WO2014156837A1 - Hollow sealing resin sheet and production method for hollow package - Google Patents
Hollow sealing resin sheet and production method for hollow package Download PDFInfo
- Publication number
- WO2014156837A1 WO2014156837A1 PCT/JP2014/057339 JP2014057339W WO2014156837A1 WO 2014156837 A1 WO2014156837 A1 WO 2014156837A1 JP 2014057339 W JP2014057339 W JP 2014057339W WO 2014156837 A1 WO2014156837 A1 WO 2014156837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hollow
- resin sheet
- resin
- group
- package
- Prior art date
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Classifications
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/561—Batch processing
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Definitions
- the present invention relates to a hollow sealing resin sheet and a method for producing a hollow package.
- a sealing resin For the production of an electronic device package, typically, one or more electronic devices fixed to a substrate or the like via bumps or the like are sealed with a sealing resin, and the sealing body is united as an electronic device as necessary. The procedure of dicing so that it becomes a package of is adopted.
- a sealing resin a sheet-shaped sealing resin may be used.
- MEMS Microelectronic devices
- SAW Surface Acoustic Wave
- CMOS Complementary Metal Oxide Semiconductor
- acceleration sensors For example, Patent Document 1 describes a technique of hollow-molding a functional element using a gel-like curable resin sheet.
- the bump diameter will be increased in the future. It is expected that measures will be taken to expand With the technique described in Patent Document 1, the electronic device can be sealed while maintaining a desired hollow structure as long as the hollow structure between the element and the substrate is a gap having a width of about several tens of ⁇ m. However, if sealing is performed while ensuring a gap having a width of approximately 100 ⁇ m as a hollow structure, it may be difficult to cope with the occurrence of resin inflow into the hollow structure, and the package manufacturing yield may be reduced.
- An object of the present invention is to provide a hollow sealing resin that can maintain a hollow structure even when the width of the void of the hollow structure is about 100 ⁇ m, and that can produce a highly reliable hollow package by preventing warpage of the package It is to provide a method for manufacturing a sheet and a hollow package.
- the hollow sealing resin sheet of the present invention contains an inorganic filler in a content of 70 vol% or more and 90 vol% or less,
- the minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement is 2000 Pa ⁇ s or more and 20000 Pa ⁇ s or less,
- the storage elastic modulus at normal temperature (20 ° C.) after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less,
- the linear expansion coefficient at the glass transition temperature or lower after thermosetting at 150 ° C. for 1 hour is 5 ppm / K or more and 15 ppm / K or less.
- the resin sheet for hollow sealing has a minimum melt viscosity of 2000 Pa ⁇ s or more and 20000 Pa ⁇ s or less due to a high content of inorganic filler, a highly reliable hollow package can be obtained by suppressing resin intrusion into the hollow structure. Can be manufactured.
- the storage elastic modulus and linear expansion coefficient after thermosetting are in a predetermined range, the package strength after curing can be ensured and package warpage can be prevented even when a high temperature is applied in a solder reflow process.
- a more reliable package can be manufactured.
- the measuring method of minimum melt viscosity, storage elastic modulus, glass transition temperature, and a linear expansion coefficient is based on description of an Example.
- the hollow sealing resin sheet is disposed on the electronic device so as to cover one or a plurality of electronic devices arranged on the adherend.
- the manufacturing method of the hollow package including the lamination process which laminates
- FIG. 1 is a cross-sectional view schematically showing a hollow sealing resin sheet (hereinafter also simply referred to as “resin sheet”) 11 according to an embodiment of the present invention.
- the resin sheet 11 is typically provided in a state of being laminated on a support 11a such as a polyethylene terephthalate (PET) film. Note that a release treatment may be performed on the support 11a in order to easily peel off the resin sheet 11.
- a support 11a such as a polyethylene terephthalate (PET) film.
- PET polyethylene terephthalate
- the minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement before curing of the resin sheet 11 may be 2000 Pa ⁇ s or more and 20000 Pa ⁇ s or less, and preferably 3000 Pa ⁇ s or more and 15000 Pa ⁇ s or less, More preferably, it is 5000 Pa ⁇ s or more and 10,000 Pa ⁇ s or less.
