WO2014115725A1 - Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device - Google Patents

Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device Download PDF

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Publication number
WO2014115725A1
WO2014115725A1 PCT/JP2014/051123 JP2014051123W WO2014115725A1 WO 2014115725 A1 WO2014115725 A1 WO 2014115725A1 JP 2014051123 W JP2014051123 W JP 2014051123W WO 2014115725 A1 WO2014115725 A1 WO 2014115725A1
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sheet
resin composition
thermosetting resin
resin
group
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PCT/JP2014/051123
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French (fr)
Japanese (ja)
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祐作 清水
豊田　英志
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日東電工株式会社
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Priority to KR1020157022786A priority Critical patent/KR20150108916A/en
Priority to SG11201505714WA priority patent/SG11201505714WA/en
Priority to CN201480005497.4A priority patent/CN104937036A/en
Publication of WO2014115725A1 publication Critical patent/WO2014115725A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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

Definitions

  • the present invention relates to a sheet-like thermosetting resin composition for encapsulating electronic components, a resin-encapsulated semiconductor device, and a method for producing a resin-encapsulated semiconductor device.
  • sealing of electronic components such as semiconductor elements, capacitors and resistor elements on a mounting substrate is performed by transfer sealing with a powdered epoxy resin composition, potting with liquid epoxy resin composition, silicone resin, dispensing, printing, etc.
  • sheet sealing using a sheet-like thermosetting resin composition has been proposed as a cheaper and simpler sealing method.
  • Patent Document 1 describes an epoxy resin composition containing a specific composite metal hydroxide and the like and satisfying the flame retardancy standard (UL94V-0).
  • the strength after curing has not been studied.
  • a sheet-like thermosetting resin composition that satisfies the flame retardancy standard (UL94V-0) and has excellent strength has not been studied.
  • the present invention has been made in view of the above problems, and is a sheet-like thermosetting resin composition for encapsulating electronic components that satisfies the flame retardancy standard (UL94V-0) and has excellent strength after curing.
  • the purpose is to provide.
  • the content of silica is 70 to 93% by weight based on the entire thermosetting resin composition for encapsulating electronic components in sheet form, satisfying the flame retardancy standard (UL94V-0),
  • the present invention relates to a sheet-like thermosetting resin composition for encapsulating electronic components having a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour.
  • the sheet-like thermosetting resin composition for sealing electronic parts of the present invention contains a specific amount of silica, satisfies the flame retardancy standard (UL94V-0), and has a strength after curing in a specific range. Since the flame retardancy standard (UL94V-0) is satisfied, the flame retardancy is excellent, and since the strength after curing is in a specific range, a highly reliable resin-encapsulated semiconductor device can be manufactured.
  • the flame retardancy standard (UL94V-0) is satisfied, the flame retardancy is excellent, and since the strength after curing is in a specific range, a highly reliable resin-encapsulated semiconductor device can be manufactured.
  • the average particle size of the silica is preferably 0.1 to 30 ⁇ m.
  • the sheet-like thermosetting resin composition for encapsulating electronic components of the present invention preferably has a viscosity before curing of 5 ⁇ 10 3 Pa ⁇ s or less at 90 ° C.
  • a viscosity before curing is 5 ⁇ 10 3 Pa ⁇ s or less at 90 ° C.
  • the sheet-like thermosetting resin composition for encapsulating electronic components of the present invention is preferably produced by kneading extrusion.
  • kneading extrusion When a specific amount of silica is blended, it is difficult to form into a sheet, but it can be easily formed into a sheet by kneading and extruding.
  • the sheet-like thermosetting resin composition for encapsulating electronic components of the present invention preferably contains a phosphazene flame retardant. If a metal hydroxide such as magnesium hydroxide for a flame retardant is blended in order to satisfy the flame retardant standard (UL94V-0), the resin strength is lowered. In the present invention, by blending a phosphazene-based flame retardant, excellent flame retardancy can be obtained, and the strength after curing can be well adjusted to a specific range.
  • the present invention also relates to a resin-encapsulated semiconductor device obtained using the sheet-like thermosetting resin composition for encapsulating electronic components.
  • the present invention also relates to a method for manufacturing a resin-encapsulated semiconductor device including a step of encapsulating an electronic component using the sheet-like thermosetting resin composition for encapsulating an electronic component.
  • the sheet-like thermosetting resin composition for encapsulating electronic parts of the present invention has a silica content of 70 to 93% by weight based on the entire thermosetting resin composition for encapsulating electronic sheets. Yes, it satisfies the flame retardancy standard (UL94V-0) and has a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour.
  • the sheet-like thermosetting resin composition of the present invention is excellent in flame retardancy and strength after curing. By containing a phosphazene-based flame retardant as necessary, flame retardancy and strength after curing can be more suitably obtained.
  • a resin component which can be used by this invention For example, an epoxy resin, a phenol resin, a thermoplastic resin etc. are mentioned.
  • the epoxy resin is not particularly limited.
  • triphenylmethane type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene type Various epoxy resins such as an epoxy resin, a phenol novolac type epoxy resin, and a phenoxy resin can be used. These epoxy resins may be used alone or in combination of two or more.
  • the epoxy equivalent is 150 to 250 and the softening point or the melting point is 50 to 130 ° C., solid at room temperature.
  • triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are preferable.
  • a modified bisphenol A type epoxy resin having a flexible skeleton such as an acetal group or a polyoxyalkylene group is preferable, and a modified bisphenol A type epoxy resin having an acetal group is liquid and has good handling. Therefore, it can be particularly preferably used.
  • bisphenol F type epoxy resin is particularly preferable.
  • the epoxy equivalent of the epoxy resin is preferably 150 g / eq. Or more, more preferably 170 g / eq. That's it.
  • the epoxy equivalent of the epoxy resin is preferably 300 g / eq. Or less, more preferably 250 g / eq. It is as follows.
  • the epoxy equivalent of the epoxy resin can be measured by a method defined in JIS K 7236-2009.
  • the content of the epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, in 100% by weight of the resin component.
  • the content of the epoxy resin is preferably 60% by weight or less, more preferably 50% by weight or less.
  • the phenol resin is not particularly limited as long as it causes a curing reaction with the epoxy resin.
  • a phenol novolac resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolak resin, a resole resin, or the like is used.
  • These phenolic resins may be used alone or in combination of two or more.
  • a phenol novolac resin can be preferably used.
  • low hygroscopic materials such as phenol aralkyl resins and biphenyl aralkyl resins can also be suitably used.
  • the hydroxyl equivalent of the phenol resin is preferably 70 g / eq. Or more, more preferably 90 g / eq. That's it.
  • the hydroxyl equivalent of the phenol resin is preferably 300 g / eq. Or less, more preferably 250 g / eq. It is as follows.
  • the mixing ratio of epoxy resin and phenol resin is such that the total of hydroxyl groups in phenol resin is 0.7 to 1.5 equivalents per 1 equivalent of epoxy groups in epoxy resin. It is preferable to use 0.9 to 1.2 equivalents.
  • the total content of the epoxy resin and the phenol resin is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 65% by weight or more in 100% by weight of the resin component. When it is 50% by weight or more, the resin strength necessary for electronic component applications can be secured satisfactorily.
  • the total content of the epoxy resin and the phenol resin is preferably 98% by weight or less, more preferably 95% by weight or less, in 100% by weight of the resin component. When it is 98% by weight or less, a sheet-like thermosetting resin composition for encapsulating electronic components with good moldability can be obtained.
  • the sheet-like thermosetting resin composition of the present invention preferably contains a thermoplastic resin. Thereby, the softness
  • Thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplasticity.
  • examples thereof include polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins.
  • styrene-isobutylene-styrene block copolymers are also included.
  • These thermoplastic resins can be used alone or in combination of two or more. Of these, a styrene-isobutylene-styrene block copolymer is preferred from the standpoint that a good resin-encapsulated semiconductor device can be secured with good adhesion and resin strength.
  • the content of the thermoplastic resin is preferably 2% by weight or more, more preferably 5% by weight or more, in 100% by weight of the resin component. When it is 2% by weight or more, flexibility and strength after curing can be obtained satisfactorily.
  • the content of the thermoplastic resin is preferably 50% by weight or less, more preferably 40% by weight or less, in 100% by weight of the resin component. A flame retardance is favorably acquired as it is 50 weight% or less.
  • a fused silica powder from the point that it is excellent in a filling property and fluidity
  • the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, it is particularly preferable to use a spherical fused silica powder.
  • the average particle diameter of silica is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more. When it is 0.1 ⁇ m or more, there is little influence on flow reduction, and good moldability is obtained.
  • the average particle diameter of silica is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less. When the thickness is 20 ⁇ m or less, a highly reliable resin-encapsulated semiconductor device can be manufactured with little damage to electronic components during molding.
  • the average particle size can be derived by, for example, using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
  • the content of silica is 70% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more with respect to the entire sheet-like thermosetting resin composition. When it is 70% by weight or more, flame retardancy and strength after curing can be obtained satisfactorily.
  • the content of silica is 93% by weight or less, preferably 90% by weight or less, based on the entire sheet-like thermosetting resin composition. When it is 93% by weight or less, there is little influence on the flow reduction, and good moldability can be obtained.
  • the sheet-like thermosetting resin composition of the present invention preferably contains a phosphazene flame retardant.
  • a metal hydroxide such as magnesium hydroxide for a flame retardant
  • the strength after curing is reduced, but by blending a phosphazene flame retardant, the strength after curing can be well adjusted to a specific range.
  • the compound represented by Formula (1) or Formula (2) is preferable from the reason that it is excellent in a flame retardance and the intensity
  • R 1 and R 2 are the same or different and are monovalent having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, an allyl group, or these groups
  • R 3 and R 5 are the same or different and are monovalent having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, an allyl group, or these groups
  • R 4 represents an organic group
  • R 4 represents a divalent organic group having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group and an allyl group
  • y represents 3 to 25 Represents an integer
  • z represents an integer of 3 to 25.
  • alkoxy group for R 1 and R 2 examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
  • Examples of the phenoxy group for R 1 and R 2 include a group represented by the formula (3).
  • R 11 represents hydrogen, a hydroxyl group, an alkyl group, an alkoxy group, a glycidyl group, or a monovalent organic group having at least one group selected from the group consisting of these groups.
  • Examples of the alkyl group for R 11 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl and the like.
  • Examples of the alkoxy group for R 11 include the same groups as the alkoxy groups for R 1 and R 2 .
  • a phenoxy group is preferable and a group represented by the formula (3) is more preferable because flame retardancy and strength after curing can be favorably obtained.
  • x represents an integer of 3 to 25, but 3 to 10 is preferable and 3 to 4 is more preferable because flame retardancy and strength after curing can be obtained satisfactorily.
  • examples of the alkoxy group of R 3 and R 5 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
  • Examples of the phenoxy group for R 3 and R 5 include a group represented by the formula (3).
  • the monovalent organic group having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group and an allyl group in R 3 and R 5 is not particularly limited.
  • a phenoxy group is preferable and a group represented by the formula (3) is more preferable because flame retardancy and strength after curing can be favorably obtained.
