WO2016085115A1 - Phosphonium-based compound, epoxy resin composition containing same, and semiconductor device manufactured using same - Google Patents

Phosphonium-based compound, epoxy resin composition containing same, and semiconductor device manufactured using same Download PDF

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WO2016085115A1
WO2016085115A1 PCT/KR2015/010729 KR2015010729W WO2016085115A1 WO 2016085115 A1 WO2016085115 A1 WO 2016085115A1 KR 2015010729 W KR2015010729 W KR 2015010729W WO 2016085115 A1 WO2016085115 A1 WO 2016085115A1
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epoxy resin
resin composition
formula
phenol
curing
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PCT/KR2015/010729
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French (fr)
Korean (ko)
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천진민
권기혁
김민겸
이동환
정주영
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삼성에스디아이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—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 catalysts used
    • C08G59/688—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 catalysts used containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • 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
    • C08G59/68—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 catalysts 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
    • C08G59/68—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 catalysts used
    • C08G59/70—Chelates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • 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
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    • 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
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/16227—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation the bump connector connecting to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92—Specific sequence of method steps
    • H01L2224/921—Connecting a surface with connectors of different types
    • H01L2224/9212—Sequential connecting processes
    • H01L2224/92122—Sequential connecting processes the first connecting process involving a bump connector
    • H01L2224/92125—Sequential connecting processes the first connecting process involving a bump connector the second connecting process involving a layer connector
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    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L24/80 - H01L24/90
    • H01L24/92—Specific sequence of method steps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a phosphonium compound, an epoxy resin composition comprising the same, and a semiconductor device manufactured using the same.
  • the epoxy resin composition includes an epoxy resin, a curing agent, a curing catalyst, and the like, and as the curing catalyst, an imidazole catalyst, an amine catalyst, and a phosphine catalyst have been generally used.
  • the progress of such a curing reaction may cause an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid.
  • such a change of state does not appear uniformly in an epoxy resin composition. Therefore, when the epoxy resin composition is actually cured at a high temperature, moldability may be decreased due to fluidity decrease, and mechanical, electrical and chemical properties of the product may be reduced after molding.
  • An object of the present invention is to provide a curing catalyst compound that can promote curing of an epoxy resin, has excellent fluidity during molding, exhibits high curing strength, and can be cured in a short curing time.
  • Another object of the present invention is to provide a compound for a curing catalyst that can promote curing of an epoxy resin even at low temperatures.
  • Still another object of the present invention is to provide an epoxy resin composition comprising the compound for the curing catalyst and a semiconductor device manufactured using the same.
  • the present invention provides a phosphonium-based compound represented by the following [Formula 1].
  • R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , Y 1 , Y 2 , Y 3 , and Y 4 are as defined in the following detailed description).
  • the phosphonium-based compound may be one of the compounds represented by the following Chemical Formulas 1a to 1e.
  • the present invention provides an epoxy resin composition
  • an epoxy resin composition comprising an epoxy resin, a curing agent, an inorganic filler and a curing catalyst, wherein the curing catalyst includes the phosphonium-based compound that acts as a curing accelerator.
  • the said epoxy resin is a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a tert- butyl catechol-type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, a cresol novolak-type epoxy Resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, phenol aralkyl type epoxy resin, and halogenated It may include one or more of the epoxy resins.
  • curing agent is a phenol aralkyl type phenol resin, a phenol novolak-type phenol resin, a xylox phenol resin, a cresol novolak-type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, a dicyclopentadiene type phenol Novolak-type phenolic resin synthesized from resin, bisphenol A and resol, polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydride including maleic anhydride and phthalic anhydride, metaphenylenediamine , Diaminodiphenylmethane and diaminodiphenylsulfone.
  • the curing catalyst may be included in 0.01 to 5% by weight of the epoxy resin composition.
  • the phosphonium-based compound may be included in 10 to 100% by weight of the curing catalyst.
  • the epoxy resin composition may include 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, and 0.01 to 5 wt% of the curing catalyst.
  • the epoxy resin composition may have a storage stability of 80% or more after 72 hours.
  • the epoxy resin composition may have a curing shrinkage ratio of less than 0.4% represented by the following [Formula 1]:
  • Cure Shrinkage Rate
  • C is the length of the specimen obtained by the transfer molding press epoxy resin composition at 175, 70kgf / cm 2 , D is obtained after the post-cure (PMC: post molding cure) at 175, and cooled) Length of the specimen).
  • the present invention provides a semiconductor device sealed with the epoxy resin composition.
  • the present invention provides a compound for a curing catalyst that can promote the curing of the epoxy resin, can promote the curing of the epoxy resin even at low temperatures, and in a mixture containing an epoxy resin, a curing agent and the like even in a predetermined range of time and temperature conditions
  • a compound for storage catalyst with high storage stability was provided.
  • FIG. 1 is a cross-sectional view of a semiconductor device in accordance with an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a semiconductor device of another embodiment of the present invention.
  • substituted in “substituted or unsubstituted” means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen, an amino group, a nitro group, a cyano group, an oxo group, a C1-C20 alkyl group, a C1-C20 haloalkyl group , C6-C30 aryl group, C3-C30 heteroaryl group, C3-C10 cycloalkyl group, C3-C10 heterocycloalkyl group, C7-C30 arylalkyl group, C1-C30 heteroalkyl group
  • the 'halo' means fluorine, chlorine, iodine or bromine.
  • aryl group refers to a substituent in which all elements of a cyclic substituent have p-orbital and p-orbital forms a conjugate, and a single ring structure or multiple at least two rings are fused. It may include, but is not limited to, a phenyl group, biphenyl group, naphthyl group, naphthol group, anthracenyl group, and the like.
  • 'hetero' in the 'heterocycloalkyl group', 'heteroaryl group', 'heterocycloalkylene group', and 'heteroarylene group' means a nitrogen, oxygen, sulfur or phosphorus atom.
  • the phosphonium-based compound of the present invention includes a phosphonium-based cation and an anion having a cyclic structure in which the central metal is zinc (Zn), and may be represented by the following Chemical Formula 1.
  • R 1 , R 2 , R 3 and R 4 are each independently substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or Substituted or unsubstituted C1-C30 hydrocarbon group containing a hetero atom,
  • X 1 and X 2 are each independently a substituted or unsubstituted C 1 to C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 6 to C 30 aromatic hydrocarbon group, or a substituted or unsubstituted C 1 to C 30 containing a hetero atom
  • a hydrocarbon group Y 1 , Y 2 , Y 3 , and Y 4 are each independently an oxygen atom (O), a sulfur atom (S) or a substituted nitrogen atom (N)).
  • the phosphonium compound of the present invention may be one of the compounds represented by the following Chemical Formulas 1a to 1e.
  • the phosphonium-based compound as described above may be a water-insoluble compound.
  • the phosphonium-based compound of the present invention may be prepared by reacting a phosphonium-based cation-containing compound with an anion-containing compound having a cyclic structure having zinc as a central metal in a molar ratio of 2: 1.
  • the phosphonium-based cation-containing compound may be prepared by combining a phosphine-based compound with an alkyl halide, an aryl halide or an aralkyl halide in a solvent, or a phosphonium-based cation-containing salt (eg, tetraphenylphosphonium halide).
  • a phosphine-based compound with an alkyl halide, an aryl halide or an aralkyl halide in a solvent, or a phosphonium-based cation-containing salt (eg, tetraphenylphosphonium halide).
  • the phosphine-based compound may be triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine, and the like.
  • the present invention is not limited thereto.
  • the anion-containing compound of the cyclic structure having zinc as the central metal may be an anion-containing salt.
  • the anion-containing compound may be prepared by combining an alkali salt and a zinc compound (eg, biscatechol zincate, bisthiocatechol zincate, bisthiosalicylic zincate) in a solvent.
  • a zinc compound eg, biscatechol zincate, bisthiocatechol zincate, bisthiosalicylic zincate
  • the present invention is not limited thereto.
  • the phosphonium-based compound of the present invention as described above can be used as a latent curing catalyst by being added to the epoxy resin composition to be described later.
  • the phosphonium-based compound reacts with the epoxide group in the epoxy resin to perform a ring-opening reaction, and the ring-opening reaction of the epoxide group by the reaction with a hydroxyl group in the epoxy resin after the ring-opening reaction, the chain terminal and the epoxide of the activated epoxy resin
  • the hardening reaction is accelerated by the reaction of .
  • the phosphonium-based compound catalyzes curing only when the desired curing temperature or more, and there is no curing catalyst activity when the phosphonium compound is not the desired curing temperature. This is believed to be because the ionic bond between the phosphonium cation and the zinc center metal anion is dissociated at a specific temperature and becomes active.
  • the progress of the curing reaction may cause an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid.
  • the phosphonium-based compound of the present invention has a catalytic activity only at the curing temperature as described above, when added to the epoxy resin composition, it is possible to minimize the viscosity change of the epoxy resin, thereby realizing excellent storage stability for a long time Can be.
  • the epoxy resin composition of the present invention may include at least one of an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst.
  • the epoxy resin may have at least one epoxy group in a molecule, for example, may have at least two or more epoxy groups in a molecule, or may have two or more epoxy groups and one or more hydroxyl groups in a molecule.
  • the epoxy resin may include at least one of a solid epoxy resin and a liquid epoxy resin, and preferably a solid epoxy resin may be used.
  • epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, tert-butyl catechol type epoxy resins, naphthalene type epoxy resins, glycidylamine type epoxy resins, and cresolno. Volac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, phenol aralkyl type epoxy resin And halogenated epoxy resins. These may be included alone or in combination of two or more thereof.
  • the epoxy resin may be a biphenyl type epoxy resin represented by the following [Formula 2] and / or a phenol aralkyl type epoxy resin represented by the following [Formula 3].
  • R is an alkyl group having 1 to 4 carbon atoms, the average value of n is 0 to 7
  • the epoxy resin may be included 2 to 17% by weight, for example 3 to 15% by weight, for example 3 to 12% by weight based on the solids content of the composition. In the above range, the curability of the composition may not be lowered.
  • the curing agent is a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylock type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, a dicyclopentadiene type phenol resin, Novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, dia Aromatic amines, such as a minodiphenylmethane and a diamino diphenyl sulfone, etc. are mentioned.
  • the curing agent may be a phenol resin having one or more hydroxyl groups.
  • the curing agent may be a xylox phenol resin of Formula 4 and / or a phenol aralkyl type phenol resin of Formula 5 below.
  • the curing agent may be included in the epoxy resin composition 0.5 to 13% by weight, for example 1 to 10% by weight, for example 2 to 8% by weight based on the solids content. In the above range, the curability of the composition may not be lowered.
  • the epoxy resin composition of the present invention may include an inorganic filler.
  • Inorganic fillers can increase the mechanical properties and low stress of the composition.
  • examples of the inorganic fillers include molten silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fibers.
  • molten silica having a low coefficient of linear expansion is preferable in terms of low stress.
  • Molten silica refers to amorphous silica having a true specific gravity of 2.3 or less, and also includes amorphous silica made by melting crystalline silica or synthesized from various raw materials.
  • the shape and particle size of the molten silica are not particularly limited, but the molten silica includes 50 to 99% by weight of spherical molten silica having an average particle diameter of 5 to 30 ⁇ m and 1 to 50% by weight of spherical molten silica having an average particle diameter of 0.001 to 1 ⁇ m.
  • the mixture it is preferable to include the mixture to be 40 to 100% by weight based on the total inorganic filler. Moreover, according to a use, the maximum particle diameter can be adjusted and used in any one of 45 micrometers, 55 micrometers, and 75 micrometers.
  • conductive carbon may be included as a foreign matter on the silica surface, but it is preferable to select a material having a small amount of polar foreign matter mixed therein.
  • the amount of the inorganic filler used depends on the required physical properties such as formability, low stress, and high temperature strength.
  • the inorganic filler may be included in 70 to 95% by weight, for example 75 to 92% by weight of the epoxy resin composition. Within this range, flame retardancy, fluidity and reliability of the epoxy resin composition can be ensured.
  • the epoxy resin composition of the present invention may include a curing catalyst containing a phosphonium-based compound represented by the above [Formula 1].
  • the phosphonium-based compound represented by [Formula 1] may be included in 0.01 to 5% by weight, for example 0.02 to 1.5% by weight, for example 0.05 to 1.5% by weight in the epoxy resin composition.
  • the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
  • the epoxy resin composition of the present invention may further include a non-phosphonium-based curing catalyst containing no phosphonium.
  • a non-phosphonium-based curing catalyst containing no phosphonium As the non-phosphonium-based curing catalysts, tertiary amine curing catalysts, organometallic compound curing catalysts, organophosphorus compound curing catalysts, imidazole curing catalysts and boron compound curing catalysts can be used.
  • Tertiary amine curing catalysts include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (dia) Minomethyl) phenol and tri-2-ethylhexyl acid salt.
  • Organometallic compound curing catalysts include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like.
  • organophosphorus curing catalysts include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct and the like.
  • the imidazole curing catalysts include 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2- Heptadecylimidazole and the like.
  • Examples of the boron compound curing catalyst include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, and the like. There is this. In addition, 1,5- diazabicyclo [4.3.0] non-5-ene (1, 5- diazabicyclo [4.3.0] non-5-ene: DBN), 1, 8- diazabicyclo [5.4.
  • undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts
  • a non-phosphonium-based curing catalyst an organophosphorus curing catalyst, a boron compound curing catalyst, an amine curing catalyst, or an imidazole curing catalyst may be used alone or in combination. It is also possible to use an adduct made by pre-reaction with an epoxy resin or a curing agent as the non-phosphonium-based curing catalyst.
  • the phosphonium-based compound of the present invention may be included in 10 to 100% by weight, for example 60 to 100% by weight of the total curing catalyst, the curing reaction time is not delayed in the above range, there is an effect of ensuring the fluidity of the composition Can be.
  • the curing catalyst may be included in 0.01 to 5% by weight, for example 0.02 to 1.5% by weight, for example 0.05 to 1.5% by weight of the epoxy resin composition. In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
  • the epoxy resin composition of the present invention may further include conventional additives included in the epoxy resin composition in addition to the above components.
  • the additive may include one or more of a coupling agent, a release agent, a stress relaxer, a crosslinking enhancer, a leveling agent, and a coloring agent.
  • the coupling agent may be one or more selected from the group consisting of epoxysilane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto.
  • the coupling agent may be included in 0.1 to 1% by weight of the epoxy resin composition.
  • the release agent may be used at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt.
  • the release agent may be included in 0.1 to 1% by weight of the epoxy resin composition.
  • the stress relaxing agent may be used one or more selected from the group consisting of modified silicone oil, silicone elastomer, silicone powder and silicone resin, but is not limited thereto.
  • the stress relaxation agent is preferably contained in 0 to 6.5% by weight, for example 0 to 1% by weight, for example 0.1 to 1% by weight in the epoxy resin composition.
  • the modified silicone oil a silicone polymer having excellent heat resistance is good, and silicone oil having an epoxy functional group, silicone oil having an amine functional group, silicone oil having a carboxyl functional group, and the like may be used alone or in combination of two or more kinds.
  • the silicone oil is preferably included in an amount of about 0.05 to 1.5% by weight based on the total epoxy resin composition.
  • the content of silicone oil exceeds 1.5% by weight, surface contamination is likely to occur and the resin bleed may be long, and when used below 0.05% by weight, sufficient low modulus of elasticity may not be obtained. have.
  • the silicone powder having a central particle diameter of 15 ⁇ m or less from the viewpoint of preventing moldability deterioration.
  • the silicon powder may be contained in 0 to 5% by weight, for example 0.1 to 5% by weight based on the total resin composition.
  • the additive may be included in 0.1 to 10% by weight, for example 0.1 to 3% by weight of the epoxy resin composition.
  • the epoxy resin composition of the present invention preferably has a flow length of about 59-75 inches (about 1.4986 m to 1.905 m) at 175 ° C. and 70 kgf / cm 2 in EMMI-1-66.
  • the flow length satisfies the above range, it may be usefully used as a sealing material of a semiconductor device.
  • the epoxy resin composition of the present invention preferably has a curing shrinkage rate of less than about 0.4%, for example, about 0.01 to about 0.39% measured by the following [formula 1].
  • the curing shrinkage satisfies the numerical range, it may be usefully used as a sealing material for semiconductor devices.
  • Cure Shrinkage Rate
  • C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 °C, 70kgf / cm 2
  • D is post-cure (PMC: post molding cure), and cooled the specimen at 175 °C Is the length of the specimen obtained).
  • the epoxy resin in the epoxy resin composition may be used alone, the additives such as the epoxy resin and the curing agent, curing catalyst, release agent, coupling agent, and stress release agent by a linear reaction such as melt master batch (melt master batch) It may be included in the form of additional compounds made.
  • the method for producing the epoxy resin composition is not particularly limited, and for example, each component contained in the composition may be uniformly mixed using a Henschel mixer or a Rodige mixer, and then 90 to 120 ° C with a roll mill or kneader. It can be prepared by melt kneading in the cooling, cooling and grinding process.
  • the epoxy resin composition preferably has a glass transition temperature of 100 °C to 130 °C, for example, about 123 °C to 125 °C.
  • a glass transition temperature of 100 °C to 130 °C, for example, about 123 °C to 125 °C.
  • the resin composition of the present invention is required for use in epoxy resin compositions such as semiconductor device sealing applications, adhesive films, insulating resin sheets such as prepregs, circuit boards, solder resists, underfill agents, die bonding materials, and component supplement resin applications. It can be applied to a wide range of applications and is not particularly limited.
  • the semiconductor element of this invention is sealed using the epoxy resin composition of this invention mentioned above.
  • a semiconductor device 100 may include a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30. ), And the gap between the wiring board 10 and the semiconductor chip 20 may be sealed by the epoxy resin composition 40, wherein the epoxy resin composition may be the epoxy resin composition of the present invention described above. have.
  • a semiconductor device 200 may include a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30. It includes, the gap between the wiring board 10 and the semiconductor chip 20 and the entire upper surface of the semiconductor chip 30 may be sealed with an epoxy resin composition 40, wherein the epoxy resin composition is It may be an epoxy resin composition of the present invention.
  • the sizes of the wiring boards, bumps, and semiconductor chips, and the number of bumps are arbitrary and may be changed.
  • the low pressure transfer molding method can be used most commonly.
  • the present invention is not limited thereto, and may be molded by an injection molding method or a casting method.
  • a semiconductor device of a copper lead frame, an iron lead frame, or a lead frame pre-plated with at least one material selected from the group consisting of palladium with nickel and copper on the lead frame, or an organic laminate frame can be manufactured. Can be.
  • NC-3000 (Nippon Kayaku), a biphenyl type epoxy resin, was used.
  • Inorganic filler A 9: 1 (weight ratio) mixture of spherical molten silica having an average particle diameter of 18 ⁇ m and spherical molten silica having an average particle diameter of 0.5 ⁇ m was used.
  • KBM-803 (Shinetsu), which is (e1) mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is (e2) methyltrimethoxysilane, were mixed and used.
  • Carnauba wax was used as the release agent (f1) and carbon black MA-600 (Matsusita Chemical) was used as the colorant (f2).
  • the components were weighed according to the composition (unit: parts by weight) of Table 1 below, and then uniformly mixed using a Henschel mixer to prepare a primary composition in powder form. After the melt kneading at 95 °C using a continuous kneader and then cooled and pulverized to prepare an epoxy resin composition for sealing a semiconductor device.
  • Cure Shrinkage Rate
  • C is the length of the specimen obtained by the transfer molding press of the epoxy resin composition at 175 °C, 70kgf / cm 2
  • D is the specimen obtained after curing and cooling the specimen at 175 °C 4 hours
  • TMA thermomechanical analyzer
  • Hygroscopicity (%): molding the epoxy resin composition to be evaluated under the conditions of mold temperature 170 ⁇ 180 °C, clamp pressure 70kgf / cm 2 , transfer pressure 1000psi, transfer rate 0.5 ⁇ 1cm / s, curing time 120 seconds
  • the obtained specimens were placed in an oven at 170 to 180 ° C., and after 4 hours of post-curing (PMC: post molding cure), they were left at 85 ° C. and 85 RH% relative humidity for 168 hours, and then the weight change due to moisture absorption was measured. The moisture absorption was calculated by 3.
  • Hygroscopicity (weight of test piece after moisture absorption-weight of test piece before moisture absorption) ⁇ (weight of test piece before moisture absorption) ⁇ 100
  • Adhesion force (kgf): A copper metal element is prepared in a size suitable for a mold for measuring adhesion, and the epoxy resin composition to be evaluated on the prepared copper metal element is at a mold temperature of 170 to 180 ° C., a clamp pressure of 70 kgf / cm 2 , and transferred. Curing specimens were obtained by molding under conditions of a pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds. The obtained specimens were put in an oven at 170 to 180 ° C. and post-cured (PMC: post molding cure) for 4 hours. At this time, the area of the epoxy resin composition in contact with the copper metal element is 40 ⁇ 1mm2, the adhesion was measured by the average value after measuring by using a universal testing machine (UTM) for 12 specimens per measurement process.
  • UPM universal testing machine
  • Shore-D Using a multi-plunger system (MPS) molding machine equipped with a mold for an eTQFP (exposed thin quad flat package) package having a width of 24 mm, a length of 24 mm, and a thickness of 1 mm containing a copper metal element. After curing the epoxy resin composition to be evaluated at 175 ° C. for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product according to the curing time was measured with a Shore-D hardness tester directly on the package on the mold. The higher the value, the better the degree of curing.
  • MPS multi-plunger system
  • Examples 1 to 5 show high fluidity, and in the case of storage stability, it can be seen that there is almost no difference in fluidity even after 72 hours. When the external crack does not occur, the crack resistance is good and no peeling occurs. It can be seen that the moisture resistance is also excellent.
  • Examples 4 and 5 show high fluidity and have low cure shrinkage when compared with Comparative Examples 1 and 2.
  • the degree of cure by curing time it can be seen that the degree of higher curing is shown even in a short curing time.
  • compositions of Comparative Examples 1 and 2 which do not contain the phosphonium-based compound of the present invention, have low storage stability, high curing shrinkage rate, low fluidity, low adhesion, and reliability problems. It can be seen that the effects of the invention can not be implemented.

Abstract

The present invention relates to a phosphonium-based compound represented by chemical formula 1, an epoxy resin containing the same, and a semiconductor device sealed by using the same.

Description

포스포늄계 화합물, 이를 포함하는 에폭시 수지 조성물, 및 이를 사용하여 제조된 반도체 소자Phosphonium-based compound, epoxy resin composition comprising the same, and semiconductor device manufactured using the same
본 발명은 포스포늄계 화합물, 이를 포함하는 에폭시 수지 조성물 및 이를 사용하여 제조된 반도체 소자에 관한 것이다. The present invention relates to a phosphonium compound, an epoxy resin composition comprising the same, and a semiconductor device manufactured using the same.
IC(Integrated Circuit), LSI(Large Scale Integration) 등과 같은 반도체 소자를 포장하고 반도체 장치를 얻는 방법으로, 저비용, 대량 생산이 가능한 에폭시 수지 조성물을 이용한 트랜스퍼(transfer) 성형이 널리 사용되고 있다. 한편, 상기 에폭시 수지 조성물을 이용한 트랜스퍼 성형의 경우, 사용되는 에폭시 수지나 경화제인 페놀 수지를 개량함으로써, 반도체 소자의 특성 및 신뢰성의 향상을 도모할 수 있다. BACKGROUND OF THE INVENTION As a method of packaging a semiconductor device such as an integrated circuit (IC) and a large scale integration (LSI) and obtaining a semiconductor device, transfer molding using an epoxy resin composition capable of producing a low cost and mass production is widely used. On the other hand, in the case of transfer molding using the said epoxy resin composition, the characteristic and reliability of a semiconductor element can be improved by improving the phenol resin which is an epoxy resin and a hardening | curing agent used.
한편, 상기 에폭시 수지 조성물은 에폭시 수지, 경화제, 경화촉매 등을 포함하며, 상기 경화촉매로는 통상 이미다졸계 촉매, 아민계 촉매, 포스핀계 촉매가 사용되어 왔다. Meanwhile, the epoxy resin composition includes an epoxy resin, a curing agent, a curing catalyst, and the like, and as the curing catalyst, an imidazole catalyst, an amine catalyst, and a phosphine catalyst have been generally used.
그러나 전자기기가 점차 소형화, 경량화, 고성능화되는 추세에 따라 반도체의 고집적화가 매년 가속화되고 있고, 반도체 소자의 표면 실장화에 대한 요구도 늘어가고 있다. 이에 따라, 종래에 사용되었던 에폭시 수지 조성물로는 해결할 수 없는 문제들이 생기고 있다. However, as electronic devices become smaller, lighter, and higher in performance, high integration of semiconductors is accelerating every year, and the demand for surface mounting of semiconductor devices is increasing. Accordingly, there are problems that cannot be solved with the epoxy resin composition used in the related art.
또한, 근래의 반도체 소자의 포장에 사용되는 재료에는 생산성의 향상을 목적으로 한 속경화성과 물류, 보관시의 취급성 향상을 목적으로 한 보존 안정성이 요구되고 있다.In addition, in recent years, materials used for packaging semiconductor devices require fast curing for the purpose of improving productivity, storage stability for the purpose of improving the handling properties in distribution and storage.
에폭시 수지의 경화성을 향상시키기 위해, 트리페닐포스핀(triphenylphosphine)과1,4-벤조퀴논(1,4-benzoquinone)의 부가생성물을 에폭시 수지 조성물의 경화촉매에 포함하여 사용하는 방법이 알려져 있다. 그러나, 이 경우 비교적 저온에서도 경화촉진 효과가 나타나서 에폭시 수지와 다른 성분들을 혼합할 때 발생하는 열 또는 외부로부터 더해지는 열에 의해 에폭시 수지 조성물의 경화가 진행될 수 있으며, 에폭시 수지 조성물을 상온에서 보관하는 경우에도 경화가 발생하여 저장 안정성이 떨어진다는 문제점이 있다. 이러한 경화반응의 진행은 에폭시 수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시 수지 조성물이 고체인 경우 점성을 발현시킬 수 있다. 또한 이러한 상태의 변화는 에폭시 수지 조성물 내에서 균일하게 나타나지 않는다. 따라서, 실제로 에폭시 수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하가 발생할 수 있으며, 성형 후 제품의 기계적, 전기적, 화학적 특성이 저하될 수 있다는 문제점이 있다.In order to improve the sclerosis | hardenability of an epoxy resin, the method of using the addition product of triphenylphosphine and 1, 4- benzoquinone (1, 4- benzoquinone) in the curing catalyst of an epoxy resin composition is known. However, in this case, the curing promoting effect is exhibited even at a relatively low temperature, and the curing of the epoxy resin composition may proceed by heat generated when mixing the epoxy resin and other components, or heat added from the outside, even when the epoxy resin composition is stored at room temperature. There is a problem that hardening occurs and the storage stability is poor. The progress of such a curing reaction may cause an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid. In addition, such a change of state does not appear uniformly in an epoxy resin composition. Therefore, when the epoxy resin composition is actually cured at a high temperature, moldability may be decreased due to fluidity decrease, and mechanical, electrical and chemical properties of the product may be reduced after molding.