- the storage elastic modulus at 20 ° C. after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less, and the lower limit thereof is preferably 1.5 GPa or more, and more preferably 2 GPa or more. Moreover, as an upper limit of this storage elastic modulus, 10 GPa or less is preferable and 5 GPa or less is more preferable.
- the strength of the package can be ensured. If the storage elastic modulus is less than the lower limit, the package strength may be insufficient and the reliability may be lowered. On the other hand, when the above upper limit is exceeded, the package becomes brittle with respect to impact and the package strength becomes insufficient, and in this case, the reliability may be lowered.
- the glass transition temperature after thermosetting at 150 ° C. for 1 hour is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 110 ° C. or higher.
- the sealing resin sheet has such a configuration, heat resistance can be improved.
- the upper limit of the glass transition temperature after the thermosetting treatment is not particularly limited, it is preferably 250 ° C. or less, and more preferably 200 ° C. or less, from the viewpoint of reducing curing shrinkage during thermosetting.
- the linear expansion coefficient below the glass transition temperature after thermosetting the resin sheet 11 at 150 ° C. for 1 hour may be 5 ppm / K or more and 15 ppm / K or less.
- the lower limit of the linear expansion coefficient is preferably 6 ppm / K or more, more preferably 7 ppm / K or more.
- the upper limit of the linear expansion coefficient is preferably 12 ppm / K or less, and more preferably 9 ppm / K or less.
- a difference in coefficient of linear expansion from a substrate having a coefficient can be reduced, and warpage of the substrate can be prevented. If the linear expansion coefficient is less than the lower limit or exceeds the upper limit, the difference in the linear expansion coefficient between the resin sheet and the substrate may increase and the package may warp.
- Resin sheet 11 preferably contains an epoxy resin and a phenol resin. Thereby, favorable thermosetting is obtained.
- 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. From the viewpoint, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are more preferable.
- 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.
- phenolic resin those having a hydroxyl equivalent weight of 70 to 250 and a softening point of 50 to 110 ° C. are preferably used from the viewpoint of reactivity with the epoxy resin, and in particular, phenol novolak from the viewpoint of high curing reactivity. Resin can be used suitably. From the viewpoint of reliability, low hygroscopic materials such as phenol aralkyl resins and biphenyl aralkyl resins can also be suitably used.
- the blending ratio of the epoxy resin and the phenol resin is blended so that the total of hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin from the viewpoint of curing reactivity. It is preferable to use 0.9 to 1.2 equivalents.
- the lower limit of the total content of epoxy resin and phenol resin in the resin sheet 11 is preferably 2.0% by weight or more, and more preferably 3.0% by weight or more. Adhesive force with respect to an electronic device, a board
- the upper limit of the total content is preferably 20% by weight or less, and more preferably 10% by weight or less. The hygroscopicity of a resin sheet can be reduced as it is 20 weight% or less.
- the resin sheet 11 preferably contains a thermoplastic resin. Thereby, the heat resistance of the resin sheet for hollow sealing obtained, flexibility, and intensity
- 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.
- Polyimide resin, polyamide resin such as 6-nylon and 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET and PBT, polyamideimide resin, fluororesin, styrene-isobutylene-styrene block copolymer Can be mentioned.
- 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 viewpoint of low stress and low water absorption in the resin sheet.
- the content of the thermoplastic resin in the resin sheet 11 is preferably 1.0% by weight or more, and more preferably 1.5% by weight or more. When it is 1.0% by weight or more, flexibility and flexibility can be suitably imparted to the resin sheet.
- the content of the thermoplastic resin in the resin sheet 11 is preferably 3.5% by weight or less, and more preferably 3.0% by weight or less.
- substrate can be improved as it is 3.5 weight% or less.
- Resin sheet 11 contains an inorganic filler in a content of 70% by volume or more and 90% by volume or less.
- the lower limit of the content is preferably 74% by volume or more, and more preferably 78% by volume or more.
- 85 volume% or less is preferable and the upper limit of the said content has more preferable 83 volume% or less.
- the content of the inorganic filler is less than the above lower limit, sufficient dilatancy-like action may not be obtained or package warping may occur. If the upper limit is exceeded, the fluidity and flexibility of the resin sheet may be increased. In some cases, the adhesiveness to the substrate or chip may decrease. In addition, when the inorganic filler is a mixture of a plurality of types of particles, the content of the mixture satisfies the above range.