  • Examples of the alkoxy group contained in the divalent organic group represented by R 4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
  • Examples of the phenoxy group contained in the divalent organic group represented by R 4 include a group represented by the formula (3).
  • y represents an integer of 3 to 25, but 3 to 10 is preferable because flame retardancy and strength after curing can be obtained satisfactorily.
  • z represents an integer of 3 to 25, but 3 to 10 is preferable because flame retardancy and strength after curing can be obtained satisfactorily.
  • the phosphorus element content contained in the phosphazene flame retardant is preferably 12% by weight or more.
  • the content of the phosphazene-based flame retardant is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.2% by weight or more with respect to the entire sheet-like thermosetting resin composition. It is. A flame retardance is favorably obtained as it is 0.05 weight% or more.
  • the content of the phosphazene-based flame retardant is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 5% by weight or less with respect to the entire sheet-like thermosetting resin composition. When the content is 30% by weight or less, there is little decrease in physical properties of the cured product (specifically, deterioration in physical properties such as glass transition temperature and high-temperature resin strength), and a highly reliable resin-encapsulated semiconductor device can be obtained.
  • the sheet-like thermosetting resin composition of the present invention preferably includes a curing accelerator.
  • the curing accelerator is not particularly limited as long as it allows curing to proceed. From the viewpoint of curability and storage stability, organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate, and imidazole. System compounds are preferably used.
  • the content of the curing accelerator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin.
  • the sheet-like thermosetting resin composition of the present invention contains other additives such as pigments including carbon black, silane coupling agents, and metal hydroxides as necessary. It can mix
  • the content of the metal hydroxide is preferably as small as possible, and is preferably 5% by weight or less, more preferably 1% by weight with respect to the whole sheet-like thermosetting resin composition. % Or less, more preferably 0% by weight.
  • strength after hardening can be favorably adjusted to a specific range as it is 5 weight% or less.
  • the sheet-like thermosetting resin composition of the present invention can be produced, for example, as follows. That is, first, each material for a sheet described above is uniformly dispersed and mixed to prepare a resin composition. And the prepared resin composition is formed in a sheet form.
  • this forming method for example, a method in which the prepared resin composition is extruded to form a sheet (kneading extrusion), or a varnish is prepared by dissolving or dispersing the prepared resin composition in an organic solvent or the like. And the method (solvent coating) etc. which manufacture this sheet
  • a plurality of the obtained sheet-like thermosetting resin compositions are laminated as necessary to obtain a sheet-like thermosetting resin composition having a predetermined thickness.
  • a release sheet such as a polyester film is bonded to protect the surface of the sheet-like thermosetting resin composition, and the sheet-like thermosetting resin composition is peeled off at the time of sealing. It may be.
  • methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, ethyl acetate etc. can be used, for example. These may be used alone or in combination of two or more. In general, it is preferable to use an organic solvent so that the solid content concentration of the varnish is in the range of 60 to 90% by weight.
  • thermosetting resin composition of the present invention By producing the sheet-like thermosetting resin composition of the present invention by kneading and extrusion, it can be easily formed into a sheet shape, and a uniform sheet with few voids (bubbles) can be obtained.
  • the above-mentioned components are melt-kneaded by a known kneader such as a mixing roll, a pressure kneader, or an extruder to prepare a kneaded product, and the obtained kneaded product is extruded. And a method of forming it into a sheet.
  • the temperature is preferably equal to or higher than the softening point of each component described above, for example, 30 to 150 ° C., and preferably 40 to 140 ° C., more preferably 60 to 120 in consideration of the thermosetting property of the epoxy resin. ° C.
  • the time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. Thereby, a kneaded material can be prepared.
  • a sheet-like thermosetting resin composition can be obtained by molding the obtained kneaded material by extrusion molding.
  • a sheet-like thermosetting resin composition can be molded by extrusion molding while keeping the kneaded material after melt-kneading in a high temperature state without cooling.
  • Such an extrusion method is not particularly limited, and examples thereof include a flat plate pressing method, a T-die extrusion method, a roll rolling method, a roll kneading method, an inflation extrusion method, a co-extrusion method, and a calendar molding method.
  • the extrusion temperature is preferably not less than the softening point of each component described above, and is 40 to 150 ° C., preferably 50 to 140 ° C., more preferably 70 to 120 ° C. in consideration of the thermosetting property and moldability of the epoxy resin. is there.
  • a sheet-like thermosetting resin composition can be shape
  • the thickness of the sheet-like thermosetting resin composition of the present invention is not particularly limited, but is preferably 0.1 mm to 1 mm, and preferably 0.1 mm to 0.7 mm. Electronic components can be satisfactorily sealed within the above range.
  • the sheet-like thermosetting resin composition of the present invention satisfies the flame retardance standard (UL94V-0) in the US UL standard.
  • the sheet-like thermosetting resin composition of the present invention preferably has a viscosity before curing of 5 ⁇ 10 5 Pa ⁇ s or less at 40 ° C. When it is 5 ⁇ 10 5 Pa ⁇ s or less, it is excellent in processability to a sheet shape or a roll shape, and can be produced in a sheet shape and a roll shape.
  • the lower limit of the viscosity is not particularly limited, but is preferably 3 ⁇ 10 2 Pa ⁇ s or more. When it is 3 ⁇ 10 2 Pa ⁇ s or more, the handling property is excellent.
  • the sheet-like thermosetting resin composition of the present invention preferably has a viscosity before curing of 5 ⁇ 10 3 Pa ⁇ s or less at 90 ° C. Good moldability is obtained as it is 5 ⁇ 10 3 Pa ⁇ s or less.
  • the lower limit of the viscosity is not particularly limited, but is preferably 3 ⁇ 10 2 Pa ⁇ s or more. When it is 3 ⁇ 10 2 Pa ⁇ s or more, molding is possible while maintaining the square shape of the resin.
  • the viscosity before curing can be measured by the method described in the examples.
  • the sheet-like thermosetting resin composition of the present invention has a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour.
  • the three-point bending strength is preferably 100 MPa or more.
  • the upper limit of the three-point bending strength is not particularly limited, but is, for example, 200 MPa or less, preferably 180 MPa or less. When it is 200 MPa or less, the processability of the cured product is excellent.
  • the three-point bending strength can be measured by the method described in the examples. In addition, in this specification, normal temperature is 23 degreeC.
  • the three-point bending strength can be controlled by the type of flame retardant, silica content, thermosetting resin content, epoxy equivalent of epoxy resin, hydroxyl equivalent of phenol resin, and the like. For example, by using a phosphazene flame retardant, increasing the amount of silica, increasing the thermosetting resin, using an epoxy resin having a large epoxy equivalent, using a phenol resin having a large hydroxyl equivalent, etc. Three-point bending strength can be increased.
  • the sheet-like thermosetting resin composition of the present invention is used for sealing electronic components such as a semiconductor wafer, a semiconductor chip, a capacitor, and a resistor. Especially, it can use suitably for sealing of a semiconductor wafer and a semiconductor chip.
  • the sheet-like thermosetting resin composition of the present invention can function as a sealing resin for protecting an electronic component and its accompanying elements from the external environment.
  • thermosetting resin composition It does not specifically limit as a sealing method, It can seal by a conventionally well-known method.
  • a method of embedding an electronic component in a sheet-like thermosetting resin composition and a method of covering an electronic component with a softened sheet-like thermosetting resin composition are representative.
  • An electronic component can be embedded in a sheet-like thermosetting resin composition by heat-pressing a laminated body provided with the composition by a parallel plate method.
  • the material of the support plate is not particularly limited, and examples thereof include metal materials such as SUS, and plastic materials such as polyimide, polyamideimide, polyether ether ketone, and polyether sulfone.
  • heat peelable adhesives such as a heat foamable adhesive, etc. are used.
  • a sheet-like thermosetting property is obtained by hot pressing a substrate, an electronic component disposed on the substrate, and a laminated structure including the sheet-like thermosetting resin composition disposed on the electronic component in a parallel plate method.
  • An electronic component can be embedded in the resin composition. It does not specifically limit as a board
  • substrate For example, a glass cloth base material epoxy resin copper clad laminated board, an iron nickel alloy board, a semiconductor wafer etc. are mentioned.
  • An electronic component can be sealed by placing the sheet-like thermosetting resin composition so as to cover the electronic component on the substrate and thermosetting the sheet-like thermosetting resin composition.
  • the resin-encapsulated semiconductor device obtained by such a method has excellent flame retardancy, strength after curing, and high reliability.
  • Epoxy resin YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin: epoxy equivalent 191, softening point 80 ° C.)
  • Phenol resin MEH7851SS manufactured by Meiwa Kasei Co., Ltd. (phenol aralkyl resin: hydroxyl group equivalent 203, softening point 67 ° C.)
  • Catalyst 2PHZ-PW (imidazole catalyst) manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Spherical fused silica FB-9454 manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Carbon black # 20 manufactured by Mitsubishi Chemical Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
  • Elastomer thermoplastic resin: SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka Corporation
  • Flame retardant A FP-100 manufactured by Fushimi Pharmaceutical (phosphazene flame retardant: compound represented by formula (4)) (In the formula, m represents an integer of 3 to 4.)
  • Flame retardant B Z-10 (magnesium hydroxide for flame retardant) manufactured by Tateho Chemical Co., Ltd.
  • Example 3 According to the blending ratio shown in Table 1, each component was mixed with a mixed solution containing methyl ethyl ketone and toluene in a ratio of 5: 5 to prepare a mixture having a component concentration of 90% by weight.
  • a varnish for coating was obtained by stirring the mixture for 10 minutes at 2000 rpm using a rotation and revolution mixer (Shinki Co., Ltd., Nertaro Awatori).
  • the coating varnish was coated on a 50 ⁇ m thick silicone-treated PET (Mitsubishi Chemical: MRF50) and then dried at 110 ° C. for 10 minutes with a hot air dryer to obtain a 100 ⁇ m thick sheet. Eight sheets were laminated by a vacuum laminator at a roll temperature of 90 ° C.
  • FIG. 1 is a diagram showing a state of a flame retardancy test.
  • Chamber Ring stand with windless test box clamp Industrial methane gas dry absorbent cotton: 50.8mm x 50.8mm x 6.4mm Constant temperature and humidity chamber: 23 ⁇ 2 °C, humidity 50 ⁇ 5%
  • test piece 1 of 127 mm x 12.7 mm x 1/32 inch was cut out from the resin sheet.
  • the test piece 1 was left in a constant temperature and humidity chamber (23 ⁇ 2 ° C., humidity 50 ⁇ 5%) for 48 hours or more and used for a flame retardancy test (pretreatment).
  • the requirements for flame retardancy standard are as follows. Regarding the test piece 1 of each example, a case where all the requirements are satisfied is indicated as “ ⁇ ”, and a case where the requirements are not satisfied is indicated as “X”. The results are shown in Table 1. 1) Each flame burning time is 10 seconds or less. 2) A set of five test pieces 1 is in contact with the flame 10 times in total, and the total flame burning time is 50 seconds or less. 3) Flame or red heat combustion does not reach clamp 2. 4) Do not ignite the dry absorbent cotton 3 placed below the test piece 1 by the flammable drops. 5) The red hot combustion time is within 30 seconds.
  • FIG. 2 is a diagram illustrating a three-point bending test.
  • a test piece 51 of 10 mm (width) ⁇ 40 mm (length) ⁇ 1 mm (thickness) was cut out from the resin sheet after being heated and cured at 150 ° C. for 1 hour.
  • a test piece 51 is placed on a support 52 having a fulcrum distance 61 of 20 mm, a pressing metal 53 is applied to the center of the test piece 51, and the test piece is tested.
  • a load was applied in a direction perpendicular to 51 (loading speed: 5 mm / min), and the three-point bending strength of the test piece 51 was measured. The measurement was performed at room temperature. The results are shown in Table 1.
  • Test piece 2 Clamp 3 Dry absorbent cotton 4 Burner 5 Flame 11 Flame height 12 Distance between test piece and top of burner 13 Distance between test piece and dry absorbent cotton 21 127 mm 22 12.7mm 51 Test Specimen 52 Support 53 Pressing Bracket 61 Distance between Supporting Points 62 Load Direction