관련 선행문헌으로 일본공개특허 제2007-262238호가 있다.As a related prior art, there is Japanese Patent Laid-Open No. 2007-262238.
본 발명의 목적은 에폭시 수지의 경화를 촉진할 수 있고, 몰딩시 유동성이 우수하며, 높은 경화 강도를 나타내고, 짧은 경화시간에 경화가 가능한 경화촉매용 화합물을 제공하는 것이다.An object of the present invention is to provide a curing catalyst compound that can promote curing of an epoxy resin, has excellent fluidity during molding, exhibits high curing strength, and can be cured in a short curing time.
본 발명의 다른 목적은 저온에서도 에폭시 수지의 경화를 촉진할 수 있는 경화촉매용 화합물을 제공하는 것이다.Another object of the present invention is to provide a compound for a curing catalyst that can promote curing of an epoxy resin even at low temperatures.
본 발명의 또 다른 목적은 원하는 경화온도가 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화촉매 활성이 없게 하는 저장안정성이 높은 경화촉매용 화합물을 제공하는 것이다.It is still another object of the present invention to provide a compound for a storage catalyst having a high storage stability, which catalyzes curing only when the desired curing temperature is reached, and when the curing temperature is not the desired curing catalyst.
본 발명의 또 다른 목적은 상기 경화촉매용 화합물을 포함하는 에폭시 수지 조성물 및 이를 사용하여 제조된 반도체 소자를 제공하는 것이다.Still another object of the present invention is to provide an epoxy resin composition comprising the compound for the curing catalyst and a semiconductor device manufactured using the same.
일 측면에서, 본 발명은 하기 [화학식 1]로 표시되는 포스포늄계 화합물을 제공한다.In one aspect, the present invention provides a phosphonium-based compound represented by the following [Formula 1].
[화학식 1][Formula 1]
Figure PCTKR2015010729-appb-I000001
Figure PCTKR2015010729-appb-I000001
(상기 화학식 1에서, R1, R2, R3, R4, X1, X2, Y1, Y2, Y3, 및Y4 는 하기 상세한 설명에 정의된 바와 같다).(In Formula 1, R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , Y 1 , Y 2 , Y 3 , and Y 4 are as defined in the following detailed description).
상기 포스포늄계 화합물은 하기 화학식 1a 내지 1e로 표시되는 화합물들 중 하나일 수 있다. The phosphonium-based compound may be one of the compounds represented by the following Chemical Formulas 1a to 1e.
[화학식 1a][Formula 1a]
Figure PCTKR2015010729-appb-I000002
Figure PCTKR2015010729-appb-I000002
[화학식 1b][Formula 1b]
Figure PCTKR2015010729-appb-I000003
Figure PCTKR2015010729-appb-I000003
[화학식 1c][Formula 1c]
Figure PCTKR2015010729-appb-I000004
Figure PCTKR2015010729-appb-I000004
[화학식 1d][Formula 1d]
Figure PCTKR2015010729-appb-I000005
Figure PCTKR2015010729-appb-I000005
[화학식 1e][Formula 1e]
Figure PCTKR2015010729-appb-I000006
Figure PCTKR2015010729-appb-I000006
다른 측면에서, 본 발명은 에폭시 수지, 경화제, 무기충전제 및 경화촉매를 포함하고, 상기 경화촉매에는 경화촉진제로서 작용하는 상기 포스포늄계 화합물을 포함하는 에폭시 수지 조성물을 제공한다. In another aspect, the present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, an inorganic filler and a curing catalyst, wherein the curing catalyst includes the phosphonium-based compound that acts as a curing accelerator.
상기 에폭시 수지는, 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시 수지, 나프탈렌형 에폭시 수지, 글리시딜아민형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비페닐형 에폭시 수지, 선형 지방족 에폭시 수지, 지환식 에폭시 수지, 복소환식 에폭시 수지, 스피로환 함유 에폭시 수지, 시클로헥산디메탄올형 에폭시 수지, 트리메틸올형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 및 할로겐화 에폭시수지 중 하나 이상을 포함할 수 있다. The said epoxy resin is a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a tert- butyl catechol-type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, a cresol novolak-type epoxy Resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, phenol aralkyl type epoxy resin, and halogenated It may include one or more of the epoxy resins.
상기 경화제는, 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄 및 디아미노디페닐설폰 중 하나 이상을 포함할 수 있다.The said hardening | curing agent is a phenol aralkyl type phenol resin, a phenol novolak-type phenol resin, a xylox phenol resin, a cresol novolak-type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, a dicyclopentadiene type phenol Novolak-type phenolic resin synthesized from resin, bisphenol A and resol, polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydride including maleic anhydride and phthalic anhydride, metaphenylenediamine , Diaminodiphenylmethane and diaminodiphenylsulfone.
상기 경화촉매는 상기 에폭시 수지 조성물 중 0.01 내지 5중량%로 포함될 수 있다.The curing catalyst may be included in 0.01 to 5% by weight of the epoxy resin composition.
상기 포스포늄계 화합물은 상기 경화촉매 중 10 내지 100중량%로 포함될 수 있다.The phosphonium-based compound may be included in 10 to 100% by weight of the curing catalyst.
상기 에폭시 수지 조성물은, 상기 에폭시 수지 2 내지 17중량%, 상기 경화제 0.5 내지 13중량%, 상기 무기 충전제 70 내지 95중량%, 상기 경화촉매 0.01 내지 5중량%를 포함할 수 있다. The epoxy resin composition may include 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, and 0.01 to 5 wt% of the curing catalyst.
상기 에폭시 수지 조성물은 72시간 경과 후 저장안정성이 80% 이상일 수 있다.The epoxy resin composition may have a storage stability of 80% or more after 72 hours.
상기 에폭시 수지 조성물은 하기 [식 1]로 표시되는 경화수축률이 0.4% 미만일 수 있다:The epoxy resin composition may have a curing shrinkage ratio of less than 0.4% represented by the following [Formula 1]:
[식 1][Equation 1]
경화수축률= ｜C - D｜/C × 100Cure Shrinkage Rate = ｜ C-D ｜ / C × 100
(상기 식 1에서, C는 에폭시 수지 조성물을 175, 70kgf/cm2에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 175에서 후경화(PMC:post molding cure)하고, 냉각시킨 후 얻은 시편의 길이이다).(In Formula 1, C is the length of the specimen obtained by the transfer molding press epoxy resin composition at 175, 70kgf / cm 2 , D is obtained after the post-cure (PMC: post molding cure) at 175, and cooled) Length of the specimen).
또 다른 측면에서, 본 발명은 상기 에폭시 수지 조성물로 밀봉된 반도체 소자를 제공한다. In another aspect, the present invention provides a semiconductor device sealed with the epoxy resin composition.
본 발명은 에폭시 수지의 경화를 촉진할 수 있고, 저온에서도 에폭시 수지의 경화를 촉진할 수 있는 경화촉매용 화합물을 제공하며, 에폭시수지, 경화제 등을 포함하는 혼합물에서 소정 범위의 시간 및 온도 조건에서도 점도 변화를 최소화하여 에폭시수지 조성물을 고온에서 경화반응 시켰을 때 유동성 저하에 따른 성형성 저하, 성형 제품의 기계적, 전기적, 화학적 특성이 저하가 없게 하고, 저장안정성이 높은 경화촉매용 화합물을 제공하였다.The present invention provides a compound for a curing catalyst that can promote the curing of the epoxy resin, can promote the curing of the epoxy resin even at low temperatures, and in a mixture containing an epoxy resin, a curing agent and the like even in a predetermined range of time and temperature conditions By minimizing the viscosity change, when the epoxy resin composition was cured at a high temperature, there was no deterioration in moldability due to fluidity decrease, and the mechanical, electrical, and chemical properties of the molded product did not decrease, and a compound for storage catalyst with high storage stability was provided.
도 1은 본 발명 일 실시예의 반도체 소자의 단면도이다.1 is a cross-sectional view of a semiconductor device in accordance with an embodiment of the present invention.
도 2는 본 발명 다른 실시예의 반도체 소자의 단면도이다.2 is a cross-sectional view of a semiconductor device of another embodiment of the present invention.
본 명세서에서 "치환 또는 비치환된"에서 "치환된"은 해당 작용기 중 하나 이상의 수소 원자가 수산기, 할로겐, 아미노기, 니트로기, 시아노기, 옥소기, C1~C20의 알킬기, C1~C20의 할로알킬기, C6~C30의 아릴기, C3~C30의 헤테로아릴기, C3~C10의 시클로알킬기, C3~C10의 헤테로시클로알킬기, C7~C30의 아릴알킬기, C1~C30의 헤테로알킬기 등으로 치환된 것을 의미한다 이때, 상기 '할로'는 불소, 염소, 요오드 또는 브롬을 의미한다.As used herein, "substituted" in "substituted or unsubstituted" means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen, an amino group, a nitro group, a cyano group, an oxo group, a C1-C20 alkyl group, a C1-C20 haloalkyl group , C6-C30 aryl group, C3-C30 heteroaryl group, C3-C10 cycloalkyl group, C3-C10 heterocycloalkyl group, C7-C30 arylalkyl group, C1-C30 heteroalkyl group In this case, the 'halo' means fluorine, chlorine, iodine or bromine.
본 명세서에서 "아릴기"는 환형인 치환기의 모든 원소가 p-오비탈을 가지며 p-오비탈이 공액을 형성하는 치환기를 의미하는 것으로, 단일 고리 구조 또는 2개 이상의 고리가 융합되어 있는(fused) 다중 고리 구조를 포함하며, 예를 들면 페닐기, 비페닐기, 나프틸기, 나프톨기, 안트라세닐기 등을 의미할 수 있지만 이에 제한되지 않는다.As used herein, the term "aryl group" refers to a substituent in which all elements of a cyclic substituent have p-orbital and p-orbital forms a conjugate, and a single ring structure or multiple at least two rings are fused. It may include, but is not limited to, a phenyl group, biphenyl group, naphthyl group, naphthol group, anthracenyl group, and the like.
본 명세서에서 "헤테로아릴기"는 C6 내지 C30의 아릴기 내에 질소, 산소, 황 및 인으로 이루어진 군에서 선택되는 원자가 1 내지 3개 포함되고 나머지는 탄소인 것을 의미하고, 예를 들면 피리디닐, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐, 퀴놀리닐, 이소퀴놀리닐, 퀴녹살리닐, 아크리디닐, 퀴나졸리닐, 신노리닐, 프탈라지닐, 티아졸릴, 벤조티아졸릴, 이속사졸릴, 벤즈이속사졸릴, 옥사졸릴, 벤즈옥사졸릴, 피라졸릴, 인다졸릴, 이미다졸릴, 벤즈이미다졸릴, 퓨리닐, 티오페닐, 벤조티오페닐, 푸라닐, 벤조푸라닐, 이소벤조푸라닐을 의미할 수 있지만 이에 제한되지 않는다. As used herein, "heteroaryl group" means one to three atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus in the aryl group of C6 to C30 and the rest are carbon, for example pyridinyl, Pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, cshinolinyl, phthalazinyl, thiazolyl, benzothiazolyl, Isoxazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, furinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, isobenzofura Neil may mean, but is not limited to such.
본 명세서에서 '헤테로시클로알킬기', '헤테로아릴기', '헤테로시클로알킬렌기', '헤테로아릴렌기'에서 '헤테로'는 질소, 산소, 황 또는 인 원자를 의미한다.In the present specification, 'hetero' in the 'heterocycloalkyl group', 'heteroaryl group', 'heterocycloalkylene group', and 'heteroarylene group' means a nitrogen, oxygen, sulfur or phosphorus atom.
본 발명의 포스포늄계 화합물은 포스포늄계 양이온과 중심 금속이 아연(Zn)인 고리형 구조의 음이온을 포함하는 것으로, 하기 화학식 1과 같이 표시될 수 있다.The phosphonium-based compound of the present invention includes a phosphonium-based cation and an anion having a cyclic structure in which the central metal is zinc (Zn), and may be represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2015010729-appb-I000007
Figure PCTKR2015010729-appb-I000007
(상기 [화학식 1]에서, R1, R2, R3 및 R4 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, (In [Formula 1], R 1 , R 2 , R 3 and R 4 are each independently substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or Substituted or unsubstituted C1-C30 hydrocarbon group containing a hetero atom,
X1 및X2는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, Y1, Y2, Y3, 및Y4 는 각각 독립적으로 산소원자(O), 황원자(S) 또는 치환된 질소원자(N)이다).X 1 and X 2 are each independently a substituted or unsubstituted C 1 to C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 6 to C 30 aromatic hydrocarbon group, or a substituted or unsubstituted C 1 to C 30 containing a hetero atom And a hydrocarbon group, Y 1 , Y 2 , Y 3 , and Y 4 are each independently an oxygen atom (O), a sulfur atom (S) or a substituted nitrogen atom (N)).
