening speed of the epoxy molding compound is too high, and molding products with good shapes are difficult to obtain.
In some embodiments, the additive further comprises any one or more of a stress relief agent, a flame retardant, an ion scavenger, and gas phase silicon.
The epoxy resins (a) used in the following examples and comparative examples are listed below:
epoxy resin A1 of the formula
，
It represents a phenylarylalkyl epoxy resin having an epoxy equivalent of 285 and a softening point of 63 ℃.
The epoxy compounds (B) used in the following examples and comparative examples are listed below:
the epoxy compound B1 has the following molecular formula:
the synthesis process is as follows:
218 g of 2, 6-dimethylphenol and 5 g anhydrous AlCl 3 Added to a four-necked round bottom flask; heating the mixture to 120 ℃ under nitrogen protection; with vigorous stirring, 33 g dicyclopentadiene (DCPD) was gradually added over 1 h, and the mixture was stirred at 120℃for 4 h; after the completion of the reaction, 5.5 g of 5 wt% aqueous solution containing NaOH was added to the mixture, and stirred for 1 h; the reaction solution was filtered, and the filtrate was washed with water 3 times; the organic phase is separated and distilled in a rotary evaporator to remove excess 2, 6-dimethylphenol; the crude product was dissolved in toluene and extracted several times with water; distilling the organic phase to remove toluene and water to obtain an intermediate 2, 6-dimethylphenol-DCPD novolac;
39 g of 2, 6-dimethylphenol-DCPD novolak, 160 mL epichlorohydrin were added to a four-necked round bottom flask; the mixture was heated to 100 ℃ under nitrogen, then 20 wt% aqueous solution containing 9 g NaOH was added to 1 h and the mixture was reacted at 100 ℃ for 2 hours; the reaction solution was filtered, and the organic phase was washed 3 times with water; the organic phase is separated and excess epichlorohydrin and water are removed in a rotary evaporator; the crude product was dissolved in ethyl acetate and washed 3 times with water; the organic phase was separated and the solvent was removed by rotary evaporation to give the target epoxy compound B1 (epoxy equivalent 259.12).
The epoxy compound B2 has the following formula:
the synthesis process is as follows:
98.0 g of 2-allylphenol was dissolved in a 10 wt% aqueous solution containing 29.2 g of NaOH to obtain an aqueous sodium phenolate solution; this aqueous solution was added at room temperature under nitrogen to a four-necked round bottom flask containing 40.0 g cyanuric chloride, 1.0 g benzyl triethylammonium chloride and 800 mL chloroform, at 1 h; the mixture was vigorously stirred at room temperature 5 h; subsequently, 10 wt% aqueous solution containing 10 g of NaOH was added to the reaction solution in 0.5. 0.5 h, and 0.5. 0.5 h was vigorously stirred; the organic phase was separated and washed several times with water, followed by rotary evaporation to remove the solvent to give the intermediate;
12.6 g of the above synthesized intermediate and 160 mL of dichloromethane were added to a four-necked round bottom flask, 20 g of m-chloroperoxybenzoic acid was added in portions under nitrogen protection, and the mixture was stirred at room temperature for 5 days; the precipitate was removed by filtration and the organic phase was washed several times with 10 wt% strength aqueous sodium sulfite, 10 wt% strength aqueous sodium carbonate and deionized water, respectively; the organic phase was separated and the solvent was removed by rotary evaporation to give the target epoxy compound B2 (epoxy equivalent 198.32).
The epoxy compound B3 has the following formula:
the synthesis process is as follows:
26.43 g of 4,4' -sulfonylbis [2- (2-propenyl) ] phenol, 7.1 g sodium hydroxide and 200 mL Ding Tongtian were added to a four-necked round bottom flask and the mixture was heated to 60 ℃ under nitrogen; 21.3 g allyl bromide was gradually added over 1 h with vigorous stirring and the mixture was allowed to react at 60 ℃ for 6 h; the precipitate was removed by filtration and the organic phase was washed several times with water; separating the organic phase and removing the solvent and the excessive allyl bromide by rotary evaporation to obtain an intermediate product;
20.5 g of the above synthesized intermediate and 300 mL of dichloromethane were added to a four-necked round bottom flask, followed by addition of 48 g m-chloroperoxybenzoic acid in portions under nitrogen and stirring of the mixture at room temperature for 5 days; the precipitate was removed by filtration and the organic phase was washed several times with 10 wt% strength aqueous sodium sulfite, 10 wt% strength aqueous sodium carbonate and deionized water, respectively; the organic phase was separated and the solvent was removed by rotary evaporation to give the target epoxy compound B3 (epoxy equivalent 160).