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Abstract

Provided are: a thermosetting resin composition for sealing a sheet-form electronic component, the thermosetting resin composition complying with flame retardancy standard UL94 V-0 and having excellent post-curing strength; a high-reliability resin sealed semiconductor device; and a method of manufacturing a resin-sealed semiconductor device. The present invention relates to a thermosetting resin composition for sealing a sheet-form electronic component, the thermosetting resin composition having a specific silica content, compliance with flame retardancy standard UL94 V-0, and a three-point bending strength at ambient temperature following heating for 1 hour at 150°C and curing of 80 MPa or higher.

Description

シート状の電子部品封止用熱硬化性樹脂組成物、樹脂封止型半導体装置、及び樹脂封止型半導体装置の製造方法Sheet-like thermosetting resin composition for encapsulating electronic components, resin-encapsulated semiconductor device, and method for producing resin-encapsulated semiconductor device
本発明は、シート状の電子部品封止用熱硬化性樹脂組成物、樹脂封止型半導体装置、及び樹脂封止型半導体装置の製造方法に関する。 The present invention relates to a sheet-like thermosetting resin composition for encapsulating electronic components, a resin-encapsulated semiconductor device, and a method for producing a resin-encapsulated semiconductor device.
従来、実装基板上の半導体素子、コンデンサ及び抵抗素子などの電子部品の封止は、粉末状エポキシ樹脂組成物によるトランスファー封止や、液状エポキシ樹脂組成物、シリコーン樹脂などによるポッティング、ディスペンス、印刷などによって行われているが、近年、より安価で簡便な封止方法としてシート状の熱硬化性樹脂組成物を用いたシート封止が提案されている。 Conventionally, sealing of electronic components such as semiconductor elements, capacitors and resistor elements on a mounting substrate is performed by transfer sealing with a powdered epoxy resin composition, potting with liquid epoxy resin composition, silicone resin, dispensing, printing, etc. In recent years, sheet sealing using a sheet-like thermosetting resin composition has been proposed as a cheaper and simpler sealing method.
例えば、特許文献１には、特定の複合化金属水酸化物などを含有し、難燃性規格（ＵＬ９４Ｖ－０）を満足するエポキシ樹脂組成物が記載されている。しかしながら、硬化後の強度については検討されていない。このように、難燃性規格（ＵＬ９４Ｖ－０）を満足し、かつ優れた強度が得られるシート状の熱硬化性樹脂組成物については検討されていない。 For example, Patent Document 1 describes an epoxy resin composition containing a specific composite metal hydroxide and the like and satisfying the flame retardancy standard (UL94V-0). However, the strength after curing has not been studied. Thus, a sheet-like thermosetting resin composition that satisfies the flame retardancy standard (UL94V-0) and has excellent strength has not been studied.
特開２００３－８２２４１号公報JP 2003-82241 A
本発明は前記問題点に鑑みなされたものであり、難燃性規格（ＵＬ９４Ｖ－０）を満足し、かつ硬化後の強度に優れたシート状の電子部品封止用熱硬化性樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and is a sheet-like thermosetting resin composition for encapsulating electronic components that satisfies the flame retardancy standard (UL94V-0) and has excellent strength after curing. The purpose is to provide.
本発明は、シリカの含有量が、シート状の電子部品封止用熱硬化性樹脂組成物全体に対して、７０～９３重量％であり、難燃性規格（ＵＬ９４Ｖ－０）を満足し、１５０℃で１時間加熱し硬化させた後の常温における３点曲げ強度が８０ＭＰａ以上であるシート状の電子部品封止用熱硬化性樹脂組成物に関する。 In the present invention, the content of silica is 70 to 93% by weight based on the entire thermosetting resin composition for encapsulating electronic components in sheet form, satisfying the flame retardancy standard (UL94V-0), The present invention relates to a sheet-like thermosetting resin composition for encapsulating electronic components having a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour.
本発明のシート状の電子部品封止用熱硬化性樹脂組成物は、シリカを特定量含有し、難燃性規格（ＵＬ９４Ｖ－０）を満足し、硬化後の強度が特定範囲である。難燃性規格（ＵＬ９４Ｖ－０）を満足するため難燃性に優れ、また、硬化後の強度が特定範囲であるため、信頼性の高い樹脂封止型半導体装置を製造できる。 The sheet-like thermosetting resin composition for sealing electronic parts of the present invention contains a specific amount of silica, satisfies the flame retardancy standard (UL94V-0), and has a strength after curing in a specific range. Since the flame retardancy standard (UL94V-0) is satisfied, the flame retardancy is excellent, and since the strength after curing is in a specific range, a highly reliable resin-encapsulated semiconductor device can be manufactured.
前記シリカの平均粒子径が０．１～３０μｍであることが好ましい。これにより、成型時の流動性に優れたシート状の電子部品用熱硬化性樹脂組成物が得られる。 The average particle size of the silica is preferably 0.1 to 30 μm. Thereby, the sheet-like thermosetting resin composition for electronic components excellent in the fluidity | liquidity at the time of shaping | molding is obtained.
本発明のシート状の電子部品封止用熱硬化性樹脂組成物は、硬化前の粘度が９０℃において５×１０３Ｐａ・ｓ以下であることが好ましい。硬化前の粘度が９０℃において５×１０３Ｐａ・ｓ以下であると、成型性に優れた樹脂組成物が得られる。 The sheet-like thermosetting resin composition for encapsulating electronic components of the present invention preferably has a viscosity before curing of 5 × 10 3 Pa · s or less at 90 ° C. When the viscosity before curing is 5 × 10 3 Pa · s or less at 90 ° C., a resin composition excellent in moldability is obtained.
本発明のシート状の電子部品封止用熱硬化性樹脂組成物は、混練押出により製造されることが好ましい。特定量のシリカを配合すると、シート状に成形し難いが、混練押出することで、容易にシート状に成形できる。 The sheet-like thermosetting resin composition for encapsulating electronic components of the present invention is preferably produced by kneading extrusion. When a specific amount of silica is blended, it is difficult to form into a sheet, but it can be easily formed into a sheet by kneading and extruding.
本発明のシート状の電子部品封止用熱硬化性樹脂組成物は、ホスファゼン系難燃剤を含むことが好ましい。難燃性規格（ＵＬ９４Ｖ－０）を満足させるために、難燃剤用水酸化マグネシウムなどの金属水酸化物を配合すると、樹脂強度が低下してしまう。本発明では、ホスファゼン系難燃剤を配合することで、優れた難燃性が得られるとともに、硬化後の強度を特定範囲に良好に調整できる。 The sheet-like thermosetting resin composition for encapsulating electronic components of the present invention preferably contains a phosphazene flame retardant. If a metal hydroxide such as magnesium hydroxide for a flame retardant is blended in order to satisfy the flame retardant standard (UL94V-0), the resin strength is lowered. In the present invention, by blending a phosphazene-based flame retardant, excellent flame retardancy can be obtained, and the strength after curing can be well adjusted to a specific range.
本発明はまた、前記シート状の電子部品封止用熱硬化性樹脂組成物を用いて得られる樹脂封止型半導体装置に関する。 The present invention also relates to a resin-encapsulated semiconductor device obtained using the sheet-like thermosetting resin composition for encapsulating electronic components.
本発明はまた、前記シート状の電子部品封止用熱硬化性樹脂組成物を用いて電子部品を封止する工程を含む樹脂封止型半導体装置の製造方法に関する。 The present invention also relates to a method for manufacturing a resin-encapsulated semiconductor device including a step of encapsulating an electronic component using the sheet-like thermosetting resin composition for encapsulating an electronic component.
難燃性試験の様子を示す図である。It is a figure which shows the mode of a flame retardance test. ３点曲げ強度試験の様子を示す図である。It is a figure which shows the mode of a 3 point | piece bending strength test.
本発明のシート状の電子部品封止用熱硬化性樹脂組成物は、シリカの含有量が、シート状の電子部品封止用熱硬化性樹脂組成物全体に対して、７０～９３重量％であり、難燃性規格（ＵＬ９４Ｖ－０）を満足し、１５０℃で１時間加熱し硬化させた後の常温における３点曲げ強度が８０ＭＰａ以上である。本発明のシート状熱硬化性樹脂組成物は難燃性、硬化後の強度が優れる。必要に応じてホスファゼン系難燃剤を含有することにより、難燃性、硬化後の強度がより好適に得られる。 The sheet-like thermosetting resin composition for encapsulating electronic parts of the present invention has a silica content of 70 to 93% by weight based on the entire thermosetting resin composition for encapsulating electronic sheets. Yes, it satisfies the flame retardancy standard (UL94V-0) and has a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour. The sheet-like thermosetting resin composition of the present invention is excellent in flame retardancy and strength after curing. By containing a phosphazene-based flame retardant as necessary, flame retardancy and strength after curing can be more suitably obtained.
本発明で使用できる樹脂成分としては特に限定されず、例えば、エポキシ樹脂、フェノール樹脂、熱可塑性樹脂などが挙げられる。 It does not specifically limit as a resin component which can be used by this invention, For example, an epoxy resin, a phenol resin, a thermoplastic resin etc. are mentioned.
エポキシ樹脂としては、特に限定されるものではない。例えば、トリフェニルメタン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、変性ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、変性ビスフェノールＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、フェノキシ樹脂などの各種のエポキシ樹脂を用いることができる。これらエポキシ樹脂は単独で用いてもよいし２種以上併用してもよい。 The epoxy resin is not particularly limited. For example, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene type Various epoxy resins such as an epoxy resin, a phenol novolac type epoxy resin, and a phenoxy resin can be used. These epoxy resins may be used alone or in combination of two or more.
エポキシ樹脂の硬化後の靭性及びエポキシ樹脂の反応性を確保する観点からは、エポキシ当量１５０～２５０、軟化点もしくは融点が５０～１３０℃の常温で固形のものが好ましく、なかでも、信頼性の観点から、トリフェニルメタン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂が好ましい。 From the viewpoint of ensuring the toughness of the epoxy resin after curing and the reactivity of the epoxy resin, it is preferable that the epoxy equivalent is 150 to 250 and the softening point or the melting point is 50 to 130 ° C., solid at room temperature. From the viewpoint, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are preferable.