예를 들면, 본 발명의 포스포늄계 화합물은 하기 화학식 1a 내지 1e 로 표시되는 화합물들 중 하나일 수 있다. For example, the phosphonium compound of the present invention may be one of the compounds represented by the following Chemical Formulas 1a to 1e.
[화학식 1a][Formula 1a]
Figure PCTKR2015010729-appb-I000008
Figure PCTKR2015010729-appb-I000008
[화학식 1b][Formula 1b]
Figure PCTKR2015010729-appb-I000009
Figure PCTKR2015010729-appb-I000009
[화학식 1c][Formula 1c]
Figure PCTKR2015010729-appb-I000010
Figure PCTKR2015010729-appb-I000010
[화학식 1d][Formula 1d]
Figure PCTKR2015010729-appb-I000011
Figure PCTKR2015010729-appb-I000011
[화학식 1e][Formula 1e]
Figure PCTKR2015010729-appb-I000012
Figure PCTKR2015010729-appb-I000012
상기와 같은 포스포늄계 화합물은 수불용성 화합물일 수 있다. The phosphonium-based compound as described above may be a water-insoluble compound.
한편, 상기 본 발명의 포스포늄계 화합물은 포스포늄계 양이온 함유 화합물과 중심금속으로 아연을 갖는 고리형 구조의 음이온 함유 화합물을 2:1의 몰수비로 반응시켜 제조될 수 있다. Meanwhile, the phosphonium-based compound of the present invention may be prepared by reacting a phosphonium-based cation-containing compound with an anion-containing compound having a cyclic structure having zinc as a central metal in a molar ratio of 2: 1.
이때, 상기 포스포늄계 양이온 함유 화합물은 용매 하에 포스핀계 화합물과 알킬 할라이드, 아릴 할라이드 또는 아랄킬 할라이드 등을 결합시켜 제조되는 것 또는 포스포늄계 양이온 함유 염(예: 테트라페닐포스포늄 할라이드 등일 수 있다. 한편, 상기 포스핀계 화합물는 트리페닐포스핀, 메틸디페닐포스핀, 디메틸페닐포스핀, 에틸디페닐포스핀, 디페닐프로필포스핀, 이소프로필디페닐포스핀, 디에틸페닐포스핀 등일 수 있지만, 이에 제한되는 것은 아니다. In this case, the phosphonium-based cation-containing compound may be prepared by combining a phosphine-based compound with an alkyl halide, an aryl halide or an aralkyl halide in a solvent, or a phosphonium-based cation-containing salt (eg, tetraphenylphosphonium halide). Meanwhile, the phosphine-based compound may be triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine, and the like. However, the present invention is not limited thereto.
한편, 상기 중심 금속으로 아연을 갖는 고리형 구조의 음이온 함유 화합물은 음이온 함유 염일 수 있다. 예를 들면, 상기 음이온 함유 화합물은, 용매 하에 알칼리 염과 징크 화합물(예: 비스카테콜 징크케이트, 비스 싸이오카테콜 징크케이트, 비스 싸이오살리실릭 징크케이트)을 결합시켜 제조 되는 것일 수 있으나, 이에 제한되는 것은 아니다. On the other hand, the anion-containing compound of the cyclic structure having zinc as the central metal may be an anion-containing salt. For example, the anion-containing compound may be prepared by combining an alkali salt and a zinc compound (eg, biscatechol zincate, bisthiocatechol zincate, bisthiosalicylic zincate) in a solvent. However, the present invention is not limited thereto.
상기와 같은 본 발명의 포스포늄계 화합물은 후술할 에폭시 수지 조성물에 첨가되어 잠재성 경화촉매로 사용될 수 있다. The phosphonium-based compound of the present invention as described above can be used as a latent curing catalyst by being added to the epoxy resin composition to be described later.
상기 포스포늄계 화합물은 에폭시 수지 내 에폭사이드기와 반응하여 개환 반응을 하게 되고, 상기 개환 반응 후에 에폭시 수지 내 수산기와의 반응에 의한 에폭사이드기의 개환 반응, 활성화된 에폭시수지의 사슬 말단과 에폭사이드의 반응 등이 일어나면서 경화반응이 촉진된다 . The phosphonium-based compound reacts with the epoxide group in the epoxy resin to perform a ring-opening reaction, and the ring-opening reaction of the epoxide group by the reaction with a hydroxyl group in the epoxy resin after the ring-opening reaction, the chain terminal and the epoxide of the activated epoxy resin The hardening reaction is accelerated by the reaction of .
한편, 상기 포스포늄계 화합물은 원하는 경화온도 이상이 될 때에만 경화를 촉매시키고 원하는 경화온도가 아닐 때에는 경화촉매 활성이 없다. 이것은 포스포늄 양이온과 아연중심금속 음이온 사이의 이온 결합이 특정 온도 이상에서 해리가 일어나게 되어 활성을 갖게 되기 때문인 것으로 판단된다.On the other hand, the phosphonium-based compound catalyzes curing only when the desired curing temperature or more, and there is no curing catalyst activity when the phosphonium compound is not the desired curing temperature. This is believed to be because the ionic bond between the phosphonium cation and the zinc center metal anion is dissociated at a specific temperature and becomes active.
일반적으로 경화반응의 진행은 에폭시 수지 조성물이 액체인 경우 점도의 상승, 유동성 저하를 가져올 수 있고, 에폭시 수지 조성물이 고체인 경우 점성을 발현시킬 수 있다. 그러나, 본 발명의 포스포늄계 화합물은 상기와 같이 경화 온도에서만 촉매 활성을 가지기 때문에, 에폭시 수지 조성물에 첨가되었을 때, 에폭시 수지의 점도 변화를 최소화할 수 있으며, 이로 인해 장시간 동안 우수한 저장 안정성을 구현할 수 있다.  In general, the progress of the curing reaction may cause an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and may exhibit viscosity when the epoxy resin composition is a solid. However, since the phosphonium-based compound of the present invention has a catalytic activity only at the curing temperature as described above, when added to the epoxy resin composition, it is possible to minimize the viscosity change of the epoxy resin, thereby realizing excellent storage stability for a long time Can be.
다음으로, 본 발명의 에폭시 수지 조성물에 대해 설명한다. Next, the epoxy resin composition of this invention is demonstrated.
본 발명의 에폭시 수지 조성물은 에폭시 수지, 경화제, 무기충전제, 경화촉매 중 하나 이상을 포함할 수 있다. The epoxy resin composition of the present invention may include at least one of an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst.
에폭시수지Epoxy resin
에폭시 수지는 분자 중에 적어도 1개 이상의 에폭시기를 갖는 것으로, 예를 들면, 분자 중에 적어도 2개 이상의 에폭시기를 갖는 것이거나, 분자 중에 2개 이상의 에폭시기 및 1개 이상의 수산기를 갖는 것일 수 있다. The epoxy resin may have at least one epoxy group in a molecule, for example, may have at least two or more epoxy groups in a molecule, or may have two or more epoxy groups and one or more hydroxyl groups in a molecule.
또한, 에폭시 수지는 고상의 에폭시 수지, 액상의 에폭시 수지 중 하나 이상을 포함할 수 있고 바람직하게는 고상의 에폭시 수지를 사용할 수 있다.In addition, the epoxy resin may include at least one of a solid epoxy resin and a liquid epoxy resin, and preferably a solid epoxy resin may be used.
상기 에폭시 수지의 구체적인 예로는, 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시 수지, 나프탈렌형 에폭시 수지, 글리시딜아민형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비페닐형 에폭시 수지, 선형 지방족 에폭시 수지, 지환식에폭시 수지, 복소환식 에폭시 수지, 스피로환 함유 에폭시 수지, 시클로헥산디메탄올형 에폭시 수지, 트리메틸올형 에폭시 수지, 페놀아랄킬형 에폭시 수지, 할로겐화 에폭시 수지 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 포함될 수도 있다. Specific examples of the epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, tert-butyl catechol type epoxy resins, naphthalene type epoxy resins, glycidylamine type epoxy resins, and cresolno. Volac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, phenol aralkyl type epoxy resin And halogenated epoxy resins. These may be included alone or in combination of two or more thereof.
보다 구체적으로는, 상기 에폭시 수지는 하기 [화학식 2]로 표시되는 비페닐형 에폭시 수지 및/또는 하기 [화학식 3]으로 표시되는 페놀아랄킬형 에폭시 수지일 수 있다.More specifically, the epoxy resin may be a biphenyl type epoxy resin represented by the following [Formula 2] and / or a phenol aralkyl type epoxy resin represented by the following [Formula 3].
[화학식 2][Formula 2]
Figure PCTKR2015010729-appb-I000013
Figure PCTKR2015010729-appb-I000013
(상기 화학식 2에서, R은 탄소수 1 내지 4의 알킬기, n의 평균치는 0 내지 7 이다 (In Formula 2, R is an alkyl group having 1 to 4 carbon atoms, the average value of n is 0 to 7
[화학식 3][Formula 3]
Figure PCTKR2015010729-appb-I000014
Figure PCTKR2015010729-appb-I000014
(상기 화학식 3에서, m의 평균치는 1 내지 7 이다.) (In Formula 3, the average value of m is 1 to 7.)
상기 에폭시 수지는 조성물 중 고형분 함량을 기준으로 2 내지 17중량%, 예를 들면 3 내지 15중량%, 예를 들면 3 내지 12중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다.The epoxy resin may be included 2 to 17% by weight, for example 3 to 15% by weight, for example 3 to 12% by weight based on the solids content of the composition. In the above range, the curability of the composition may not be lowered.
경화제Hardener
경화제는 페놀아랄킬형 페놀수지, 페놀노볼락형 페놀수지, 자일록형 페놀수지, 크레졸 노볼락형 페놀수지, 나프톨형 페놀수지, 테르펜형 페놀수지, 다관능형 페놀수지, 디시클로펜타디엔계 페놀수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄, 디아미노디페닐설폰등의 방향족 아민 등을 들 수 있다. 바람직하게는, 상기 경화제는 1개 이상의 수산기를 갖는 페놀수지일 수 있다. The curing agent is a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylock type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, a dicyclopentadiene type phenol resin, Novolac-type phenolic resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, dia Aromatic amines, such as a minodiphenylmethane and a diamino diphenyl sulfone, etc. are mentioned. Preferably, the curing agent may be a phenol resin having one or more hydroxyl groups.
예를 들면, 상기 경화제는 하기 화학식 4의 자일록형 페놀수지 및/또는 하기 화학식 5의 페놀아랄킬형 페놀수지일 수 있다.For example, the curing agent may be a xylox phenol resin of Formula 4 and / or a phenol aralkyl type phenol resin of Formula 5 below.
[화학식 4][Formula 4]
Figure PCTKR2015010729-appb-I000015
Figure PCTKR2015010729-appb-I000015
(상기 화학식 4에서 a의 평균치는 0 내지 7이다.)(The average value of a in Formula 4 is 0 to 7.)
[화학식 5][Formula 5]
Figure PCTKR2015010729-appb-I000016
Figure PCTKR2015010729-appb-I000016
(상기 화학식 5에서 b의 평균치는 1 내지 7이다)(In Formula 5, the average value of b is 1 to 7)
경화제는 에폭시 수지 조성물 중 고형분 함량을 기준으로 0.5 내지 13중량%, 예를 들면 1 내지 10중량%, 예를 들면 2 내지 8중량% 포함될 수 있다. 상기 범위에서, 조성물의 경화성이 저하되지 않을 수 있다. The curing agent may be included in the epoxy resin composition 0.5 to 13% by weight, for example 1 to 10% by weight, for example 2 to 8% by weight based on the solids content. In the above range, the curability of the composition may not be lowered.
무기충전제Inorganic filler
본 발명의 에폭시 수지 조성물은 무기충전제를 포함할 수 있다. 무기충전제는 조성물의 기계적 물성의 향상과 저응력화를 높일 수 있다. 무기충전제의 예로는 용융실리카, 결정성실리카, 탄산칼슘, 탄산마그네슘, 알루미나, 마그네시아, 클레이(clay), 탈크(talc), 규산칼슘, 산화티탄, 산화안티몬, 유리섬유 등을 들 수 있다. The epoxy resin composition of the present invention may include an inorganic filler. Inorganic fillers can increase the mechanical properties and low stress of the composition. Examples of the inorganic fillers include molten silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fibers.