- the content of the inorganic filler can be explained by using “wt%” as a unit. Typically, the content of silica will be described in units of “% by weight”. Since silica usually has a specific gravity of 2.2 g / cm 3 , the preferred range of the silica content (% by weight) is as follows. That is, the content of silica in the resin sheet 11 is preferably 81% by weight or more, and more preferably 84% by weight or more. 94 weight% or less is preferable and, as for content of the silica in the resin sheet 11, 91 weight% or less is more preferable.
- the preferred range of the alumina content is as follows. That is, the content of alumina in the resin sheet 11 is preferably 88% by weight or more, and more preferably 90% by weight or more. 97 weight% or less is preferable and, as for content of the alumina in the resin sheet 11, 95 weight% or less is more preferable.
- the shape of the inorganic filler is not particularly limited, and may be any shape such as a spherical shape (including an ellipsoidal shape), a polyhedron shape, a polygonal column shape, an indefinite shape, etc., but in a highly filled state near the hollow structure. From the viewpoints of achievement and appropriate fluidity, a spherical shape is preferable.
- the inorganic filler is not particularly limited, and various conventionally known fillers can be used.
- quartz glass, talc, silica such as fused silica and crystalline silica
- alumina aluminum nitride, silicon nitride And boron nitride powder.
- silica and alumina are preferable, and silica is more preferable because the linear expansion coefficient can be satisfactorily reduced.
- silica powder is preferable, and fused silica powder is more preferable.
- fused silica powder examples include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, spherical fused silica powder is preferable.
- the average particle diameter of the inorganic filler is preferably 50 ⁇ m or less, more preferably 0.1 to 30 ⁇ m, and particularly preferably 0.5 to 25 ⁇ m. preferable.
- the average particle diameter can be derived by using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
- the resin sheet 11 preferably contains a curing accelerator.
- the curing accelerator is not particularly limited as long as it can cure the epoxy resin and the phenol resin, and examples thereof include organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; 2-phenyl-4, And imidazole compounds such as 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
- organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate
- 2-phenyl-4, And imidazole compounds such as 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
- 2-phenyl-4,5-dihydroxymethylimidazole is preferable because the curing reaction does not rapidly proceed even when the temperature rises during kneading and the resin sheet 11 can be satisfactorily produced.
- 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.
- Resin sheet 11 preferably contains a flame retardant component. This can reduce the expansion of combustion when ignition occurs due to component short-circuiting or heat generation.
- a flame retardant component for example, various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, complex metal hydroxides; phosphazene flame retardants, etc. should be used. Can do. Of these, phosphazene-based flame retardants are preferred, and compounds represented by formula (1) or formula (2) are preferred because they are excellent in flame retardancy and strength after curing.
- 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 content of the phosphorus element contained in the phosphazene flame retardant is preferably 12% by weight or more.
- the content of the flame retardant component in the resin sheet 11 is preferably 10% by weight or more, more preferably 15% by weight or more in the total organic components. A flame retardance is favorably acquired as it is 10 weight% or more.
- the content of the thermoplastic resin in the resin sheet 11 is preferably 30% by weight or less, and more preferably 25% by weight or less in the total organic components. When the content is 30% by weight or less, there is a tendency that there is little decrease in physical properties of the cured product (specifically, physical properties such as glass transition temperature and high-temperature resin strength).
- the resin sheet 11 preferably contains a silane coupling agent.
- the silane coupling agent is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxysilane.
- the content of the silane coupling agent in the resin sheet 11 is preferably 0.1 to 3% by weight.
- the strength of the cured resin sheet can be increased and the water absorption rate can be reduced.
- production of outgas can be suppressed as the said content is 3 weight% or less.
- the resin sheet 11 preferably contains a pigment.
- the pigment is not particularly limited, and examples thereof include carbon black.
- the content of the pigment in the resin sheet 11 is preferably 0.1 to 2% by weight. When the content is 0.1% by weight or more, good marking properties can be obtained. On the other hand, the intensity
- Method for producing hollow sealing resin sheet Although the manufacturing method of the resin sheet 11 is not specifically limited, The method of preparing a kneaded material and processing the obtained kneaded material into a sheet form is preferable. Specifically, a kneaded material is prepared by melt kneading the above-described components with a known kneader such as a mixing roll, a pressure kneader, or an extruder, and the obtained kneaded material is processed into a sheet shape.