また、低応力性の観点から、アセタール基やポリオキシアルキレン基などの柔軟性骨格を有する変性ビスフェノールＡ型エポキシ樹脂が好ましく、アセタール基を有する変性ビスフェノールＡ型エポキシ樹脂は、液体状で取り扱いが良好であることから、特に好適に用いることができる。 Also, from the viewpoint of low stress, a modified bisphenol A type epoxy resin having a flexible skeleton such as an acetal group or a polyoxyalkylene group is preferable, and a modified bisphenol A type epoxy resin having an acetal group is liquid and has good handling. Therefore, it can be particularly preferably used.
シート状の電子部品封止用熱硬化性樹脂組成物の柔軟性という点から、ビスフェノールＦ型エポキシ樹脂が特に好ましい。 From the viewpoint of flexibility of the sheet-like thermosetting resin composition for encapsulating electronic components, bisphenol F type epoxy resin is particularly preferable.
エポキシ樹脂のエポキシ当量は、好ましくは１５０ｇ／ｅｑ．以上、より好ましくは１７０ｇ／ｅｑ．以上である。一方、エポキシ樹脂のエポキシ当量は、好ましくは３００ｇ／ｅｑ．以下、より好ましくは２５０ｇ／ｅｑ．以下である。
なお、エポキシ樹脂のエポキシ当量は、ＪＩＳ Ｋ ７２３６－２００９に規定された方法で測定できる。 The epoxy equivalent of the epoxy resin is preferably 150 g / eq. Or more, more preferably 170 g / eq. That's it. On the other hand, the epoxy equivalent of the epoxy resin is preferably 300 g / eq. Or less, more preferably 250 g / eq. It is as follows.
The epoxy equivalent of the epoxy resin can be measured by a method defined in JIS K 7236-2009.
エポキシ樹脂の含有量は、樹脂成分１００重量％中、好ましくは２０重量％以上、より好ましくは３０重量％以上である。また、エポキシ樹脂の含有量は、好ましくは６０重量％以下、より好ましくは５０重量％以下である。 The content of the epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, in 100% by weight of the resin component. The content of the epoxy resin is preferably 60% by weight or less, more preferably 50% by weight or less.
フェノール樹脂は、エポキシ樹脂との間で硬化反応を生起するものであれば特に限定されるものではない。例えば、フェノールノボラック樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ジシクロペンタジエン型フェノール樹脂、クレゾールノボラック樹脂、レゾール樹脂などが用いられる。これらフェノール樹脂は単独で用いてもよいし、２種以上併用してもよい。 The phenol resin is not particularly limited as long as it causes a curing reaction with the epoxy resin. For example, a phenol novolac resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolak resin, a resole resin, or the like is used. These phenolic resins may be used alone or in combination of two or more.
フェノール樹脂としては、エポキシ樹脂との反応性の観点から、水酸基当量が７０～２５０、軟化点が５０～１１０℃（好ましくは７０～９０℃）のものを用いることが好ましく、なかでも硬化反応性が高いという観点から、フェノールノボラック樹脂を好適に用いることができる。また、信頼性の観点から、フェノールアラルキル樹脂やビフェニルアラルキル樹脂のような低吸湿性のものも好適に用いることができる。 From the viewpoint of reactivity with the epoxy resin, it is preferable to use a phenol resin having a hydroxyl group equivalent of 70 to 250 and a softening point of 50 to 110 ° C. (preferably 70 to 90 ° C.). From the viewpoint of high, a phenol novolac resin can be preferably used. From the viewpoint of reliability, low hygroscopic materials such as phenol aralkyl resins and biphenyl aralkyl resins can also be suitably used.
フェノール樹脂の水酸基当量は、好ましくは７０ｇ／ｅｑ．以上、より好ましくは９０ｇ／ｅｑ．以上である。一方、フェノール樹脂の水酸基当量は、好ましくは３００ｇ／ｅｑ．以下、より好ましくは２５０ｇ／ｅｑ．以下である。 The hydroxyl equivalent of the phenol resin is preferably 70 g / eq. Or more, more preferably 90 g / eq. That's it. On the other hand, the hydroxyl equivalent of the phenol resin is preferably 300 g / eq. Or less, more preferably 250 g / eq. It is as follows.
エポキシ樹脂とフェノール樹脂の配合割合は、硬化反応性という観点から、エポキシ樹脂中のエポキシ基１当量に対して、フェノール樹脂中の水酸基の合計が０．７～１．５当量となるように配合することが好ましく、より好ましくは０．９～１．２当量である。 From the viewpoint of curing reactivity, the mixing ratio of epoxy resin and phenol resin is such that the total of hydroxyl groups in phenol resin is 0.7 to 1.5 equivalents per 1 equivalent of epoxy groups in epoxy resin. It is preferable to use 0.9 to 1.2 equivalents.
エポキシ樹脂及びフェノール樹脂の合計含有量は、樹脂成分１００重量％中、好ましくは５０重量％以上、より好ましくは６０重量％以上、更に好ましくは６５重量％以上である。５０重量％以上であると、電子部品用途向けに必要な樹脂強度を良好に確保できる。
エポキシ樹脂及びフェノール樹脂の合計含有量は、樹脂成分１００重量％中、好ましくは９８重量％以下、より好ましくは９５重量％以下である。９８重量％以下であると、成型性の良好なシート状の電子部品封止用熱硬化性樹脂組成物が得られる。 The total content of the epoxy resin and the phenol resin is preferably 50% by weight or more, more preferably 60% by weight or more, and still more preferably 65% by weight or more in 100% by weight of the resin component. When it is 50% by weight or more, the resin strength necessary for electronic component applications can be secured satisfactorily.
The total content of the epoxy resin and the phenol resin is preferably 98% by weight or less, more preferably 95% by weight or less, in 100% by weight of the resin component. When it is 98% by weight or less, a sheet-like thermosetting resin composition for encapsulating electronic components with good moldability can be obtained.
本発明のシート状熱硬化性樹脂組成物は、熱可塑性樹脂を含むことが好ましい。これにより、柔軟性、硬化後の強度が良好に得られる。 The sheet-like thermosetting resin composition of the present invention preferably contains a thermoplastic resin. Thereby, the softness | flexibility and the intensity | strength after hardening are acquired favorably.
熱可塑性樹脂としては、天然ゴム、ブチルゴム、イソプレンゴム、クロロプレンゴム、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸共重合体、エチレン－アクリル酸エステル共重合体、ポリブタジエン樹脂、ポリカーボネート樹脂、熱可塑性ポリイミド樹脂、６－ナイロンや６，６－ナイロンなどのポリアミド樹脂、フェノキシ樹脂、アクリル樹脂、ＰＥＴやＰＢＴなどの飽和ポリエステル樹脂、ポリアミドイミド樹脂、又はフッ素樹脂などが挙げられる。また、スチレン－イソブチレン－スチレンブロック共重合体なども挙げられる。これらの熱可塑性樹脂は単独で、又は２種以上を併用して用いることができる。なかでも、接着力と樹脂強度を良好に確保でき、信頼性の高い樹脂封止型半導体装置を製造できるという点から、スチレン－イソブチレン－スチレンブロック共重合体が好ましい。 Thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, thermoplasticity. Examples thereof include polyimide resins, polyamide resins such as 6-nylon and 6,6-nylon, phenoxy resins, acrylic resins, saturated polyester resins such as PET and PBT, polyamideimide resins, and fluorine resins. Also included are styrene-isobutylene-styrene block copolymers. These thermoplastic resins can be used alone or in combination of two or more. Of these, a styrene-isobutylene-styrene block copolymer is preferred from the standpoint that a good resin-encapsulated semiconductor device can be secured with good adhesion and resin strength.
熱可塑性樹脂の含有量は、樹脂成分１００重量％中、好ましくは２重量％以上、より好ましくは５重量％以上である。２重量％以上であると、柔軟性、硬化後の強度が良好に得られる。熱可塑性樹脂の含有量は、樹脂成分１００重量％中、好ましくは５０重量％以下、より好ましくは４０重量％以下である。５０重量％以下であると、難燃性が良好に得られる。 The content of the thermoplastic resin is preferably 2% by weight or more, more preferably 5% by weight or more, in 100% by weight of the resin component. When it is 2% by weight or more, flexibility and strength after curing can be obtained satisfactorily. The content of the thermoplastic resin is preferably 50% by weight or less, more preferably 40% by weight or less, in 100% by weight of the resin component. A flame retardance is favorably acquired as it is 50 weight% or less.
シリカとしては特に限定されないが、充填性、流動性に優れるという点から、溶融シリカ粉末を用いることがより好ましい。溶融シリカ粉末としては、球状溶融シリカ粉末、破砕溶融シリカ粉末が挙げられるが、流動性という観点から、球状溶融シリカ粉末を用いることが特に好ましい。 Although it does not specifically limit as silica, It is more preferable to use a fused silica powder from the point that it is excellent in a filling property and fluidity | liquidity. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, it is particularly preferable to use a spherical fused silica powder.
シリカの平均粒子径は、好ましくは０．１μｍ以上、より好ましくは０．３μｍ以上である。０．１μｍ以上であると、流動低下へ影響が少なく，良好な成型性が得られる。シリカの平均粒子径は、好ましくは３０μｍ以下、より好ましくは２０μｍ以下である。２０μｍ以下であると、成型時に電子部品へのダメージが少なく，信頼性の高い樹脂封止型半導体装置を製造できる。
なお、平均粒子径は、例えば、母集団から任意に抽出される試料を用い、レーザー回折散乱式粒度分布測定装置を用いて測定することにより導き出すことができる。 The average particle diameter of silica is preferably 0.1 μm or more, more preferably 0.3 μm or more. When it is 0.1 μm or more, there is little influence on flow reduction, and good moldability is obtained. The average particle diameter of silica is preferably 30 μm or less, more preferably 20 μm or less. When the thickness is 20 μm or less, a highly reliable resin-encapsulated semiconductor device can be manufactured with little damage to electronic components during molding.
The average particle size can be derived by, for example, using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
シリカの含有量は、シート状熱硬化性樹脂組成物全体に対して、７０重量％以上、好ましくは８０重量％以上、より好ましくは８５重量％以上である。７０重量％以上であると、難燃性、硬化後の強度が良好に得られる。シリカの含有量は、シート状熱硬化性樹脂組成物全体に対して、９３重量％以下、好ましくは９０重量％以下である。９３重量％以下であると、流動低下へ影響が少なく，良好な成型性が得られる。 The content of silica is 70% by weight or more, preferably 80% by weight or more, and more preferably 85% by weight or more with respect to the entire sheet-like thermosetting resin composition. When it is 70% by weight or more, flame retardancy and strength after curing can be obtained satisfactorily. The content of silica is 93% by weight or less, preferably 90% by weight or less, based on the entire sheet-like thermosetting resin composition. When it is 93% by weight or less, there is little influence on the flow reduction, and good moldability can be obtained.
本発明のシート状熱硬化性樹脂組成物は、ホスファゼン系難燃剤を含むことが好ましい。難燃剤用水酸化マグネシウムなどの金属水酸化物を配合すると、硬化後の強度が低下してしまうが、ホスファゼン系難燃剤を配合することで、硬化後の強度を特定範囲に良好に調整できる。 The sheet-like thermosetting resin composition of the present invention preferably contains a phosphazene flame retardant. When a metal hydroxide such as magnesium hydroxide for a flame retardant is blended, the strength after curing is reduced, but by blending a phosphazene flame retardant, the strength after curing can be well adjusted to a specific range.
ホスファゼン系難燃剤としては特に限定されないが、難燃性、硬化後の強度に優れるという理由から、式（１）又は式（２）で表される化合物が好ましい。 Although it does not specifically limit as a phosphazene type flame retardant, The compound represented by Formula (1) or Formula (2) is preferable from the reason that it is excellent in a flame retardance and the intensity | strength after hardening.
Figure JPOXMLDOC01-appb-C000001
  