이 중에서도, 선팽창계수가 낮은 용융실리카가 저응력화 측면에서 바람직하다. 용융실리카는 진비중(true specific gravity)이 2.3이하인 비결정성 실리카를 의미하는 것으로, 결정성 실리카를 용융하여 만들거나 다양한 원료로부터 합성한 비결정성 실리카도 포함된다. 용융실리카의 형상 및 입경은 특별히 한정되지는 않지만, 평균 입경 5 내지 30㎛의 구상 용융실리카를 50 내지 99중량%, 평균입경 0.001 내지 1㎛의 구상 용융실리카를 1내지 50중량%를 포함한 용융실리카 혼합물을 전체 무기충전제에 대하여 40 내지 100중량%가 되도록 포함하는 것이 좋다. 또한, 용도에 맞춰 그 최대 입경을 45㎛, 55㎛ 및 75㎛ 중 어느 하나로 조정해서 사용할 수가 있다. 상기 구상 용융실리카에는 도전성의 카본이 실리카 표면에 이물질로서 포함되는 경우가 있으나 극성 이물질의 혼입이 적은 물질을 선택하는 것이 바람직하다.Among them, molten silica having a low coefficient of linear expansion is preferable in terms of low stress. Molten silica refers to amorphous silica having a true specific gravity of 2.3 or less, and also includes amorphous silica made by melting crystalline silica or synthesized from various raw materials. The shape and particle size of the molten silica are not particularly limited, but the molten silica includes 50 to 99% by weight of spherical molten silica having an average particle diameter of 5 to 30 µm and 1 to 50% by weight of spherical molten silica having an average particle diameter of 0.001 to 1 µm. It is preferable to include the mixture to be 40 to 100% by weight based on the total inorganic filler. Moreover, according to a use, the maximum particle diameter can be adjusted and used in any one of 45 micrometers, 55 micrometers, and 75 micrometers. In the spherical molten silica, conductive carbon may be included as a foreign matter on the silica surface, but it is preferable to select a material having a small amount of polar foreign matter mixed therein.
무기충전제의 사용량은 성형성, 저응력성, 및 고온강도 등의 요구 물성에 따라 다르다. 구체예에서는 무기충전제는 에폭시수지 조성물 중 70 내지 95중량%, 예를 들면 75 내지 92중량%로 포함될 수 있다. 상기 범위에서, 에폭시 수지 조성물의 난연성, 유동성 및 신뢰성을 확보할 수 있다.The amount of the inorganic filler used depends on the required physical properties such as formability, low stress, and high temperature strength. In embodiments, the inorganic filler may be included in 70 to 95% by weight, for example 75 to 92% by weight of the epoxy resin composition. Within this range, flame retardancy, fluidity and reliability of the epoxy resin composition can be ensured.
경화촉매Curing catalyst
본 발명의 에폭시 수지 조성물은 상기 [화학식 1]로 표시되는 포스포늄계 화합물을 포함하는 경화촉매를 포함할 수 있다. 이때, 상기 [화학식 1]로 표시되는 포스포늄계 화합물은 에폭시 수지 조성물 중 0.01 내지 5중량%, 예를 들면 0.02 내지 1.5중량%, 예를 들면 0.05 내지 1.5중량%로 포함될 수 있다. 상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다. The epoxy resin composition of the present invention may include a curing catalyst containing a phosphonium-based compound represented by the above [Formula 1]. In this case, the phosphonium-based compound represented by [Formula 1] may be included in 0.01 to 5% by weight, for example 0.02 to 1.5% by weight, for example 0.05 to 1.5% by weight in the epoxy resin composition. In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
한편, 본 발명의 에폭시 수지 조성물은 포스포늄을 포함하지 않는 비-포스포늄계 경화촉매를 더 포함할 수 있다. 비-포스포늄계 경화촉매로는 3급 아민 경화촉매, 유기금속화합물 경화촉매, 유기인화합물 경화촉매, 이미다졸 경화촉매 및 붕소화합물 경화촉매 등이 사용 가능하다. 3급 아민 경화촉매에는 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디에틸아미노에탄올, 트리(디메틸아미노메틸)페놀, 2-2-(디메틸아미노메틸)페놀, 2,4,6-트리스(디아미노메틸)페놀과 트리-2-에틸헥실산염 등이 있다. 유기 금속화합물 경화촉매에는 크로뮴아세틸아세토네이트, 징크아세틸아세토네이트, 니켈아세틸아세토네이트 등이 있다. 유기인화합물 경화촉매에는 트리스-4-메톡시포스핀, 트리페닐포스핀, 트리페닐포스핀트리페닐보란, 트리페닐포스핀-1,4-벤조퀴논 부가물 등이 있다. 이미다졸류 경화촉매에는 2-메틸이미다졸,　2-페닐이미다졸, 2-아미노이미다졸, 2-메틸-1-비닐이미다졸, 2-에틸-4-메틸이미다졸, 2-헵타데실이미다졸 등이 있다. 붕소화합물 경화촉매에는 트리페닐포스핀 테트라페닐보레이트, 테트라페닐보론염, 트리플루오로보란-n-헥실아민, 트리플루오로보란모노에틸아민, 테트라플루오로보란트리에틸아민, 테트라플루오로보란아민 등이 있다. 이외에도 1,5-디아자바이시클로[4.3.0]논-5-엔(1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 1,8-디아자바이시클로[5.4.0]운덱-7-엔(1,8-diazabicyclo[5.4.0]undec-7-ene: DBU) 및 페놀노볼락 수지염 등을 사용할 수 있다. 특히 바람직하게는, 상기 비-포스포늄계 경화촉매로 유기인화합물 경화촉매, 붕소화합물 경화촉매, 아민계 경화촉매, 또는 이미다졸계 경화촉매 등을 단독 혹은 혼합하여 사용할 수 있다. 또한, 상기 비-포스포늄계 경화촉매로 에폭시 수지 또는 경화제와 선반응하여 만든 부가물을 사용하는 것도 가능하다. On the other hand, the epoxy resin composition of the present invention may further include a non-phosphonium-based curing catalyst containing no phosphonium. As the non-phosphonium-based curing catalysts, tertiary amine curing catalysts, organometallic compound curing catalysts, organophosphorus compound curing catalysts, imidazole curing catalysts and boron compound curing catalysts can be used. Tertiary amine curing catalysts include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (dia) Minomethyl) phenol and tri-2-ethylhexyl acid salt. Organometallic compound curing catalysts include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Examples of organophosphorus curing catalysts include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct and the like. The imidazole curing catalysts include 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole, 2- Heptadecylimidazole and the like. Examples of the boron compound curing catalyst include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, and the like. There is this. In addition, 1,5- diazabicyclo [4.3.0] non-5-ene (1, 5- diazabicyclo [4.3.0] non-5-ene: DBN), 1, 8- diazabicyclo [5.4. 0] undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts may be used. Particularly preferably, as the non-phosphonium-based curing catalyst, an organophosphorus curing catalyst, a boron compound curing catalyst, an amine curing catalyst, or an imidazole curing catalyst may be used alone or in combination. It is also possible to use an adduct made by pre-reaction with an epoxy resin or a curing agent as the non-phosphonium-based curing catalyst.
본 발명의 포스포늄계 화합물은 전체 경화촉매 중 10 내지 100중량%, 예를 들면 60 내지 100중량%로 포함될 수 있고, 상기 범위에서 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보 효과가 있을 수 있다. The phosphonium-based compound of the present invention may be included in 10 to 100% by weight, for example 60 to 100% by weight of the total curing catalyst, the curing reaction time is not delayed in the above range, there is an effect of ensuring the fluidity of the composition Can be.
한편, 상기 경화촉매는 에폭시수지 조성물 중 0.01 내지 5중량%, 예를 들면 0.02 내지 1.5중량%, 예를 들면 0.05 내지 1.5중량%로 포함될 수 있다. 상기 범위에서, 경화 반응 시간이 지연되지 않고, 조성물의 유동성이 확보될 수 있다.On the other hand, the curing catalyst may be included in 0.01 to 5% by weight, for example 0.02 to 1.5% by weight, for example 0.05 to 1.5% by weight of the epoxy resin composition. In the above range, the curing reaction time is not delayed, and the fluidity of the composition can be ensured.
한편, 본 발명의 에폭시 수지 조성물은 상기 성분들 이외에 에폭시 수지 조성물에 포함되는 통상의 첨가제를 더 포함할 수 있다. 상기 첨가제는 커플링제, 이형제, 응력 완화제, 가교 증진제, 레벨링제, 착색제 중 하나 이상을 포함할 수 있다.Meanwhile, the epoxy resin composition of the present invention may further include conventional additives included in the epoxy resin composition in addition to the above components. The additive may include one or more of a coupling agent, a release agent, a stress relaxer, a crosslinking enhancer, a leveling agent, and a coloring agent.
상기 커플링제로는 에폭시실란, 아미노실란, 머캡토실란, 알킬실란 및 알콕시실란으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 상기 커플링제는 에폭시수지 조성물 중 0.1 내지 1중량%로 포함될 수 있다.The coupling agent may be one or more selected from the group consisting of epoxysilane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto. The coupling agent may be included in 0.1 to 1% by weight of the epoxy resin composition.
상기 이형제로는 파라핀계 왁스, 에스테르계 왁스, 고급 지방산, 고급 지방산 금속염, 천연 지방산 및 천연 지방산 금속염으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다. 상기 이형제는 에폭시수지 조성물 중 0.1 내지 1중량%로 포함될 수 있다.The release agent may be used at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt. The release agent may be included in 0.1 to 1% by weight of the epoxy resin composition.
상기 응력 완화제로는 변성 실리콘 오일, 실리콘 엘라스토머, 실리콘 파우더 및 실리콘 레진으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있지만, 이에 제한되지 않는다. 상기 응력 완화제는 에폭시 수지 조성물 중 0 내지 6.5중량%, 예를 들면 0 내지 1중량%, 예를 들면 0.1 내지 1중량%로 함유되는 것이 바람직하다. 이때, 상기 변성 실리콘 오일로는 내열성이 우수한 실리콘 중합체가 좋으며, 에폭시 관능기를 갖는 실리콘 오일, 아민 관능기를 갖는 실리콘 오일 및 카르복실 관능기를 갖는 실리콘 오일 등을 1종 또는 2종 이상 혼합하여 사용할 수 있다. 상기 실리콘 오일은 전체 에폭시 수지 조성물에 대해 0.05 내지 1.5 중량% 정도의 함량으로 포함되는 것이 바람직하다. 실리콘 오일의 함량이 1.5 중량% 를 초과할 경우에는 표면 오염이 발생하기 쉽고 레진 블리드(bleed)가 길어질 우려가 있으며, 0.05 중량% 미만으로 사용 시에는 충분한 저탄성률을 얻을 수가 없게 되는 문제점이 있을 수 있다. 또한, 상기 실리콘 파우더는 중심입경이 15㎛ 이하인 것을 사용하는 것이 성형성 저하 방지의 측면에서 바람직하다. 한편, 상기 실리콘 파우더는 전체 수지 조성물에 대하여 0 내지 5중량%, 예를 들면 0.1 내지 5중량%로 함유될 수 있다.The stress relaxing agent may be used one or more selected from the group consisting of modified silicone oil, silicone elastomer, silicone powder and silicone resin, but is not limited thereto. The stress relaxation agent is preferably contained in 0 to 6.5% by weight, for example 0 to 1% by weight, for example 0.1 to 1% by weight in the epoxy resin composition. In this case, as the modified silicone oil, a silicone polymer having excellent heat resistance is good, and silicone oil having an epoxy functional group, silicone oil having an amine functional group, silicone oil having a carboxyl functional group, and the like may be used alone or in combination of two or more kinds. . The silicone oil is preferably included in an amount of about 0.05 to 1.5% by weight based on the total epoxy resin composition. If the content of silicone oil exceeds 1.5% by weight, surface contamination is likely to occur and the resin bleed may be long, and when used below 0.05% by weight, sufficient low modulus of elasticity may not be obtained. have. In addition, it is preferable to use the silicone powder having a central particle diameter of 15 μm or less from the viewpoint of preventing moldability deterioration. On the other hand, the silicon powder may be contained in 0 to 5% by weight, for example 0.1 to 5% by weight based on the total resin composition.
상기 첨가제는 에폭시 수지 조성물 중 0.1 내지 10중량%, 예를 들면 0.1 내지 3중량%로 포함될 수 있다.The additive may be included in 0.1 to 10% by weight, for example 0.1 to 3% by weight of the epoxy resin composition.
한편, 본 발명의 에폭시 수지 조성물은 EMMI-1-66에서 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스에 의한 유동길이가 약 59-75inch(약 1.4986m~1.905m)정도인 것이 바람직하다. 유동 길이가 상기 범위를 만족할 경우, 반도체 소자의 밀봉 소재로 유용하게 사용될 수 있다. Meanwhile, the epoxy resin composition of the present invention preferably has a flow length of about 59-75 inches (about 1.4986 m to 1.905 m) at 175 ° C. and 70 kgf / cm 2 in EMMI-1-66. When the flow length satisfies the above range, it may be usefully used as a sealing material of a semiconductor device.
또한, 본 발명의 에폭시 수지 조성물은 하기 [식 1]에 의해 측정된 경화수축률이 약0.4% 미만, 예를 들면 약 0.01 내지 약 0.39% 정도인 것이 바람직하다. 경화수축률이 상기 수치 범위를 만족할 경우, 반도체 소자의 밀봉 소재로 유용하게 사용될 수 있다. In addition, the epoxy resin composition of the present invention preferably has a curing shrinkage rate of less than about 0.4%, for example, about 0.01 to about 0.39% measured by the following [formula 1]. When the curing shrinkage satisfies the numerical range, it may be usefully used as a sealing material for semiconductor devices.
[식 1][Equation 1]
경화수축률= ｜C - D｜/C × 100Cure Shrinkage Rate = ｜ C-D ｜ / C × 100
(상기 식 1에서, C는 에폭시 수지 조성물을 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 175℃에서 후경화(PMC:post molding cure)하고, 냉각시킨 후 얻은 시편의 길이이다).(In Formula 1, C is the length of the specimen obtained by transfer molding press the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is post-cure (PMC: post molding cure), and cooled the specimen at 175 ℃ Is the length of the specimen obtained).