- a known kneader such as a mixing roll, a pressure kneader, or an extruder
- 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.
- the kneading is preferably performed under reduced pressure conditions (under reduced pressure atmosphere).
- the upper limit of the pressure under reduced pressure is preferably 0.1 kg / cm 2 or less, more preferably 0.05 kg / cm 2 or less.
- the lower limit of the pressure under reduced pressure is preferable, it may be 1 ⁇ 10 ⁇ 4 kg / cm 2 or more from the viewpoint of productivity and physical limit.
- the kneaded material after melt kneading is preferably processed in a high temperature state without cooling.
- the processing 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 processing temperature is preferably higher than the softening point of each component described above, and is, for example, 40 to 150 ° C., preferably 50 to 140 ° C., and more preferably 70 to 120 ° C. in consideration of the thermosetting property and moldability of the epoxy resin. .
- the thickness of the resin sheet 11 is not particularly limited, but is preferably 100 to 2000 ⁇ m.
- An electronic device can be favorably sealed as it is in the said range. Further, by making the resin sheet thin, the amount of heat generation can be reduced, and curing shrinkage hardly occurs. As a result, the amount of package warpage can be reduced, and a more reliable hollow package can be obtained.
- the resin sheet 11 may have a single layer structure or a multilayer structure in which two or more resin sheets are laminated, but there is no fear of delamination, the sheet thickness is highly uniform, and the moisture absorption is reduced.
- a single layer structure is preferred because it is easy.
- the resin sheet 11 is a SAW (Surface Acoustic Wave) filter; MEMS (Micro Electro Mechanical Systems) such as pressure sensors and vibration sensors; ICs such as LSIs; semiconductors such as transistors; capacitors; resistors; sealings of electronic devices such as CMOS sensors. Used for stopping. Especially, it can use suitably for the sealing of the electronic device (specifically SAW filter, MEMS) which needs hollow sealing, and can use it especially suitably for sealing of a SAW filter.
- SAW Surface Acoustic Wave
- MEMS Micro Electro Mechanical Systems
- FIGS. 2A to 2C are views schematically showing one step of the method for manufacturing the hollow package according to the embodiment of the present invention. It does not specifically limit as a hollow sealing method, It can seal by a conventionally well-known method. For example, a method of laminating (mounting) an uncured resin sheet 11 on a substrate while maintaining a hollow structure so as to cover an electronic device on an adherend, and then curing and sealing the resin sheet 11 Can be mentioned.
- the adherend is not particularly limited, and examples thereof include a printed wiring board, a ceramic substrate, a silicon substrate, and a metal substrate.
- the SAW chip 13 mounted on the printed wiring board 12 is hollow-sealed with the resin sheet 11 to produce a hollow package.
- a printed wiring board 12 on which a plurality of SAW chips 13 are mounted is prepared (see FIG. 2A).
- the SAW chip 13 can be formed by dicing a piezoelectric crystal on which predetermined comb-shaped electrodes are formed by a known method.
- a known device such as a flip chip bonder or a die bonder can be used.
- the SAW chip 13 and the printed wiring board 12 are electrically connected via protruding electrodes 13a such as bumps.
- a hollow portion 14 is maintained between the SAW chip 13 and the printed wiring board 12 so as not to inhibit the propagation of the surface acoustic wave on the surface of the SAW filter.
- the distance between the SAW chip 13 and the printed wiring board 12 can be set as appropriate, and is generally about 10 to 100 ⁇ m.
- the resin sheet 11 is laminated on the printed wiring board 12 so as to cover the SAW chip 13, and the SAW chip 13 is resin-sealed with the resin sheet 11 (see FIG. 2B).
- the resin sheet 11 functions as a sealing resin for protecting the SAW chip 13 and its accompanying elements from the external environment.
- the method of laminating the resin sheet 11 on the printed wiring board 12 is not particularly limited, and can be performed by a known method such as hot press or laminator.
- hot press conditions the temperature is, for example, 40 to 100 ° C., preferably 50 to 90 ° C.
- the pressure is, for example, 0.1 to 10 MPa, preferably 0.5 to 8 MPa
- the time is, for example, 0.3 to 10 minutes, preferably 0.5 to 5 minutes.