 
（式中、Ｒ１及びＲ２は、同一若しくは異なって、アルコキシ基、フェノキシ基、アミノ基、水酸基、アリル基又はこれらの基からなる群より選択される少なくとも１種の基を有する１価の有機基を表す。ｘは３～２５の整数を表す。）
Figure JPOXMLDOC01-appb-C000001

(Wherein R 1 and R 2 are the same or different and are monovalent having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, an allyl group, or these groups) Represents an organic group, x represents an integer of 3 to 25)
Figure JPOXMLDOC01-appb-C000002
  
 
（式中、Ｒ３及びＲ５は、同一若しくは異なって、アルコキシ基、フェノキシ基、アミノ基、水酸基、アリル基又はこれらの基からなる群より選択される少なくとも１種の基を有する１価の有機基を表す。Ｒ４は、アルコキシ基、フェノキシ基、アミノ基、水酸基及びアリル基からなる群より選択される少なくとも１種の基を有する２価の有機基を表す。ｙは３～２５の整数を表す。ｚは３～２５の整数を表す。）
Figure JPOXMLDOC01-appb-C000002

(Wherein R 3 and R 5 are the same or different and are monovalent having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group, an allyl group, or these groups) R 4 represents an organic group, R 4 represents a divalent organic group having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group and an allyl group, and y represents 3 to 25 Represents an integer, and z represents an integer of 3 to 25.)
Ｒ１及びＲ２のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基などが挙げられる。なかでも、炭素数４～１０のアルコキシ基が好ましい。 Examples of the alkoxy group for R 1 and R 2 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
Ｒ１及びＲ２のフェノキシ基としては、例えば、式（３）で表される基が挙げられる。
Figure JPOXMLDOC01-appb-C000003
  