한편, 상기 에폭시 수지 조성물 중 에폭시 수지는 단독으로 사용될 수도 있고, 에폭시 수지와 경화제, 경화촉매, 이형제, 커플링제, 및 응력완화제 등의 첨가제를 멜트 마스터 배치(melt master batch)와 같은 선반응을 시켜 만든 부가 화합물 형태로 포함될 수 있다. 에폭시 수지 조성물을 제조하는 방법은 특별히 제한되지 않으며, 예를 들면, 조성물에 포함되는 각 구성성분을 헨셀 믹서나 뢰디게 믹서를 이용하여 균일하게 혼합한 후, 롤 밀이나 니이더로 90~120℃에서 용융 혼련하고, 냉각 및 분쇄 과정을 거쳐 제조될 수 있다.On the other hand, the epoxy resin in the epoxy resin composition may be used alone, the additives such as the epoxy resin and the curing agent, curing catalyst, release agent, coupling agent, and stress release agent by a linear reaction such as melt master batch (melt master batch) It may be included in the form of additional compounds made. The method for producing the epoxy resin composition is not particularly limited, and for example, each component contained in the composition may be uniformly mixed using a Henschel mixer or a Rodige mixer, and then 90 to 120 ° C with a roll mill or kneader. It can be prepared by melt kneading in the cooling, cooling and grinding process.
한편, 상기 에폭시 수지 조성물은 유리전이온도가 100℃ 내지 130℃, 예를 들면 123℃ 내지 125℃ 정도인 것이 바람직하다. 유리전이온도가 상기 온도 범위을 만족할 때, 저온 경화의 효과가 있을 수 있다.On the other hand, the epoxy resin composition preferably has a glass transition temperature of 100 ℃ to 130 ℃, for example, about 123 ℃ to 125 ℃. When the glass transition temperature satisfies the temperature range, there may be an effect of low temperature curing.
본 발명의 수지 조성물의 용도는 반도체 소자 밀봉용도, 접착필름, 프리프레그 등의 절연수지시트, 회로기판, 솔더레지스트, 언더필제, 다이본딩재, 부품 보충 수지 용도 등의 에폭시 수지 조성물이 필요로 하는 광범위한 용도에 적용될 수 있으며, 특별히 제한되지 않는다.The resin composition of the present invention is required for use in epoxy resin compositions such as semiconductor device sealing applications, adhesive films, insulating resin sheets such as prepregs, circuit boards, solder resists, underfill agents, die bonding materials, and component supplement resin applications. It can be applied to a wide range of applications and is not particularly limited.
반도체 소자 Semiconductor device
다음으로 본 발명의 반도체 소자에 대해 설명한다. Next, the semiconductor element of this invention is demonstrated.
본 발명의 반도체 소자는 상기한 본 발명의 에폭시 수지 조성물을 사용하여 밀봉된다.The semiconductor element of this invention is sealed using the epoxy resin composition of this invention mentioned above.
도 1은 본 발명의 일 실시예에 따른 반도체 소자를 도시한 단면도이다. 도 1을 참조하면, 본 발명의 일 실시예에 따른 반도체 소자(100)는 배선기판(10), 상기 배선기판(10) 위에 형성된 범프(30), 상기 범프(30) 위에 형성된 반도체칩(20)을 포함하고, 상기 배선기판(10)과 반도체칩(20) 간의 갭이 에폭시 수지 조성물(40)에 의해 봉지될 수 있으며, 이때, 상기 에폭시 수지 조성물은 상기한 본 발명의 에폭시 수지 조성물일 수 있다.1 is a cross-sectional view illustrating a semiconductor device in accordance with an embodiment of the present invention. Referring to FIG. 1, a semiconductor device 100 according to an exemplary embodiment may include a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30. ), And the gap between the wiring board 10 and the semiconductor chip 20 may be sealed by the epoxy resin composition 40, wherein the epoxy resin composition may be the epoxy resin composition of the present invention described above. have.
도 2는 본 발명 다른 실시예에 따른 반도체 소자를 도시한 단면도이다. 도 2를 참조하면, 본 발명 다른 실시예에 따른 반도체 소자(200)는 배선기판(10), 상기 배선기판(10) 위에 형성된 범프(30), 상기 범프(30) 위에 형성된 반도체칩(20)을 포함하고, 상기 배선기판(10)과 반도체칩(20) 간의 갭 및 상기 반도체칩(30) 상부면 전체가 에폭시 수지 조성물(40)로 봉지될 수 있으며, 이때, 상기 에폭시 수지 조성물은 상기한 본 발명의 에폭시 수지 조성물일 수 있다.2 is a cross-sectional view illustrating a semiconductor device in accordance with another embodiment of the present invention. Referring to FIG. 2, a semiconductor device 200 according to another embodiment of the present invention may include a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30. It includes, the gap between the wiring board 10 and the semiconductor chip 20 and the entire upper surface of the semiconductor chip 30 may be sealed with an epoxy resin composition 40, wherein the epoxy resin composition is It may be an epoxy resin composition of the present invention.
도 1과 도 2에서 배선기판, 범프, 반도체 칩의 각각의 크기, 범프의 개수는 임의의 도시된 것으로서, 변경될 수 있다.In FIG. 1 and FIG. 2, the sizes of the wiring boards, bumps, and semiconductor chips, and the number of bumps are arbitrary and may be changed.
한편, 본 발명의 에폭시 수지 조성물을 이용하여 반도체 소자를 밀봉하는 방법으로는, 저압 트랜스퍼 성형 방법이 가장 일반적으로 사용될 수 있다. 그러나, 이에 한정되는 것은 아니며, 인젝션(injection) 성형 방법이나 캐스팅(casting) 방법 등의 방법으로도 성형될 수 있다. 상기 방법에 의해 구리 리드프레임, 철 리드프레임, 또는 상기 리드프레임에 니켈 및 구리로 팔라듐으로 이루어진 군으로부터 선택되는 1종 이상의 물질로 프리플레이팅된 리드프레임, 또는 유기계 라미네이트 프레임의 반도체 소자를 제조할 수 있다.On the other hand, as the method of sealing a semiconductor element using the epoxy resin composition of this invention, the low pressure transfer molding method can be used most commonly. However, the present invention is not limited thereto, and may be molded by an injection molding method or a casting method. By the above method, a semiconductor device of a copper lead frame, an iron lead frame, or a lead frame pre-plated with at least one material selected from the group consisting of palladium with nickel and copper on the lead frame, or an organic laminate frame can be manufactured. Can be.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 다만, 하기 실시예에 의해 본 발명이 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited by the following examples.
실시예 및 비교예에서 사용된 성분의 구체적인 사양은 다음과 같다.Specific specifications of the components used in Examples and Comparative Examples are as follows.
(A) 에폭시수지(A) epoxy resin
비페닐형 에폭시수지인 NC-3000(Nippon Kayaku)를 사용하였다.NC-3000 (Nippon Kayaku), a biphenyl type epoxy resin, was used.
(B) 경화제(B) curing agent
자일록형 페놀수지인　HE100C-10(Air Water)를 사용하였다.Xylol-type phenolic resin CHE100C-10 (Air Water) was used.
(C) 경화촉매(C) curing catalyst
(C1)1.7g 의 2,3-dihydroxynaphtalene을 메탄올 50ml 에 녹이고 Potassium hydroxide 1M을 10ml 첨가하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g 의 Zinc acetate를 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2　g의 Tetraphenylphosphonium bromide를 용액 메탄올5.0 mL에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1a의 화합물을 얻어냈다(수율: 85 %). NMR 데이타로 하기 화학식 1a 의 화합물임을 확인하였다.(C1) 1.7 g of 2,3-dihydroxynaphtalene was dissolved in 50 ml of methanol, 10 ml of Potassium hydroxide 1M was added, the mixture was stirred at room temperature for 1 hour, and 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.2 g of Tetraphenylphosphonium bromide was dissolved in 5.0 mL of methanol solution, and then reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and then the solvent of the obtained solution was removed at low pressure to obtain a compound of Formula 1a (yield: 85%). NMR data confirmed that the compound of Formula 1a.
[화학식 1a] [Formula 1a]
Figure PCTKR2015010729-appb-I000017
Figure PCTKR2015010729-appb-I000017
1H NMR (400 MHz, DMSO) 7.96 (t, J= 2.4Hz, 8H), 7.85-7.80 (m, 16H), 7.75-7.70 (m, 16H), 7.42-7.39 (d, 4H), 7.03-7.00 (d, 4H), 6.90 (s, 4H) ppm; 31P NMR (166 MHz, DMSO) 24.20 ppm1 H NMR (400 MHz, DMSO) 7.96 (t, J = 2.4 Hz, 8H), 7.85-7.80 (m, 16H), 7.75-7.70 (m, 16H), 7.42-7.39 (d, 4H), 7.03-7.00 (d, 4H), 6.90 (s, 4H) ppm; 31P NMR (166 MHz, DMSO) 24.20 ppm
(C2)1.1g 의 catechol 을 메탄올 50ml 에 녹이고 Potassium hydroxide 1M을 10ml 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 Zinc acetate 0.9 g을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2 g의 Tetraphenylphosphonium bromide 를 메탄올 5.0 mL에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1b의 화합물을 얻어냈다(수율: 83 %). NMR 데이타로 하기 화학식 1b의 화합물임을 확인하였다.(C2) 1.1 g of catechol was dissolved in 50 ml of methanol, 10 ml of Potassium hydroxide 1M was added, the mixture was stirred at room temperature for 1 hour, and 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.2 g of Tetraphenylphosphonium bromide was dissolved in 5.0 mL of methanol, and then reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and then the solvent of the obtained solution was removed at low pressure to obtain a compound of Formula 1b (yield: 83%). NMR data confirmed that the compound of Formula 1b.
[화학식 1b][Formula 1b]
Figure PCTKR2015010729-appb-I000018
Figure PCTKR2015010729-appb-I000018
1H NMR (400 MHz, DMSO) 7.97 (t, J　= 2.4Hz, 8H), 7.84-7.81 (m, 16H), 7.76-7.72 (m, 16H), 6.46 (s, 8H) ppm; 31P NMR (166 MHz, DMSO) 24.30 ppm1 H NMR (400 MHz, DMSO) 7.97 (t, J = 2.4 Hz, 8H), 7.84-7.81 (m, 16H), 7.76-7.72 (m, 16H), 6.46 (s, 8H) ppm; 31P NMR (166 MHz, DMSO) 24.30 ppm
(C3)1.3g 의 2-hydroxybenzenethiol 을 메탄올 50ml에 녹이고 Potassium hydroxide 1M을 10ml 첨가하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate 을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.2 g의 Tetraphenylphosphonium bromide 을 메탄올 5.0 mL에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1c의 화합물을 얻어냈다(수율: 86 %). NMR 데이타로 하기 화학식 1c의 화합물임을 확인하였다.(C3) 1.3 g of 2-hydroxybenzenethiol was dissolved in 50 ml of methanol, 10 ml of Potassium hydroxide 1M was added, the mixture was stirred at room temperature for 1 hour, and 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.2 g of Tetraphenylphosphonium bromide was dissolved in 5.0 mL of methanol, and then reacted at room temperature for about 2 hours. After the reaction was completed, insoluble solids were removed by filtration, and then the solvent of the obtained solution was removed at low pressure to obtain a compound of Formula 1c (yield: 86%). NMR data confirmed that the compound of Formula 1c.
[화학식 1c][Formula 1c]
Figure PCTKR2015010729-appb-I000019
Figure PCTKR2015010729-appb-I000019
1H NMR (400 MHz, DMSO) 7.96 (t, J= 2.4Hz, 8H), 7.84-7.80 (m, 16H), 7.76-7.72 (m, 16H), 7.27-7.24 (dd, 2H), 7.05-7.01 (dt, 2H), 6.70-6.67 (dd, 2H), 6.56-6.51 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm1 H NMR (400 MHz, DMSO) 7.96 (t, J = 2.4 Hz, 8H), 7.84-7.80 (m, 16H), 7.76-7.72 (m, 16H), 7.27-7.24 (dd, 2H), 7.05-7.01 (dt, 2H), 6.70-6.67 (dd, 2H), 6.56-6.51 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm
(C4)1.6g 의 thiosalicylic acid을 메탄올 50ml 에 녹이고　Potassium hydroxide 1M을 10ml 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate을 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.3 g의 (4-Hydroxy-phenyl)-triphenylphosphonium bromide 를 메탄올 5.0 mL에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1d의 화합물을 얻어냈다(수율: 92%). NMR 데이타로 하기 화학식 1d의 화합물임을 확인하였다.(C4) 1.6 g of thiosalicylic acid was dissolved in 50 ml of methanol, 10 ml of Potassium hydroxide 1M was added, the mixture was stirred at room temperature for 1 hour, and 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.3 g of (4-Hydroxy-phenyl) -triphenylphosphonium bromide was dissolved in 5.0 mL of methanol, and then reacted at room temperature for about 2 hours. After the reaction was completed, insoluble solids were removed by filtration, and then the solvent of the obtained solution was removed at low pressure to obtain a compound of formula 1d (yield: 92%). NMR data confirmed that the compound of Formula 1d.