- it is preferable to press under reduced pressure conditions for example, 0.1 to 5 kPa).
- the resin sheet 11 is thermally cured to form the sealing body 15 (see FIG. 2B).
- the heating temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
- the upper limit of the heating temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
- the heating time is preferably 10 minutes or more, more preferably 30 minutes or more.
- the upper limit of the heating time is preferably 180 minutes or less, more preferably 120 minutes or less.
- the upper limit is preferably 10 MPa or less, more preferably 5 MPa or less.
- a substrate mounting process can be performed in which rewiring and bumps are formed on the hollow package 18 and mounted on a separate substrate (not shown).
- a known device such as a flip chip bonder or a die bonder can be used.
- each compounding component is kneaded with a kneader or the like to prepare a kneaded product, and the kneaded product is extruded to form a sheet.
- distributed each component in the organic solvent etc. is applied, and it forms in a sheet form.
- the above components and other additives as necessary are mixed as appropriate according to a conventional method, and uniformly dissolved or dispersed in an organic solvent to prepare a varnish.
- the resin sheet 11 for hollow sealing can be obtained by apply
- the organic solvent is not particularly limited, and various conventionally known organic solvents such as methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, and ethyl acetate can be used. These may be used alone or in combination of two or more. Usually, it is preferable to use an organic solvent so that the solid content concentration of the varnish is in the range of 30 to 95% by weight.
- the thickness of the sheet after drying the organic solvent is not particularly limited, but is usually preferably set to 5 to 100 ⁇ m, more preferably 20 to 70 ⁇ m, from the viewpoint of thickness uniformity and the amount of residual solvent. is there.
- Epoxy resin 1 YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin, epkin equivalent 200 g / eq., Softening point 80 ° C.)
- Epoxy resin 2 EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 169 g / eq., Softening point 60 ° C.)
- Phenol resin 1 MEH-7851-SS manufactured by Meiwa Kasei Co., Ltd.
- Phenol resin 2 MEH-7500 manufactured by Meiwa Kasei Co., Ltd. (phenol equivalent 97 g / eq., Softening point 111 ° C.)
- Thermoplastic resin SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka Corporation
- Inorganic filler 1 FB-9454FC (fused spherical silica, average particle size 20 ⁇ m) manufactured by Denki Kagaku Kogyo Co., Ltd.
- Inorganic filler 2 SE-40 (fused spherical silica, average particle size 38 ⁇ m) manufactured by Tokuyama Corporation
- Inorganic filler 3 FB-5SDC (fused spherical silica, average particle size 5 ⁇ m) manufactured by Denki Kagaku Kogyo Co., Ltd.
- Inorganic filler 4 SO-25R manufactured by Admatechs Co., Ltd. (fused spherical silica, average particle size 0.5 ⁇ m)
- Silane coupling agent KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
- Carbon black # 20 manufactured by Mitsubishi Chemical Flame retardant: 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.) Curing accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
- Examples 1 to 4 and Comparative Examples 1 to 4 Each component was blended according to the blending ratio shown in Table 1, and melt-kneaded in a roll kneader at 60 to 120 ° C. for 10 minutes under reduced pressure conditions (0.01 kg / cm 2 ) to prepare a kneaded product. Next, the obtained kneaded material was molded into a sheet (50 mm ⁇ 50 mm) by a flat plate pressing method, and a hollow sealing resin sheet having a thickness shown in Table 1 was produced.
- Example 5 According to the blending ratio shown in Table 1, each component was dissolved or dispersed in a 1: 1 mixed solvent of methyl ethyl ketone and toluene to prepare a varnish having a solid content of 40% by weight. Next, a varnish is applied on the PET film subjected to the release treatment so that the thickness of the coating film after drying the solvent is 50 ⁇ m, and then the coating film is dried at 120 ° C. for 3 minutes. Thus, a resin sheet having a thickness of 50 ⁇ m was obtained. The obtained resin sheet was laminated using a laminator to a thickness of 200 ⁇ m to produce a hollow sealing resin sheet having a thickness of 200 ⁇ m.