（式中、Ｒ１１は、水素、水酸基、アルキル基、アルコキシ基、グリシジル基又はこれらの基からなる群より選択される少なくとも１種の基を有する１価の有機基を表す。） Examples of the phenoxy group for R 1 and R 2 include a group represented by the formula (3).
Figure JPOXMLDOC01-appb-C000003
(In the formula, R 11 represents hydrogen, a hydroxyl group, an alkyl group, an alkoxy group, a glycidyl group, or a monovalent organic group having at least one group selected from the group consisting of these groups.)
Ｒ１１のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、へキシル基、へプチル基、２－エチルヘキシル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、オクタデシル基などが挙げられる。Ｒ１１のアルコキシ基としては、Ｒ１及びＲ２のアルコキシ基と同様の基が挙げられる。 Examples of the alkyl group for R 11 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl and the like. Examples of the alkoxy group for R 11 include the same groups as the alkoxy groups for R 1 and R 2 .
Ｒ１及びＲ２としては、難燃性、硬化後の強度が良好に得られるという理由から、フェノキシ基が好ましく、式（３）で表される基がより好ましい。 As R 1 and R 2 , a phenoxy group is preferable and a group represented by the formula (3) is more preferable because flame retardancy and strength after curing can be favorably obtained.
ｘは３～２５の整数を表すが、難燃性、硬化後の強度が良好に得られるという理由から、３～１０が好ましく、３～４がより好ましい。 x represents an integer of 3 to 25, but 3 to 10 is preferable and 3 to 4 is more preferable because flame retardancy and strength after curing can be obtained satisfactorily.
式（２）において、Ｒ３及びＲ５のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基などが挙げられる。なかでも、炭素数４～１０のアルコキシ基が好ましい。 In the formula (2), examples of the alkoxy group of R 3 and R 5 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
Ｒ３及びＲ５のフェノキシ基としては、例えば、前記式（３）で表される基が挙げられる。 Examples of the phenoxy group for R 3 and R 5 include a group represented by the formula (3).
Ｒ３及びＲ５におけるアルコキシ基、フェノキシ基、アミノ基、水酸基及びアリル基からなる群より選択される少なくとも１種の基を有する１価の有機基としては特に限定されない。 The monovalent organic group having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amino group, a hydroxyl group and an allyl group in R 3 and R 5 is not particularly limited.
Ｒ３及びＲ５としては、難燃性、硬化後の強度が良好に得られるという理由から、フェノキシ基が好ましく、式（３）で表される基がより好ましい。 As R 3 and R 5 , a phenoxy group is preferable and a group represented by the formula (3) is more preferable because flame retardancy and strength after curing can be favorably obtained.
Ｒ４の２価の有機基が有するアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基などが挙げられる。なかでも、炭素数４～１０のアルコキシ基が好ましい。 Examples of the alkoxy group contained in the divalent organic group represented by R 4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, alkoxy groups having 4 to 10 carbon atoms are preferable.
Ｒ４の２価の有機基が有するフェノキシ基としては、例えば、前記式（３）で表される基が挙げられる。 Examples of the phenoxy group contained in the divalent organic group represented by R 4 include a group represented by the formula (3).
ｙは３～２５の整数を表すが、難燃性、硬化後の強度が良好に得られるという理由から、３～１０が好ましい。 y represents an integer of 3 to 25, but 3 to 10 is preferable because flame retardancy and strength after curing can be obtained satisfactorily.
ｚは３～２５の整数を表すが、難燃性、硬化後の強度が良好に得られるという理由から、３～１０が好ましい。 z represents an integer of 3 to 25, but 3 to 10 is preferable because flame retardancy and strength after curing can be obtained satisfactorily.
少量でも難燃効果を発揮するという観点から、ホスファゼン系難燃剤に含まれるリン元素の含有率は、１２重量％以上であることが好ましい。 From the viewpoint of exhibiting a flame retardant effect even in a small amount, the phosphorus element content contained in the phosphazene flame retardant is preferably 12% by weight or more.
ホスファゼン系難燃剤の含有量は、シート状熱硬化性樹脂組成物全体に対して、好ましくは０．０５重量％以上、より好ましくは０．１重量％以上、更に好ましくは０．２重量％以上である。０．０５重量％以上であると、難燃性が良好に得られる。ホスファゼン系難燃剤の含有量は、シート状熱硬化性樹脂組成物全体に対して、好ましくは３０重量％以下、より好ましくは２０重量％以下、更に好ましくは５重量％以下である。３０重量％以下であると、硬化物の物性低下（具体的には、ガラス転移温度や高温樹脂強度などの物性の低下）が少なく、信頼性の高い樹脂封止型半導体装置が得られる。 The content of the phosphazene-based flame retardant is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.2% by weight or more with respect to the entire sheet-like thermosetting resin composition. It is. A flame retardance is favorably obtained as it is 0.05 weight% or more. The content of the phosphazene-based flame retardant is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 5% by weight or less with respect to the entire sheet-like thermosetting resin composition. When the content is 30% by weight or less, there is little decrease in physical properties of the cured product (specifically, deterioration in physical properties such as glass transition temperature and high-temperature resin strength), and a highly reliable resin-encapsulated semiconductor device can be obtained.
本発明のシート状熱硬化性樹脂組成物は、硬化促進剤を含むことが好ましい。硬化促進剤は、硬化を進行させるものであれば特に限定されるものではないが、硬化性と保存性の観点から、トリフェニルホスフィンやテトラフェニルホスホニウムテトラフェニルボレートなどの有機リン系化合物や、イミダゾール系化合物が好適に用いられる。 The sheet-like thermosetting resin composition of the present invention preferably includes a curing accelerator. The curing accelerator is not particularly limited as long as it allows curing to proceed. From the viewpoint of curability and storage stability, organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate, and imidazole. System compounds are preferably used.
硬化促進剤の含有量は、エポキシ樹脂及びフェノール樹脂の合計１００重量部に対して０．１～５重量部であることが好ましい。 The content of the curing accelerator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin.
なお、本発明のシート状熱硬化性樹脂組成物は、上記の各成分以外に必要に応じて、カーボンブラックをはじめとする顔料、シランカップリング剤、金属水酸化物など、他の添加剤を適宜配合することができる。 In addition to the above components, the sheet-like thermosetting resin composition of the present invention contains other additives such as pigments including carbon black, silane coupling agents, and metal hydroxides as necessary. It can mix | blend suitably.
本発明のシート状熱硬化性樹脂組成物において、金属水酸化物の含有量は少ないほど好ましく、シート状熱硬化性樹脂組成物全体に対して、好ましくは５重量％以下、より好ましくは１重量％以下、更に好ましくは０重量％である。５重量％以下であると、硬化後の強度を特定範囲に良好に調整できる。 In the sheet-like thermosetting resin composition of the present invention, the content of the metal hydroxide is preferably as small as possible, and is preferably 5% by weight or less, more preferably 1% by weight with respect to the whole sheet-like thermosetting resin composition. % Or less, more preferably 0% by weight. The intensity | strength after hardening can be favorably adjusted to a specific range as it is 5 weight% or less.
［シート状熱硬化性樹脂組成物の製造方法］
本発明のシート状熱硬化性樹脂組成物は、例えば、つぎのようにして製造することができる。
すなわち、まず、先に述べたシート用の各材料を均一に分散混合し、樹脂組成物を調製する。そして、調製された樹脂組成物を、シート状に形成する。この形成方法としては、例えば、調製された樹脂組成物を押出成形してシート状に形成する方法（混練押出）や、調製された樹脂組成物を有機溶剤等に溶解または分散してワニスを調製し、このワニスを、ポリエステル等の基材上に塗工し乾燥させることによりシートを製造する方法（溶剤塗工）等があげられる。溶剤塗工では、得られたシート状熱硬化性樹脂組成物を必要に応じて複数積層して、所定厚みのシート状熱硬化性樹脂組成物を得る。なお、シート状熱硬化性樹脂組成物の表面には、必要に応じ、シート状熱硬化性樹脂組成物の表面を保護するためにポリエステルフィルム等の剥離シートを貼り合わせ、封止時に剥離するようにしてもよい。 [Method for producing sheet-like thermosetting resin composition]
The sheet-like thermosetting resin composition of the present invention can be produced, for example, as follows.
That is, first, each material for a sheet described above is uniformly dispersed and mixed to prepare a resin composition. And the prepared resin composition is formed in a sheet form. As this forming method, for example, a method in which the prepared resin composition is extruded to form a sheet (kneading extrusion), or a varnish is prepared by dissolving or dispersing the prepared resin composition in an organic solvent or the like. And the method (solvent coating) etc. which manufacture this sheet | seat by apply | coating this varnish on base materials, such as polyester, and drying are mention | raise | lifted. In the solvent coating, a plurality of the obtained sheet-like thermosetting resin compositions are laminated as necessary to obtain a sheet-like thermosetting resin composition having a predetermined thickness. In addition, on the surface of the sheet-like thermosetting resin composition, if necessary, a release sheet such as a polyester film is bonded to protect the surface of the sheet-like thermosetting resin composition, and the sheet-like thermosetting resin composition is peeled off at the time of sealing. It may be.
ワニスを調製する際に用いる有機溶剤としては、例えば、メチルエチルケトン、アセトン、シクロヘキサノン、ジオキサン、ジエチルケトン、トルエン、酢酸エチル等を用いることができる。これらは単独でもしくは二種以上併せて用いられる。また、通常、ワニスの固形分濃度が６０～９０重量％の範囲となるように有機溶剤を用いることが好ましい。 As an organic solvent used when preparing a varnish, methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, ethyl acetate etc. can be used, for example. These may be used alone or in combination of two or more. In general, it is preferable to use an organic solvent so that the solid content concentration of the varnish is in the range of 60 to 90% by weight.
本発明のシート状熱硬化性樹脂組成物を混練押出により製造することにより、シート状に容易に成形でき、ボイド（気泡）などの少ない均一なシートとすることができる。 By producing the sheet-like thermosetting resin composition of the present invention by kneading and extrusion, it can be easily formed into a sheet shape, and a uniform sheet with few voids (bubbles) can be obtained.
混練押出により製造する方法としては、例えば、上述の各成分をミキシングロール、加圧式ニーダー、押出機などの公知の混練機で溶融混練することにより混練物を調製し、得られた混練物を押し出してシート状に成形する方法などが挙げられる。
混練条件として、温度は、上述の各成分の軟化点以上であることが好ましく、例えば３０～１５０℃、エポキシ樹脂の熱硬化性を考慮すると、好ましくは４０～１４０℃、さらに好ましくは６０～１２０℃である。時間は、例えば１～３０分間、好ましくは５～１５分間である。これによって、混練物を調製することができる。 As a method for producing by kneading extrusion, for example, the above-mentioned components are melt-kneaded by a known kneader such as a mixing roll, a pressure kneader, or an extruder to prepare a kneaded product, and the obtained kneaded product is extruded. And a method of forming it into a sheet.