The phenolic resins (C) used in the following examples and comparative examples are listed below:
phenolic resin C1: the biphenyl aralkyl type phenolic resin has hydroxyl equivalent of 203 and softening point of 65 ℃;
phenolic resin C2: a phenol novolac resin having a hydroxyl equivalent weight of 104 and a softening point of 60 ℃; the method comprises the steps of carrying out a first treatment on the surface of the
The inorganic filler (D) used in the following examples and comparative examples is exemplified as follows:
SiO 2 the powder is a fused spherical silica D having an average particle diameter of 5 to 8 μm and a cut point particle diameter of 45 μm.
The curing accelerator (E) used in the following examples and comparative examples was triphenylphosphine.
The silane coupling agent (F) used in the following examples and comparative examples was gamma-anilinopropyl trimethoxysilane.
The mold release agent (G) used in the following examples and comparative examples was oxidized polyethylene wax having a number average molecular weight of 1000.
The colorant (H) used in the following examples and comparative examples was a carbon black colorant.
Examples 1 to 8, comparative examples 1 to 4
The components and parts by weight of the epoxy molding compound described in tables 1,2 and 3 were mixed, kneaded and kneaded at an extrusion temperature of 150 ℃, cooled and pulverized to obtain an epoxy molding compound.
Performance testing
The epoxy molding compounds prepared in examples 1 to 8 and comparative examples 1 to 4 were tested for glass transition temperature, flexural strength, modulus, and dielectric characteristics, and the results are shown in tables 1 to 3. Specific test methods for glass transition temperature, flexural strength, modulus and dielectric properties are described in GB/T40564-2021.
TABLE 1
As can be seen from comparative examples 1 to 4, the epoxy resin A is replaced by epoxy compounds B1 to B3, respectively, and the glass transition temperature, the bending strength, the dielectric constant and the dielectric loss of the epoxy molding compound are all obviously changed; when the epoxy compound B1 containing dicyclopentadiene structure is introduced, the dielectric constant of the epoxy molding compound is reduced, and the glass transition temperature is not sacrificed; when the epoxy compound B2 is introduced, dielectric loss can be effectively reduced and the glass transition temperature can be improved; when the epoxy compound B3 containing a sulfone group and a tetracyclic energy is introduced, the glass transition temperature thereof is remarkably increased although there is no remarkable improvement in dielectric characteristics.
TABLE 2
As can be seen from examples 1 to 3, the epoxy compound B and the epoxy resin a were used in a blending manner, so that the dielectric constant and dielectric loss were reduced to some extent while the glass transition temperature was increased; further comparing examples 1-3 and 4-8; the epoxy compound B and the epoxy resin A are reasonably compounded, so that the glass transition temperature can be further improved, and the dielectric constant and dielectric loss can be effectively reduced.
In conclusion, the epoxy plastic packaging material provided by the invention can realize high T g Low dielectric and good mechanical properties.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
TABLE 3 Table 3
/>

Claims (10)

1. An epoxy molding compound, comprising: an epoxy resin (A), an epoxy compound (B), a phenolic resin (C), an inorganic filler (D), a curing accelerator (E) and a silane coupling agent (F);
wherein the epoxy compound (B) is an epoxy compound having a dicyclopentadiene alicyclic structure, a triazine ring structure or a sulfone group.