- the minimum melt viscosity of each hollow sealing resin sheet is determined by measuring the viscoelasticity measuring device “ARES” manufactured by TA Instruments (measuring conditions: measuring temperature range 60 to 130 ° C., heating rate 10 ° C./min, frequency 0. Table 1 shows the result of measuring the minimum value of the viscosity when the viscosity change was traced at 1 Hz).
- the linear expansion coefficient was measured using a thermomechanical analyzer (manufactured by Rigaku Corporation: model: TMA8310). Specifically, each hollow sealing resin sheet was heated and cured at 150 ° C. for 1 hour, and a measurement sample was obtained from this cured product with a sample size of 25 mm long ⁇ 4.9 mm wide ⁇ 200 ⁇ m thick. Thereafter, the measurement sample was set on a film tensile measurement jig and measured under conditions of a tensile load of 4.9 mN and a temperature increase rate of 10 ° C./min to obtain a linear expansion coefficient. The results are shown in Table 1.
- the gap width between the SAW chip and the glass substrate was 30 ⁇ m, and in Example 4, it was 90 ⁇ m.
- Each hollow sealing resin sheet was stuck on the obtained SAW chip mounting substrate by a vacuum press under the heating and pressurization conditions shown below.
- the resin sheet for hollow sealing was thermoset in a hot air dryer at 150 ° C. for 1 hour to obtain a sealed body. After the sealing body is cooled to room temperature, the resin enters the hollow portion between the SAW chip and the glass substrate from the glass substrate side using an electron microscope (trade name “Digital Microscope”, 200 ⁇ , manufactured by KEYENCE). The amount was measured. The amount of resin penetration is confirmed and memorized by the electron microscope from the glass substrate side before sealing with the hollow sealing resin sheet, and observed again from the glass substrate side with the electron microscope after sealing.
- the amount of warpage of the sealed body cooled to room temperature is measured by scanning the surface on the resin sheet side using a laser three-dimensional measuring device ("LS-220-MT50" manufactured by TETECH Co., Ltd.). Was evaluated as “ ⁇ ” when 1 mm or less, and “X” when exceeding 1 mm.
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Abstract
Provided are a hollow sealing resin sheet which is capable of maintaining a hollow structure even if the width of the void in the hollow structure is approximately 100 μm and is capable of preparing a hollow package having high reliability by preventing warping of the package, and a production method for a hollow package. This hollow sealing resin sheet includes an inorganic filler in an amount of 70 vol% to 90 vol% inclusive, and has a minimum melt viscosity measured by dynamic mechanical analysis at 60-130°C of 2000 Pa·s to 20000 Pa·s inclusive, a storage modulus at 20°C of 1 GPa to 20 GPa inclusive following heat curing for one hour at 150°C, and a linear expansion coefficient at or below the glass transition temperature of 5 ppm/K to 15 ppm/K inclusive following heat curing for one hour at 150°C.
Description
本発明は、中空封止用樹脂シート及び中空パッケージの製造方法に関する。
The present invention relates to a hollow sealing resin sheet and a method for producing a hollow package.
電子デバイスパッケージの作製には、代表的に、バンプ等を介して基板などに固定された1又は複数の電子デバイスを封止樹脂にて封止し、必要に応じて封止体を電子デバイス単位のパッケージとなるようにダイシングするという手順が採用されている。このような封止樹脂として、シート状の封止樹脂が用いられることがある。
For the production of an electronic device package, typically, one or more electronic devices fixed to a substrate or the like via bumps or the like are sealed with a sealing resin, and the sealing body is united as an electronic device as necessary. The procedure of dicing so that it becomes a package of is adopted. As such a sealing resin, a sheet-shaped sealing resin may be used.
近年、半導体パッケージと並んで、SAW(Surface Acoustic Wave)フィルタや、CMOS(Complementary Metal Oxide Semiconductor)センサ、加速度センサ等のMEMSと称される微小電子デバイスの開発が進められている。これらの電子デバイスを封止したパッケージは、それぞれ一般的に表面弾性波の伝播、光学系の維持、電子デバイスの可動部材の可動性を確保するための中空構造を有している。この中空構造は、基板と素子との間の空隙として設けられることが多い。封止の際には、可動部材の作動信頼性や素子の接続信頼性を確保するよう中空構造を維持しつつ封止する必要がある。例えば、特許文献1には、ゲル状の硬化性樹脂シートを用いて機能素子を中空モールドする技術が記載されている。
In recent years, along with semiconductor packages, development of microelectronic devices called MEMS, such as SAW (Surface Acoustic Wave) filters, CMOS (Complementary Metal Oxide Semiconductor) sensors, and acceleration sensors, has been promoted. Each of the packages encapsulating these electronic devices generally has a hollow structure for ensuring the propagation of surface acoustic waves, maintaining the optical system, and movability of the movable member of the electronic device. This hollow structure is often provided as a gap between the substrate and the element. When sealing, it is necessary to seal while maintaining the hollow structure so as to ensure the operation reliability of the movable member and the connection reliability of the element. For example, Patent Document 1 describes a technique of hollow-molding a functional element using a gel-like curable resin sheet.