[화학식 1d][Formula 1d]
Figure PCTKR2015010729-appb-I000020
Figure PCTKR2015010729-appb-I000020
1H NMR (400 MHz, DMSO) 7.94 (t, J= 2.4Hz, 6H), 7.82-7.76 (m, 12H), 7.73-7.66 (m, 12H), 7.56-7.54 (dd, 2H), 7.48-7.41 (m, 4H), 7.21-7.18 (dd, 2H), 7.11-7.09 (dd, 4H), 6.87-6.82 (dt, 2H), 6.75-6.70 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm1 H NMR (400 MHz, DMSO) 7.94 (t, J = 2.4 Hz, 6H), 7.82-7.76 (m, 12H), 7.73-7.66 (m, 12H), 7.56-7.54 (dd, 2H), 7.48-7.41 (m, 4H), 7.21-7.18 (dd, 2H), 7.11-7.09 (dd, 4H), 6.87-6.82 (dt, 2H), 6.75-6.70 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.40 ppm
(C5)(C5)
2.2g의 2-Hydroxy-N-phenyl-benzamide을 메탄올 50ml 에 녹이고 Potassium hydroxide 1M을 10ml 첨가 하여 이 혼합물을 1시간 동안 실온에서 교반시킨 후 0.9 g의 Zinc acetate를 첨가하였다. 이 혼합물을 실온에서 3시간 교반시킨 후 4.3 g의 (3-Hydroxy-phenyl)-triphenylphosphonium bromide을 메탄올 5.0 mL에 녹여 첨가한 후 상온에서 약 2시간 정도 반응시켰다. 반응이 끝난 뒤에 불용인 고체를 필터링으로 제거한 후 얻어진 용액의 용매를 저압에서 제거하여 화학식 1e의 화합물을 얻어냈다(수율: 90%). NMR 데이타로 하기 화학식 1e의 화합물임을 확인하였다.2.2 g of 2-Hydroxy-N-phenyl-benzamide was dissolved in 50 ml of methanol, 10 ml of Potassium hydroxide 1M was added, the mixture was stirred at room temperature for 1 hour, and 0.9 g of Zinc acetate was added thereto. After the mixture was stirred at room temperature for 3 hours, 4.3 g of (3-Hydroxy-phenyl) -triphenylphosphonium bromide was dissolved in 5.0 mL of methanol, and then reacted at room temperature for about 2 hours. After the reaction was completed, insoluble solids were removed by filtration, and then the solvent of the obtained solution was removed at low pressure to obtain a compound of Formula 1e (yield: 90%). NMR data confirmed that the compound of Formula 1e.
[화학식 1e][Formula 1e]
Figure PCTKR2015010729-appb-I000021
Figure PCTKR2015010729-appb-I000021
1H NMR (400 MHz, DMSO) 7.94-7.89 (t, J= 2.4Hz, 6H),7.82-7.66 (m, 30H), 7.36-7.33 (dd, 2H), 7.31-7.26 (dt, 4H), 7.15-7.09 (m, 4H), 7.02-6.91 (m, 6H), 6.66-6.63 (dd, 2H), 6.47-6.42 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.50 ppm1 H NMR (400 MHz, DMSO) 7.94-7.89 (t, J = 2.4 Hz, 6H), 7.82-7.66 (m, 30H), 7.36-7.33 (dd, 2H), 7.31-7.26 (dt, 4H), 7.15 -7.09 (m, 4H), 7.02-6.91 (m, 6H), 6.66-6.63 (dd, 2H), 6.47-6.42 (dt, 2H) ppm; 31P NMR (166 MHz, DMSO) 24.50 ppm
(C6) 트리페닐 포스핀 (Triphenyl phosphine)(C6) Triphenyl phosphine
(C7) 트리페닐 포스핀과 1,4-벤조퀴논의 부가 생성물(C7) addition product of triphenyl phosphine and 1,4-benzoquinone
(D) 무기 충전제: 평균입경 18㎛의 구상 용융실리카와 평균입경 0.5㎛의 구상 용융실리카의 9:1(중량비) 혼합물을 사용하였다.(D) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical molten silica having an average particle diameter of 18 µm and spherical molten silica having an average particle diameter of 0.5 µm was used.
(E) 커플링제(E) coupling agent
(e1) 머캡토프로필트리메톡시실란인 KBM-803(Shinetsu)과 (e2) 메틸트리메톡시실란인 SZ-6070(Dow Corning chemical)을 혼합하여 사용하였다. KBM-803 (Shinetsu), which is (e1) mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is (e2) methyltrimethoxysilane, were mixed and used.
(F) 첨가제 (F) additive
(f1) 이형제로 카르나우바왁스 및 (f2) 착색제로 카본 블랙 MA-600(Matsusita Chemical)을 사용하였다.Carnauba wax was used as the release agent (f1) and carbon black MA-600 (Matsusita Chemical) was used as the colorant (f2).
실시예 1~5 및 비교예 1~2Examples 1-5 and Comparative Examples 1-2
상기 각 성분들을 하기 표 1의 조성(단위: 중량부)에 따라 각 성분들을 평량한 후 헨셀 믹서를 이용하여 균일하게 혼합하여 분말 상태의 1차 조성물을 제조하였다. 이후 연속 니이더를 이용하여 95℃에서 용융 혼련한 후 냉각 및 분쇄하여 반도체 소자 밀봉용 에폭시수지 조성물을 제조하였다.The components were weighed according to the composition (unit: parts by weight) of Table 1 below, and then uniformly mixed using a Henschel mixer to prepare a primary composition in powder form. After the melt kneading at 95 ℃ using a continuous kneader and then cooled and pulverized to prepare an epoxy resin composition for sealing a semiconductor device.
구분division 실시예Example 비교예Comparative example
1One 22 33 44 55 1One 22
(A)(A) 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9 8.98.9
(B)(B) 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7 4.74.7
(C)(C) (C1)(C1) 0.40.4
(C2)(C2) 0.40.4
(C3)(C3) 0.40.4
(C4)(C4) 0.40.4
(C5)(C5) 0.40.4
(C6)(C6) 0.40.4
(C7)(C7) 0.40.4
(D)(D) 8585 8585 8585 8585 8585 8585 8585
(E)(E) (e1)(e1) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
(e2)(e2) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
(F)(F) (f1)(f1) 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
(f2)(f2) 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
실시예 1~5와 비교예1~2에 의해 제조한 에폭시 수지 조성물에 대해 이하에서 서술하는 측정방법을 통하여 물성을 평가하였다. 물성 평가 결과는 하기 표 2에 나타내었다.Physical properties were evaluated through the measuring method described below about the epoxy resin composition manufactured by Examples 1-5 and Comparative Examples 1-2. Physical property evaluation results are shown in Table 2 below.
(1) 유동성(inch): EMMI-1-66에 준하여 평가용 금형을 사용하여 175℃, 70kgf/cm2 에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 평가하고자 하는 에폭시 수지 조성물의 유동 길이를 측정하였다. 측정값이 높을수록 유동성이 우수하다. (1) Flowability (inch): The flow length of the epoxy resin composition to be evaluated using a transfer molding press at 175 ° C. and 70 kgf / cm 2 using an evaluation mold according to EMMI-1-66. Measured. The higher the measured value, the better the fluidity.
(2) 경화 수축율(%): 굴곡 강도 시편 제작용 금형을 사용하여 175℃, 70kgf/cm2에서 트랜스퍼 몰딩 프레스(transfer molding press)를 이용하여 평가하고자 하는 에폭시 수지 조성물의 성형시편(125×12.6×6.4mm)을 얻었다. 상기 성형시편을 175℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 다음 냉각한 후 성형시편의 길이를 캘리퍼스로 측정하였다. 경화 수축율은 다음과 같은 [식 1]로부터 계산하였다.(2) Hardening shrinkage (%): Molded specimen of epoxy resin composition to be evaluated by transfer molding press at 175 ° C. and 70 kgf / cm 2 using a bending strength specimen mold (125 × 12.6) X 6.4 mm). The molded specimen was placed in an oven at 175 ° C., and then cured for 4 hours, and then cooled. The length of the molded specimen was measured by a caliper. Cure shrinkage was calculated from the following [formula 1].
[식 1] [Equation 1]
경화수축률= ｜C - D｜/ C x 100Cure Shrinkage Rate = ｜ C-D ｜ / C x 100
(상기 [식 1]에서, C는 에폭시수지 조성물을 175℃, 70kgf/cm2의 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 175℃에서 4시간 후경화하고 냉각시킨 후 얻은 시편의 길이이다.)(In [Formula 1], C is the length of the specimen obtained by the transfer molding press of the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is the specimen obtained after curing and cooling the specimen at 175 ℃ 4 hours) Length.)
(3) 유리전이온도(℃): 열기계 분석기(Thermomechanical Analyzer, TMA)를 이용하여 에폭시 수지 조성물의 유리전이온도를 측정하였다. 이 때 TMA는 25℃에서 분당 10℃씩 온도를 상승시켜 300℃까지 측정하는 조건으로 설정하였다.(3) Glass transition temperature (° C.): The glass transition temperature of the epoxy resin composition was measured using a thermomechanical analyzer (TMA). At this time, TMA was set to the conditions of increasing the temperature by 10 ℃ per minute at 25 ℃ measured to 300 ℃.
(4) 흡습율(%): 평가하고자 하는 에폭시 수지 조성물을 금형 온도 170~180℃, 클램프 압력 70kgf/cm2, 이송 압력 1000psi, 이송 속도 0.5~1cm/s, 경화 시간 120초의 조건으로 성형하여 직경 50mm, 두께 1.0mm의 디스크 형태의 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시킨 직후 85℃, 85RH% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 흡습에 의한 무게 변화를 측정하여 다음 식 3에 의하여 흡습율을 계산하였다.(4) Hygroscopicity (%): molding the epoxy resin composition to be evaluated under the conditions of mold temperature 170 ~ 180 ℃, clamp pressure 70kgf / cm 2 , transfer pressure 1000psi, transfer rate 0.5 ~ 1cm / s, curing time 120 seconds A cured specimen in the form of a disk having a diameter of 50 mm and a thickness of 1.0 mm was obtained. The obtained specimens were placed in an oven at 170 to 180 ° C., and after 4 hours of post-curing (PMC: post molding cure), they were left at 85 ° C. and 85 RH% relative humidity for 168 hours, and then the weight change due to moisture absorption was measured. The moisture absorption was calculated by 3.
[식 3][Equation 3]
흡습율 = (흡습 후 시험편의 무게 - 흡습 전 시험편의 무게) ÷ (흡습 전 시험편의 무게)×100Hygroscopicity = (weight of test piece after moisture absorption-weight of test piece before moisture absorption) ÷ (weight of test piece before moisture absorption) × 100
(5) 부착력(kgf): 구리 금속 소자를 부착 측정용 금형에 맞는 규격으로 준비하고, 준비된 구리 금속 소자에 평가하고자 하는 에폭시 수지 조성물을 금형 온도170~180℃, 클램프 압력 70kgf/cm2, 이송 압력 1000psi, 이송속도 0.5~1cm/s, 경화　시간 120초의 조건으로 성형하여 경화 시편을 얻었다. 얻은 시편을 170~180℃의 오븐에 넣어 4시간 동안 후경화(PMC:post molding cure)시켰다. 이때 구리 금속 소자에 닿는 에폭시 수지 조성물의 면적은 40±1mm2이고, 부착력 측정은 각 측정 공정 당 12개의 시편에 대하여 UTM(Universal Testing Machine)을 이용하여 측정한 후 평균값으로 계산하였다.(5) Adhesion force (kgf): A copper metal element is prepared in a size suitable for a mold for measuring adhesion, and the epoxy resin composition to be evaluated on the prepared copper metal element is at a mold temperature of 170 to 180 ° C., a clamp pressure of 70 kgf / cm 2 , and transferred. Curing specimens were obtained by molding under conditions of a pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds. The obtained specimens were put in an oven at 170 to 180 ° C. and post-cured (PMC: post molding cure) for 4 hours. At this time, the area of the epoxy resin composition in contact with the copper metal element is 40 ± 1mm2, the adhesion was measured by the average value after measuring by using a universal testing machine (UTM) for 12 specimens per measurement process.
(6) 경화도(shore-D): 구리 금속 소자를 포함하는 가로 24mm, 세로 24mm, 두께 1mm인 eTQFP(exposed Thin Quad Flat Package) 패키지용 금형이 장착된 MPS(Multi Plunger System) 성형기를 이용하여 175℃에서 50, 60, 70, 80 그리고 90초간 평가하고자 하는 에폭시 수지 조성물을 경화시킨 후 금형 위의 패키지에 직접 Shore-D형 경도계로 경화시간에 따른 경화물의 경도를 측정하였다. 값이 높을 수록 경화도가 우수하다. (6) Shore-D: Using a multi-plunger system (MPS) molding machine equipped with a mold for an eTQFP (exposed thin quad flat package) package having a width of 24 mm, a length of 24 mm, and a thickness of 1 mm containing a copper metal element. After curing the epoxy resin composition to be evaluated at 175 ° C. for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product according to the curing time was measured with a Shore-D hardness tester directly on the package on the mold. The higher the value, the better the degree of curing.