2. The epoxy molding compound according to claim 1, wherein the epoxy compound (B) is at least one selected from compounds having a structure represented by the formula (1) to formula (3):
（1）
（2）
（3）。
3. the epoxy molding compound according to claim 1, wherein the epoxy resin (a) is at least one selected from the group consisting of phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, alkyl substituted or unsubstituted diglycidyl ether type epoxy resin, 1, 2-stilbene type epoxy resin, sulfone group-containing epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, epoxy resin obtained by co-condensation of dicyclopentadiene with phenols and/or naphthols, naphthalene ring-containing epoxy resin, trimethylolpropane type epoxy resin, alicyclic epoxy resin and phenyl aralkyl type epoxy resin;
and/or the phenolic resin (C) is selected from at least one of phenol novolac resin, biphenyl aralkyl novolac resin, cresol novolac epoxy resin, biphenyl novolac resin, triphenylmethane novolac resin, naphthol novolac resin and aralkyl novolac resin;
and/or the inorganic filler (D) is selected from at least one of silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and barium titanate; the average particle size of the inorganic filler is 0.1-45 mu m;
and/or the curing accelerator (E) is selected from at least one of 1, 8-diaza-bicyclo [5.4.0] undecene-7, 1, 5-diaza-bicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo [5.4.0] undecene-7, 2-methylimidazoline, 2-phenylimidazoline, 2-phenyl-4-methylimidazoline, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine;
and/or the silane coupling agent (F) is selected from at least one of silane coupling agents shown as a formula (4):
（4）；
in the formula (4), b is an integer between 1 and 3; a is an integer of 0 to 3;
R 5 selected from the group consisting of、/>、H 2 N-、/>、/>、HS-and->Any one of them; (X) j Any one selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms;
R 6 and R is 7 Each independently selected from methyl or ethyl.
4. The epoxy molding compound according to claim 3, wherein the silane coupling agent (F) is at least one selected from the group consisting of amino organosilane coupling agents represented by formula (5):
（5）；
in the formula (5), b is an integer between 1 and 3; a is an integer of 0 to 3; (X) j Any one selected from hydrogen atoms and alkyl groups with 1-6 carbon atoms; r is R 6 、R 7 Each independently selected from methyl or ethyl.
5. The epoxy molding compound of claim 1, further comprising an additive; the additive comprises any one or more of a release agent (G) and a colorant (H).
6. The epoxy molding compound according to claim 1, wherein the epoxy molding compound comprises the following components in parts by mass: 0.5 to 25 parts of epoxy resin (A), 1 to 20 parts of epoxy compound (B), 3 to 15 parts of phenolic resin (C), 60 to 92 parts of inorganic filler (D), 0.05 to 2 parts of curing accelerator (E), 0.05 to 5 parts of silane coupling agent (F), 0.005 to 2 parts of release agent (G) and 0.1 to 0.6 part of colorant (H).
7. The epoxy molding compound according to claim 1, wherein the mass of the epoxy compound (B) is 30% -91% of the total mass of the epoxy resin (a) and the epoxy compound (B).
8. A method for preparing the epoxy molding compound according to any one of claims 1 to 7, comprising the steps of:
and mixing the components in proportion, and kneading and mixing to obtain the epoxy plastic packaging material.
9. The method according to claim 8, characterized in that it comprises the steps of:
and mixing the components in proportion, and kneading and mixing at the extrusion temperature of 100-180 ℃ to obtain the epoxy molding compound.
10. Use of the epoxy molding compound according to any one of claims 1-7 in semiconductor packaging.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053799A (en) * 1959-04-22 1962-09-11 Dal Mon Research Co Polymerizable triazines and polymers thereof
US4789711A (en) * 1986-12-02 1988-12-06 Ciba-Geigy Corporation Multifunctional epoxide resins
JPH10287793A (en) * 1997-04-16 1998-10-27 Hitachi Chem Co Ltd Epoxy resin composition for semiconductor sealing and semiconductor device sealed therewith
JP2014088509A (en) * 2012-10-30 2014-05-15 Panasonic Corp Epoxy resin composition, prepreg, metal-clad laminate and printed wiring board
CN111205595A (en) * 2020-02-18 2020-05-29 联茂(无锡)电子科技有限公司 Halogen-free low dielectric composition, laminate and printed wiring board

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053799A (en) * 1959-04-22 1962-09-11 Dal Mon Research Co Polymerizable triazines and polymers thereof
US4789711A (en) * 1986-12-02 1988-12-06 Ciba-Geigy Corporation Multifunctional epoxide resins
JPH10287793A (en) * 1997-04-16 1998-10-27 Hitachi Chem Co Ltd Epoxy resin composition for semiconductor sealing and semiconductor device sealed therewith
JP2014088509A (en) * 2012-10-30 2014-05-15 Panasonic Corp Epoxy resin composition, prepreg, metal-clad laminate and printed wiring board
CN111205595A (en) * 2020-02-18 2020-05-29 联茂(无锡)电子科技有限公司 Halogen-free low dielectric composition, laminate and printed wiring board

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