As the kneading conditions, the temperature is preferably equal to or higher than the softening point of each component described above, for example, 30 to 150 ° C., and preferably 40 to 140 ° C., more preferably 60 to 120 in consideration of the thermosetting property of the epoxy resin. ° C. The time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes. Thereby, a kneaded material can be prepared.
得られる混練物を押出成形により成形することにより、シート状熱硬化性樹脂組成物を得ることができる。具体的には、溶融混練後の混練物を冷却することなく高温状態のままで、押出成形することで、シート状熱硬化性樹脂組成物を成形することができる。このような押出方法としては、特に制限されず、平板プレス法、Ｔダイ押出法、ロール圧延法、ロール混練法、インフレーション押出法、共押出法、カレンダー成形法などが挙げられる。押出温度としては、上述の各成分の軟化点以上が好ましく、エポキシ樹脂の熱硬化性及び成形性を考慮すると、例えば４０～１５０℃、好ましくは５０～１４０℃、さらに好ましくは７０～１２０℃である。以上により、シート状熱硬化性樹脂組成物を成形することができる。 A sheet-like thermosetting resin composition can be obtained by molding the obtained kneaded material by extrusion molding. Specifically, a sheet-like thermosetting resin composition can be molded by extrusion molding while keeping the kneaded material after melt-kneading in a high temperature state without cooling. Such an extrusion method is not particularly limited, and examples thereof include a flat plate pressing method, a T-die extrusion method, a roll rolling method, a roll kneading method, an inflation extrusion method, a co-extrusion method, and a calendar molding method. The extrusion temperature is preferably not less than the softening point of each component described above, and is 40 to 150 ° C., preferably 50 to 140 ° C., more preferably 70 to 120 ° C. in consideration of the thermosetting property and moldability of the epoxy resin. is there. By the above, a sheet-like thermosetting resin composition can be shape | molded.
本発明のシート状熱硬化性樹脂組成物の厚さは特に限定されないが、０．１ｍｍ～１ｍｍであることが好ましく、０．１ｍｍ～０．７ｍｍであることが好ましい。上記範囲内であると、電子部品を良好に封止できる。 The thickness of the sheet-like thermosetting resin composition of the present invention is not particularly limited, but is preferably 0.1 mm to 1 mm, and preferably 0.1 mm to 0.7 mm. Electronic components can be satisfactorily sealed within the above range.
本発明のシート状熱硬化性樹脂組成物は、米国ＵＬ規格における難燃性規格（ＵＬ９４Ｖ－０）を満足する。 The sheet-like thermosetting resin composition of the present invention satisfies the flame retardance standard (UL94V-0) in the US UL standard.
本発明のシート状熱硬化性樹脂組成物は、硬化前の粘度が４０℃において５×１０５Ｐａ・ｓ以下であることが好ましい。５×１０５Ｐａ・ｓ以下であると、シート状やロール状への加工性に優れ、シート状およびロール状に製造可能となる。該粘度の下限は特に限定されないが、好ましくは３×１０2Ｐａ・ｓ以上である。３×１０2Ｐａ・ｓ以上であると、ハンドリング性に優れる。 The sheet-like thermosetting resin composition of the present invention preferably has a viscosity before curing of 5 × 10 5 Pa · s or less at 40 ° C. When it is 5 × 10 5 Pa · s or less, it is excellent in processability to a sheet shape or a roll shape, and can be produced in a sheet shape and a roll shape. The lower limit of the viscosity is not particularly limited, but is preferably 3 × 10 2 Pa · s or more. When it is 3 × 10 2 Pa · s or more, the handling property is excellent.
本発明のシート状熱硬化性樹脂組成物は、硬化前の粘度が９０℃において５×１０３Ｐａ・ｓ以下であることが好ましい。５×１０３Ｐａ・ｓ以下であると、良好な成型性が得られる。該粘度の下限は特に限定されないが、好ましくは３×１０2Ｐａ・ｓ以上である。３×１０2Ｐａ・ｓ以上であると、樹脂の角形状を維持したまま成型が可能である。 The sheet-like thermosetting resin composition of the present invention preferably has a viscosity before curing of 5 × 10 3 Pa · s or less at 90 ° C. Good moldability is obtained as it is 5 × 10 3 Pa · s or less. The lower limit of the viscosity is not particularly limited, but is preferably 3 × 10 2 Pa · s or more. When it is 3 × 10 2 Pa · s or more, molding is possible while maintaining the square shape of the resin.
硬化前の粘度は、実施例に記載の方法で測定できる。 The viscosity before curing can be measured by the method described in the examples.
本発明のシート状熱硬化性樹脂組成物は、１５０℃で１時間加熱し硬化させた後の常温における３点曲げ強度が８０ＭＰａ以上である。８０ＭＰａ以上であると、樹脂が割れにくく高い信頼性の樹脂封止型半導体装置が得られる。該３点曲げ強度は、１００ＭＰａ以上が好ましい。
該３点曲げ強度の上限は特に限定されないが、例えば、２００ＭＰａ以下、好ましくは１８０ＭＰａ以下である。２００ＭＰａ以下であると、硬化物の加工性に優れる。
該３点曲げ強度は、実施例に記載の方法で測定できる。なお、本明細書において、常温とは２３℃である。 The sheet-like thermosetting resin composition of the present invention has a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour. When the pressure is 80 MPa or more, a highly reliable resin-encapsulated semiconductor device in which the resin is difficult to break can be obtained. The three-point bending strength is preferably 100 MPa or more.
The upper limit of the three-point bending strength is not particularly limited, but is, for example, 200 MPa or less, preferably 180 MPa or less. When it is 200 MPa or less, the processability of the cured product is excellent.
The three-point bending strength can be measured by the method described in the examples. In addition, in this specification, normal temperature is 23 degreeC.
なお、３点曲げ強度は、難燃剤の種類、シリカの含有量、熱硬化性樹脂の含有量、エポキシ樹脂のエポキシ当量、フェノール樹脂の水酸基当量などによりコントロールできる。例えば、ホスファゼン系難燃剤を使用すること、シリカを増量すること、熱硬化性樹脂を増量すること、エポキシ当量が大きいエポキシ樹脂を使用すること、水酸基当量が大きいフェノール樹脂を使用することなどにより、３点曲げ強度を高めることができる。 The three-point bending strength can be controlled by the type of flame retardant, silica content, thermosetting resin content, epoxy equivalent of epoxy resin, hydroxyl equivalent of phenol resin, and the like. For example, by using a phosphazene flame retardant, increasing the amount of silica, increasing the thermosetting resin, using an epoxy resin having a large epoxy equivalent, using a phenol resin having a large hydroxyl equivalent, etc. Three-point bending strength can be increased.
本発明のシート状熱硬化性樹脂組成物は、半導体ウェハ、半導体チップ、コンデンサ、抵抗などの電子部品の封止に使用される。なかでも、半導体ウェハ、半導体チップの封止に好適に使用できる。本発明のシート状熱硬化性樹脂組成物は、電子部品及びそれに付随する要素を外部環境から保護するための封止樹脂として機能できる。 The sheet-like thermosetting resin composition of the present invention is used for sealing electronic components such as a semiconductor wafer, a semiconductor chip, a capacitor, and a resistor. Especially, it can use suitably for sealing of a semiconductor wafer and a semiconductor chip. The sheet-like thermosetting resin composition of the present invention can function as a sealing resin for protecting an electronic component and its accompanying elements from the external environment.
封止方法としては特に限定されず、従来公知の方法で封止できる。例えば、シート状熱硬化性樹脂組成物に電子部品を埋め込む方法、軟化させたシート状熱硬化性樹脂組成物で電子部品を覆う方法が代表的である。 It does not specifically limit as a sealing method, It can seal by a conventionally well-known method. For example, a method of embedding an electronic component in a sheet-like thermosetting resin composition and a method of covering an electronic component with a softened sheet-like thermosetting resin composition are representative.
例えば、支持板、支持板上に積層された仮固定材及び仮固定材上に仮固定された半導体チップを備えるチップ仮固定体と、チップ仮固定体上に配置されたシート状熱硬化性樹脂組成物とを備える積層体を、平行平板方式で熱プレスすることにより、シート状熱硬化性樹脂組成物に電子部品を埋め込むことができる。支持板の材料としては特に限定されず、例えば、ＳＵＳなどの金属材料、ポリイミド、ポリアミドイミド、ポリエーテルエーテルケトン、ポリエーテルサルフォンなどのプラスチック材料などである。仮固定材としては特に限定されないが、容易に剥離できるという理由から、通常は、熱発泡性粘着剤などの熱剥離性粘着剤などを使用する。 For example, a support plate, a temporary fixing material laminated on the support plate, a chip temporary fixing body including a semiconductor chip temporarily fixed on the temporary fixing material, and a sheet-like thermosetting resin disposed on the chip temporary fixing body An electronic component can be embedded in a sheet-like thermosetting resin composition by heat-pressing a laminated body provided with the composition by a parallel plate method. The material of the support plate is not particularly limited, and examples thereof include metal materials such as SUS, and plastic materials such as polyimide, polyamideimide, polyether ether ketone, and polyether sulfone. Although it does not specifically limit as a temporary fixing material, From the reason that it can peel easily, Usually, heat peelable adhesives, such as a heat foamable adhesive, etc. are used.
例えば、基板、基板上に配置された電子部品及び電子部品上に配置されたシート状熱硬化性樹脂組成物を備える積層構造体を、平行平板方式で熱プレスすることにより、シート状熱硬化性樹脂組成物に電子部品を埋め込むことができる。基板としては特に限定されず、例えば、ガラス布基材エポキシ樹脂銅張積層板、鉄ニッケル合金板、半導体ウェハなどが挙げられる。 For example, a sheet-like thermosetting property is obtained by hot pressing a substrate, an electronic component disposed on the substrate, and a laminated structure including the sheet-like thermosetting resin composition disposed on the electronic component in a parallel plate method. An electronic component can be embedded in the resin composition. It does not specifically limit as a board | substrate, For example, a glass cloth base material epoxy resin copper clad laminated board, an iron nickel alloy board, a semiconductor wafer etc. are mentioned.
基板上の電子部品を覆うようにシート状熱硬化性樹脂組成物を載置し、シート状熱硬化性樹脂組成物を熱硬化することで電子部品を封止することができる。 An electronic component can be sealed by placing the sheet-like thermosetting resin composition so as to cover the electronic component on the substrate and thermosetting the sheet-like thermosetting resin composition.
このような方法により得られた樹脂封止型半導体装置は、難燃性、硬化後の強度に優れ、信頼性が高い。 The resin-encapsulated semiconductor device obtained by such a method has excellent flame retardancy, strength after curing, and high reliability.
以下、本発明に関し実施例を用いて詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。また、各例中、部は特記がない限りいずれも重量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In each example, all parts are based on weight unless otherwise specified.
実施例で使用した成分について説明する。
エポキシ樹脂：新日鐵化学社製のＹＳＬＶ－８０ＸＹ（ビスフェノールＦ型エポキシ樹脂：エポキシ当量　１９１、軟化点　８０℃）
フェノール樹脂：明和化成社製のＭＥＨ７８５１ＳＳ（フェノールアラルキル樹脂：水酸基当量２０３、軟化点６７℃）
触媒：四国化成工業社製の２ＰＨＺ－ＰＷ（イミダゾール系触媒）
球状溶融シリカ：電気化学工業社製のＦＢ－９４５４（溶融球状シリカ、平均粒子径　２０μｍ）
カーボンブラック：三菱化学社製の＃２０
シランカップリング剤：信越化学社製のＫＢＭ－４０３（３－グリシドキシプロピルトリメトキシシラン）
エラストマー（熱可塑性樹脂）：カネカ社製のＳＩＢＳＴＥＲ　０７２Ｔ（スチレン－イソブチレン－スチレンブロック共重合体）
難燃剤Ａ：伏見製薬所製のＦＰ－１００（ホスファゼン系難燃剤：式（４）で表される化合物）
 