(7) 저장안정성: 에폭시수지 조성물을 25℃/50RH%로 설정된 항온항습기에 1주간 보존하면서 24시간 간격으로 상기 (1)의 유동성 측정과 같은 방법으로 유동길이를 측정하고, 제조 직후의 유동길이에 대한 백분율(%)을 구했다. 이 백분율의 수치가 클수록 저장안정성이 양호한 것을 나타낸다. (7) Storage stability: The flow length was measured in the same manner as the flowability measurement of (1) at 24 hours intervals while keeping the epoxy resin composition in a constant temperature and humidity chamber set at 25 ° C / 50RH% for 1 week, and the flow length immediately after the preparation. The percentage for was obtained. The larger the value of this percentage, the better the storage stability.
(8) 신뢰성: 상기 휨 특성 평가용 eTQFP 패키지를 125℃에서 24시간 동안 건조시킨 후 5 사이클(1 사이클은 패키지를 -65℃에서 10분, 25℃에서 10분, 150℃에서 10분씩 방치하는 것을 나타냄)의 열충격 시험을 수행하였다. 이후 패키지를 85℃, 60% 상대 습도 조건 하에서 168시간 동안 방치시킨 후 260℃에서 30초 동안 IR 리플로우를 1회 통과시키는 것을 3회 반복하는 프리컨디션 조건 이후에 패키지의 외관 크랙 발생 유무를 광학 현미경으로 관찰하였다. 이후 비파괴 검사인 C-SAM(Scanning Acoustic Microscopy)를 이용하여 에폭시 수지 조성물과 리드프레임 간의 박리 발생 유무를 평가하였다.　패키지의 외관에 크랙이 발생하거나 에폭시 수지 조성물과 리드프레임간의 박리가 발생할 경우에는 패키지의 신뢰성을 확보할 수 없다.(8) Reliability: After drying the eTQFP package for evaluation of bending characteristics for 24 hours at 125 ℃ (5 cycles (1 cycle is 10 minutes at -65 ℃, 10 minutes at 25 ℃, 10 minutes at 150 ℃) Thermal shock test). After the package was left at 85 ° C. and 60% relative humidity for 168 hours, the package was subjected to optical cracking after preconditioning, which was repeated three times at 260 ° C. for 30 seconds. It was observed under a microscope. Then, the presence of peeling between the epoxy resin composition and the lead frame was evaluated by using a non-destructive test C-SAM (Scanning Acoustic Microscopy). If a crack occurs in the appearance of the package or peeling between the epoxy resin composition and the lead frame, the reliability of the package cannot be secured.
평가 항목Evaluation item 실시예Example 비교예Comparative example
1One 22 33 44 55 1One 22
기본물성Basic property 유동성(inch)Inch 7070 7171 7373 7676 7474 5252 5858
경화수축율(%)Hardening Shrinkage (%) 0.390.39 0.370.37 0.380.38 0.340.34 0.350.35 0.420.42 0.400.40
유리전이온도(℃)Glass transition temperature (℃) 123123 123123 124124 123123 124124 121121 122122
흡습율(%)Hygroscopicity (%) 0.250.25 0.250.25 0.240.24 0.250.25 0.240.24 0.250.25 0.260.26
부착력(kgf)Adhesion force (kgf) 7777 7474 7575 7777 7676 7272 7474
패키지평가Package Evaluation 경화 시간별 경화도(Shore-D)Curing degree by curing time (Shore-D) 50초50 seconds 7272 6969 7171 7373 6868 5252 6060
60초60 seconds 7373 7070 7373 7575 7272 6060 6464
70초70 seconds 7575 7373 7676 7777 7474 6464 6666
80초80 sec 7676 7575 7676 7878 7676 6767 7070
90초90 sec 7777 7676 7878 7979 7878 6767 7171
저장 안정성Storage stability 24시간24 hours 96%96% 97%97% 97%97% 98%98% 98%98% 90%90% 92%92%
48시간48 hours 94%94% 95%95% 92%92% 94%94% 94%94% 84%84% 88%88%
72시간72 hours 92%92% 93%93% 90%90% 92%92% 90%90% 74%74% 79%79%
신뢰성responsibility 외관크랙발생수Exterior cracking water 00 00 00 00 00 00 00
박리 발생수Peeling occurrence number 00 00 00 00 00 4545 2020
시험한 반도체수Number of semiconductors tested 8888 8888 8888 8888 8888 8888 8888
실시예 1~5는 높은 유동성을 나타내며, 저장안정성의 경우 72 시간 후의 결과에서도 유동성의 차이가 거의 없는 것을 확인할 수 있고, 외관 크랙이 발생하지 않아 내크랙성이 양호하며 박리발생이 없는 것으로 볼 때 내습 신뢰성도 우수하다는 것을 알 수 있다.Examples 1 to 5 show high fluidity, and in the case of storage stability, it can be seen that there is almost no difference in fluidity even after 72 hours. When the external crack does not occur, the crack resistance is good and no peeling occurs. It can be seen that the moisture resistance is also excellent.
실시예 4 및 5는 비교예 1 및 2와 비교할 때, 높은 유동성을 나타내며 경화 수축률이 작다. 또한 경화시간별 경화도를 비교할 때 짧은 경화시간에서도 더 높은 경화도를 나타내고 있는 것을 확인할 수 있다. 또한 저장안정성의 경우 72hr 후의 결과에서도 유동성의 차이가 거의 없는 것을 확인할 수 있다.Examples 4 and 5 show high fluidity and have low cure shrinkage when compared with Comparative Examples 1 and 2. In addition, when comparing the degree of cure by curing time, it can be seen that the degree of higher curing is shown even in a short curing time. In addition, it can be seen that there is little difference in fluidity even after 72hr in the case of storage stability.
반면에, 본 발명의 포스포늄계 화합물을 포함하지 않는 비교예 1및 2의 조성물은 저장안정성이 낮고, 경화수축률은 높고, 유동성은 낮으며, 부착력이 낮고, 신뢰성에 문제가 있으므로 패키지에 사용시 본 발명의 효과를 구현할 수 없음을 확인할 수 있다.On the other hand, the compositions of Comparative Examples 1 and 2, which do not contain the phosphonium-based compound of the present invention, have low storage stability, high curing shrinkage rate, low fluidity, low adhesion, and reliability problems. It can be seen that the effects of the invention can not be implemented.
이상 본 발명의 실시예들을 설명하였으나, 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (11)

  1. 하기 [화학식 1]로 표시되는 포스포늄계 화합물.A phosphonium compound represented by the following [Formula 1].
    [화학식 1][Formula 1]
    Figure PCTKR2015010729-appb-I000022
    Figure PCTKR2015010729-appb-I000022
    (상기 [화학식 1]에서, R1, R2, R3 및 R4 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, (In [Formula 1], R 1 , R 2 , R 3 and R 4 are each independently substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or Substituted or unsubstituted C1-C30 hydrocarbon group containing a hetero atom,
    X1 및X2는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, Y1, Y2, Y3, 및Y4 는 각각 독립적으로 산소원자(O), 황원자(S) 또는 치환된 질소원자(N)이다).X 1 and X 2 are each independently a substituted or unsubstituted C 1 to C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 6 to C 30 aromatic hydrocarbon group, or a substituted or unsubstituted C 1 to C 30 containing a hetero atom And a hydrocarbon group, Y 1 , Y 2 , Y 3 , and Y 4 are each independently an oxygen atom (O), a sulfur atom (S) or a substituted nitrogen atom (N)).
  2. 제1항에 있어서, 상기 포스포늄계 화합물은 하기 [화학식 1a] 내지 [화학식 1e]로 표시되는 화합물들 중 하나인 포스포늄계 화합물: The phosphonium compound of claim 1, wherein the phosphonium compound is one of the compounds represented by the following [Formula 1a] to [Formula 1e]:
    [화학식 1a][Formula 1a]
    Figure PCTKR2015010729-appb-I000023
    Figure PCTKR2015010729-appb-I000023
    [화학식 1b][Formula 1b]
    Figure PCTKR2015010729-appb-I000024
    Figure PCTKR2015010729-appb-I000024
    [화학식 1c][Formula 1c]
    Figure PCTKR2015010729-appb-I000025
    Figure PCTKR2015010729-appb-I000025
    [화학식 1d][Formula 1d]
    Figure PCTKR2015010729-appb-I000026
    Figure PCTKR2015010729-appb-I000026
    [화학식 1e][Formula 1e]
    Figure PCTKR2015010729-appb-I000027
    Figure PCTKR2015010729-appb-I000027
  3. 에폭시수지, 경화제, 무기충전제 및 경화촉매를 포함하고,Epoxy resin, hardener, inorganic filler and curing catalyst,
    상기 경화촉매는 제1항 및 제2항 중 어느 한 항의 포스포늄계 화합물을 포함하는 에폭시 수지 조성물.The curing catalyst is an epoxy resin composition comprising a phosphonium-based compound of any one of claims 1 and 2.
  4. 제3항에 있어서, 상기 에폭시 수지는 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 페놀노볼락형 에폭시 수지, tert-부틸 카테콜형 에폭시 수지, 나프탈렌형 에폭시 수지, 글리시딜아민형 에폭시 수지, 크레졸노볼락형 에폭시 수지, 비페닐형 에폭시 수지, 선형 지방족 에폭시 수지, 지환식 에폭시 수지, 복소환식 에폭시 수지, 스피로환 함유 에폭시 수지, 시클로헥산디메탄올형 에폭시 수지, 트리메틸올형 에폭시 수지, 페놀아랄킬형 에폭시 수지 및 할로겐화 에폭시 수지 중 하나 이상을 포함하는 에폭시 수지 조성물. The epoxy resin of claim 3, wherein the epoxy resin is a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, phenol aralkyl type An epoxy resin composition comprising at least one of an epoxy resin and a halogenated epoxy resin.
  5. 제3항에 있어서, 상기 경화제는, 페놀아랄킬형 페놀 수지, 페놀노볼락형 페놀 수지, 자일록형 페놀 수지, 크레졸 노볼락형 페놀 수지, 나프톨형 페놀수지, 테르펜형 페놀 수지, 다관능형 페놀 수지, 디시클로펜타디엔계 페놀 수지, 비스페놀 A와 레졸로부터 합성된 노볼락형 페놀수지, 트리스(하이드록시페닐)메탄, 디하이드록시바이페닐을 포함하는 다가 페놀 화합물, 무수 말레인산 및 무수 프탈산을 포함하는 산무수물, 메타페닐렌디아민, 디아미노디페닐메탄, 및 디아미노디페닐설폰 중 하나 이상을 포함하는 에폭시수지 조성물.The phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylox phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, polyfunctional type phenol resin, Dicyclopentadiene-based phenol resins, novolac-type phenol resins synthesized from bisphenol A and resol, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, maleic anhydride and phthalic anhydride An epoxy resin composition comprising at least one of anhydride, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
  6. 제3항에 있어서, 상기 경화촉매는 상기 에폭시 수지 조성물 중 0.01 내지 5중량%로 포함되는 에폭시수지 조성물.The epoxy resin composition of claim 3, wherein the curing catalyst is included in an amount of 0.01 to 5 wt% in the epoxy resin composition.
  7. 제3항에 있어서, 상기 포스포늄계 화합물은 상기 경화촉매 중 10 내지 100중량%로 포함되는 에폭시 수지 조성물.The epoxy resin composition of claim 3, wherein the phosphonium-based compound is included in an amount of 10 to 100 wt% in the curing catalyst.
  8. 제3항에 있어서, 상기 에폭시 수지 조성물은, 상기 에폭시수지 2 내지 17중량%, 상기 경화제 0.5 내지 13중량%, 상기 무기 충전제 70 내지 95중량%, 상기 경화촉매 0.01 내지 5중량%를 포함하는 에폭시 수지 조성물.The epoxy resin composition of claim 3, wherein the epoxy resin composition comprises 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, and 0.01 to 5 wt% of the curing catalyst. Resin composition.
  9. 제3항에 있어서, 상기 에폭시 수지 조성물은 72시간 경과 후 저장안정성이 80%이상인 에폭시 수지 조성물. The epoxy resin composition of claim 3, wherein the epoxy resin composition has a storage stability of 80% or more after 72 hours.
  10. 제4항에 있어서, 상기 에폭시 수지 조성물은 하기 [식 1]로 표시되는 경화수축률이 0.4% 미만인 에폭시 수지 조성물:The epoxy resin composition of claim 4, wherein the epoxy resin composition has a curing shrinkage ratio of less than 0.4% represented by the following [Formula 1]:
    [식 1] [Equation 1]
    경화수축률= ｜C - D｜/C × 100Cure Shrinkage Rate = ｜ C-D ｜ / C × 100
    (상기 식 1에서, C는 에폭시 수지 조성물을 175℃, 70kgf/cm2의 트랜스퍼 몰딩 프레스하여 얻은 시편의 길이, D는 상기 시편을 175℃에서 4시간 후경화하고 냉각시킨 후 얻은 시편의 길이이다).(In Formula 1, C is the length of the specimen obtained by the transfer molding press of the epoxy resin composition at 175 ℃, 70kgf / cm 2 , D is the length of the specimen obtained after curing and cooling the specimen at 175 ℃ 4 hours ).
  11. 제3항의 에폭시 수지 조성물을 사용하여 밀봉된 반도체 소자.The semiconductor element sealed using the epoxy resin composition of Claim 3.
PCT/KR2015/010729 2014-11-28 2015-10-12 Phosphonium-based compound, epoxy resin composition containing same, and semiconductor device manufactured using same WO2016085115A1 (en)

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