（式中、ｍは３～４の整数を表す。）
難燃剤Ｂ：タテホ化学工業社製のＺ－１０（難燃剤用水酸化マグネシウム） The components used in the examples will be described.
Epoxy resin: YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin: epoxy equivalent 191, softening point 80 ° C.)
Phenol resin: MEH7851SS manufactured by Meiwa Kasei Co., Ltd. (phenol aralkyl resin: hydroxyl group equivalent 203, softening point 67 ° C.)
Catalyst: 2PHZ-PW (imidazole catalyst) manufactured by Shikoku Kasei Kogyo Co., Ltd.
Spherical fused silica: FB-9454 manufactured by Denki Kagaku Kogyo Co., Ltd. (fused spherical silica, average particle size 20 μm)
Carbon black: # 20 manufactured by Mitsubishi Chemical
Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
Elastomer (thermoplastic resin): SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka Corporation
Flame retardant A: FP-100 manufactured by Fushimi Pharmaceutical (phosphazene flame retardant: compound represented by formula (4))

(In the formula, m represents an integer of 3 to 4.)
Flame retardant B: Z-10 (magnesium hydroxide for flame retardant) manufactured by Tateho Chemical Co., Ltd.
［樹脂シートの作製］
実施例１～２及び比較例１～４
表１に記載の配合比に従い、各成分を２軸混練り機により、１２０℃で１０分間混練し、混練物を調製した。次に、上記混練物を押出成形し、厚さ０．８ｍｍの樹脂シートを得た。 [Production of resin sheet]
Examples 1-2 and Comparative Examples 1-4
According to the blending ratio shown in Table 1, each component was kneaded with a biaxial kneader at 120 ° C. for 10 minutes to prepare a kneaded product. Next, the kneaded product was extruded to obtain a resin sheet having a thickness of 0.8 mm.
実施例３
表１に記載の配合比に従い、各成分をメチルエチルケトンとトルエンを５：５で含む混合液と混合し、成分濃度９０重量％の混合物を作製した。混合物を自転公転式ミキサー（シンキ―社製、あわとり練太郎）を用いて、２０００ｒｐｍで１０分間撹拌することで、塗工用ワニスを得た。塗工用ワニスを厚み５０μｍのシリコーン処理ＰＥＴ（三菱化学製：ＭＲＦ５０）上に塗工し、次いで熱風乾燥機で１１０℃１０分間乾燥させることにより、厚さ１００μｍのシートを得た。８枚のシートを真空ラミネーターにより、ロール温度９０℃、速度０．４ｍ／ｍｉｎで積層することにより、厚さ０．８ｍｍの樹脂シートを得た。なお、メチルエチルケトンとトルエンを含む混合液を使用したのは、エラストマーであるＳＩＢＳＴＡＲ　０７２Ｔがメチルエチルケトンに溶解しにくいためである。 Example 3
According to the blending ratio shown in Table 1, each component was mixed with a mixed solution containing methyl ethyl ketone and toluene in a ratio of 5: 5 to prepare a mixture having a component concentration of 90% by weight. A varnish for coating was obtained by stirring the mixture for 10 minutes at 2000 rpm using a rotation and revolution mixer (Shinki Co., Ltd., Nertaro Awatori). The coating varnish was coated on a 50 μm thick silicone-treated PET (Mitsubishi Chemical: MRF50) and then dried at 110 ° C. for 10 minutes with a hot air dryer to obtain a 100 μm thick sheet. Eight sheets were laminated by a vacuum laminator at a roll temperature of 90 ° C. and a speed of 0.4 m / min to obtain a resin sheet having a thickness of 0.8 mm. The reason why the mixed solution containing methyl ethyl ketone and toluene was used is that SIBSTAR 072T, which is an elastomer, is difficult to dissolve in methyl ethyl ketone.
［評価］
得られた樹脂シートを用いて以下の評価を行った。結果を表１に示す。 [Evaluation]
The following evaluation was performed using the obtained resin sheet. The results are shown in Table 1.
＜難燃性＞
図１を用いて、難燃性の測定方法について説明する。
図１は、難燃性試験の様子を示す図である。 <Flame retardance>
A method for measuring flame retardancy will be described with reference to FIG.
FIG. 1 is a diagram showing a state of a flame retardancy test.
まず、難燃性試験に使用した装置などについて説明する。
チャンバー：無風状態の試験箱
クランプ付きリングスタンド
工業用メタンガス
乾燥脱脂綿：５０．８ｍｍ　×　５０．８ｍｍ　×　６．４ｍｍ
恒温恒湿器：２３±２℃、湿度５０±５％ First, the apparatus used for the flame retardancy test will be described.
Chamber: Ring stand with windless test box clamp Industrial methane gas dry absorbent cotton: 50.8mm x 50.8mm x 6.4mm
Constant temperature and humidity chamber: 23 ± 2 ℃, humidity 50 ± 5%
試験片の作製
樹脂シートから、１２７ｍｍ　×　１２．７ｍｍ　×　１／３２ｉｎｃｈの試験片１を切り出した。試験片１を、恒温恒湿器（２３±２℃、湿度５０±５％）に４８時間以上放置し、難燃性試験に用いた（前処理）。 Preparation of test piece A test piece 1 of 127 mm x 12.7 mm x 1/32 inch was cut out from the resin sheet. The test piece 1 was left in a constant temperature and humidity chamber (23 ± 2 ° C., humidity 50 ± 5%) for 48 hours or more and used for a flame retardancy test (pretreatment).
難燃性試験の手順
チャンバー内に、クランプ付きリングスタンドを配置し、試験片１をクランプ２に取り付けた。また、試験片１の下方に乾燥脱脂綿３を配置した。
次いで、バーナー４を点火し、青色炎になるよう調整した。バーナー４を試験片１の下方に配置し、試験片１下部に１０秒間炎５を当てた。このとき、炎５の高さ１１はバーナー４の頂点から２０±１ｍｍであった。試験片１とバーナー４の頂点との距離１２は１０±１ｍｍであった。試験片１と乾燥脱脂綿３との距離１３は３００±１０ｍｍであった。炎５を試験片１から離した後、有炎燃焼時間を測定した。
試験片１の炎が消えた後（有炎燃焼時間の測定後）、再度、試験片１下部へ１０秒間接炎した。炎５を試験片１から離した後、有炎燃焼時間と赤熱時間を測定した。 Flame Retardancy Test Procedure A ring stand with a clamp was placed in the chamber and the test piece 1 was attached to the clamp 2. A dry absorbent cotton 3 was placed below the test piece 1.
Subsequently, the burner 4 was ignited and adjusted so as to give a blue flame. The burner 4 was placed below the test piece 1 and the flame 5 was applied to the lower part of the test piece 1 for 10 seconds. At this time, the height 11 of the flame 5 was 20 ± 1 mm from the top of the burner 4. The distance 12 between the test piece 1 and the top of the burner 4 was 10 ± 1 mm. The distance 13 between the test piece 1 and the dry absorbent cotton 3 was 300 ± 10 mm. After the flame 5 was separated from the test piece 1, the flame burning time was measured.
After the flame of the test piece 1 disappeared (after measurement of the flaming combustion time), an indirect flame was again applied to the lower part of the test piece 1 for 10 seconds. After the flame 5 was separated from the test piece 1, the flame burning time and the red hot time were measured.
難燃性規格（ＵＬ９４Ｖ－０）の要求事項
難燃性規格（ＵＬ９４Ｖ－０）の要求事項は以下の通りである。各例の試験片１について、全ての要求事項を満たす場合を○、満たさない場合を×とした。結果を表１に示す。
１）各有炎燃焼時間が１０秒以下であること。
２）１組５個の試験片１に合計１０回接炎し、合計の有炎燃焼時間が５０秒以下であること。
３）有炎燃焼又は赤熱燃焼がクランプ２まで達しないこと。
４）有炎滴下物により、試験片１の下方に置かれた乾燥脱脂綿３に着火しないこと。
５）赤熱燃焼時間が３０秒以内であること。 Requirements for flame retardancy standard (UL94V-0) The requirements for flame retardancy standard (UL94V-0) are as follows. Regarding the test piece 1 of each example, a case where all the requirements are satisfied is indicated as “◯”, and a case where the requirements are not satisfied is indicated as “X”. The results are shown in Table 1.
1) Each flame burning time is 10 seconds or less.
2) A set of five test pieces 1 is in contact with the flame 10 times in total, and the total flame burning time is 50 seconds or less.
3) Flame or red heat combustion does not reach clamp 2.
4) Do not ignite the dry absorbent cotton 3 placed below the test piece 1 by the flammable drops.
5) The red hot combustion time is within 30 seconds.
＜樹脂強度（３点曲げ強度）＞
図２を用いて、樹脂強度の測定方法について説明する。
図２は、３点曲げ試験の様子を示す図である。 <Resin strength (3-point bending strength)>
A method for measuring the resin strength will be described with reference to FIG.
FIG. 2 is a diagram illustrating a three-point bending test.
１５０℃で１時間加熱し硬化させた後の樹脂シートから、１０ｍｍ（幅）×４０ｍｍ（長さ）×１ｍｍ（厚み）の試験片５１を切り出した。次いで、オートグラフ　ＡＧ－５００Ｃ（島津製作所社製）を用いて、支点間距離６１が２０ｍｍである支持体５２に試験片５１を載せ、試験片５１の中央部に押し金具５３を当て、試験片５１と垂直方向に荷重を加え（荷重速度５ｍｍ／分）、試験片５１の３点曲げ強度を測定した。なお、測定は、常温で行った。
結果を表１に示す。 A test piece 51 of 10 mm (width) × 40 mm (length) × 1 mm (thickness) was cut out from the resin sheet after being heated and cured at 150 ° C. for 1 hour. Next, using Autograph AG-500C (manufactured by Shimadzu Corporation), a test piece 51 is placed on a support 52 having a fulcrum distance 61 of 20 mm, a pressing metal 53 is applied to the center of the test piece 51, and the test piece is tested. A load was applied in a direction perpendicular to 51 (loading speed: 5 mm / min), and the three-point bending strength of the test piece 51 was measured. The measurement was performed at room temperature.
The results are shown in Table 1.
＜柔軟性＞
樹脂シートについて、ティーエイインスツルメント社製の粘弾性測定装置ＡＲＥＳを用いて、４０℃及び９０℃における粘度を測定した（測定条件：直径８ｍｍのパラレルプレート、昇温速度１０℃／分、周波数１Ｈｚ、歪み５％）。結果を表１に示す。 <Flexibility>
About the resin sheet, the viscosity in 40 degreeC and 90 degreeC was measured using the viscoelasticity measuring apparatus ARES made from TI Instruments (measuring conditions: Parallel plate of diameter 8mm, temperature increase rate of 10 degree-C / min, frequency 1 Hz, distortion 5%). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
１　　　試験片
２　　　クランプ
３　　　乾燥脱脂綿
４　　　バーナー
５　　　炎
１１　　炎の高さ
１２　　試験片とバーナーの頂点との距離
１３　　試験片と乾燥脱脂綿との距離
２１　　１２７ｍｍ
２２　　１２．７ｍｍ
５１　　試験片
５２　　支持体
５３　　押し金具
６１　　支点間距離
６２　　荷重方向 1 Test piece 2 Clamp 3 Dry absorbent cotton 4 Burner 5 Flame 11 Flame height 12 Distance between test piece and top of burner 13 Distance between test piece and dry absorbent cotton 21 127 mm
22 12.7mm
51 Test Specimen 52 Support 53 Pressing Bracket 61 Distance between Supporting Points 62 Load Direction

Claims (7)

  1. シリカの含有量が、シート状の電子部品封止用熱硬化性樹脂組成物全体に対して、７０～９３重量％であり、
    難燃性規格（ＵＬ９４Ｖ－０）を満足し、
    １５０℃で１時間加熱し硬化させた後の常温における３点曲げ強度が８０ＭＰａ以上であるシート状の電子部品封止用熱硬化性樹脂組成物。     The content of silica is 70 to 93% by weight based on the whole sheet-like thermosetting resin composition for sealing electronic parts,
    Satisfies flame retardant standard (UL94V-0),
    A thermosetting resin composition for sealing a sheet-like electronic component having a three-point bending strength of 80 MPa or more at room temperature after being cured by heating at 150 ° C. for 1 hour.
  2. 前記シリカの平均粒子径が０．１～３０μｍである請求項１に記載のシート状の電子部品封止用熱硬化性樹脂組成物。 The sheet-like thermosetting resin composition for sealing electronic parts according to claim 1, wherein the silica has an average particle diameter of 0.1 to 30 µm.
  3. 硬化前の粘度が９０℃において５×１０３Ｐａ・ｓ以下である請求項１又は２に記載のシート状の電子部品封止用熱硬化性樹脂組成物。 The thermosetting resin composition for encapsulating sheet-like electronic components according to claim 1 or 2, wherein the viscosity before curing is 5 x 10 3 Pa · s or less at 90 ° C.
  4. 混練押出により製造される請求項１～３のいずれか１項に記載のシート状の電子部品封止用熱硬化性樹脂組成物。 The sheet-like thermosetting resin composition for sealing electronic parts according to any one of claims 1 to 3, which is produced by kneading extrusion.
  5. ホスファゼン系難燃剤を含む請求項１～４のいずれか１項に記載のシート状の電子部品封止用熱硬化性樹脂組成物。 The sheet-like thermosetting resin composition for sealing an electronic component according to any one of claims 1 to 4, comprising a phosphazene flame retardant.
  6. 請求項１～５のいずれか１項に記載のシート状の電子部品封止用熱硬化性樹脂組成物を用いて得られる樹脂封止型半導体装置。 A resin-encapsulated semiconductor device obtained by using the sheet-like thermosetting resin composition for encapsulating electronic components according to any one of claims 1 to 5.
  7. 請求項１～５のいずれか１項に記載のシート状の電子部品封止用熱硬化性樹脂組成物を用いて電子部品を封止する工程を含む樹脂封止型半導体装置の製造方法。 A method for producing a resin-encapsulated semiconductor device, comprising a step of encapsulating an electronic component using the sheet-like thermosetting resin composition for encapsulating an electronic component according to any one of claims 1 to 5.
PCT/JP2014/051123 2013-01-23 2014-01-21 Thermosetting resin composition for sealing sheet-form electronic component, resin-sealed semiconductor device, and method of manufacturing resin-sealed semiconductor device WO2014115725A1 (en)

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