上記中空構造を与えるバンプはそのサイズが小さいほどコストが高くなるという事情や、上記可動部材の複雑化や複合化のための中空構造の拡大という要求に鑑み、今後はバンプ径を増加させて空隙を拡大するという方策が採られることが予想される。上記特許文献1に記載の技術では、素子と基板との間の中空構造として幅が数十μm程度の空隙までであれば所望の中空構造を維持しながら電子デバイスを封止することができる。しかしなら、中空構造として幅が100μm近い空隙を確保しながら封止するとなると、中空構造への樹脂流入が発生する等して対応が困難となり、パッケージ作製の歩留まりが低下する場合がある。
In view of the fact that the bumps that give the hollow structure have a higher cost as the size is smaller, and that there is a need to expand the hollow structure in order to make the movable member more complex and complex, the bump diameter will be increased in the future. It is expected that measures will be taken to expand With the technique described in Patent Document 1, the electronic device can be sealed while maintaining a desired hollow structure as long as the hollow structure between the element and the substrate is a gap having a width of about several tens of μm. However, if sealing is performed while ensuring a gap having a width of approximately 100 μm as a hollow structure, it may be difficult to cope with the occurrence of resin inflow into the hollow structure, and the package manufacturing yield may be reduced.
また、中空構造の拡大とパッケージ全体のダウンサイジングという相反する要求のためにチップの厚さを従来に比してより薄型化する必要が生じる。しかしながら、チップの厚さを薄くすると、チップ自体の強度が低下して基板の反りの影響を受けやすくなり、パッケージの信頼性が低下する場合がある。
Also, due to the conflicting demands of expanding the hollow structure and downsizing the entire package, it is necessary to make the chip thickness thinner than before. However, if the thickness of the chip is reduced, the strength of the chip itself is reduced, and it is easily affected by the warp of the substrate, which may reduce the reliability of the package.
本発明の目的は、中空構造の空隙の幅が100μm程度であっても中空構造を維持可能であるとともに、パッケージの反りを防止して信頼性の高い中空パッケージを作製可能な中空封止用樹脂シート及び中空パッケージの製造方法を提供することにある。
An object of the present invention is to provide a hollow sealing resin that can maintain a hollow structure even when the width of the void of the hollow structure is about 100 μm, and that can produce a highly reliable hollow package by preventing warpage of the package It is to provide a method for manufacturing a sheet and a hollow package.
本発明者らは、鋭意検討した結果、下記構成を採用することにより上記課題を解決できることを見出し、本発明を完成させた。
As a result of intensive studies, the present inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention.
すなわち、本発明の中空封止用樹脂シートは、無機充填剤を70体積%以上90体積%以下の含有量で含み、
動的粘弾性測定による60~130℃での最低溶融粘度が2000Pa・s以上20000Pa・s以下であり、
150℃で1時間熱硬化させた後の常温(20℃)における貯蔵弾性率が1GPa以上20GPa以下であり、
150℃で1時間熱硬化させた後のガラス転移温度以下における線膨張係数が5ppm/K以上15ppm/K以下である。 That is, the hollow sealing resin sheet of the present invention contains an inorganic filler in a content of 70 vol% or more and 90 vol% or less,
The minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement is 2000 Pa · s or more and 20000 Pa · s or less,
The storage elastic modulus at normal temperature (20 ° C.) after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less,
The linear expansion coefficient at the glass transition temperature or lower after thermosetting at 150 ° C. for 1 hour is 5 ppm / K or more and 15 ppm / K or less.
動的粘弾性測定による60~130℃での最低溶融粘度が2000Pa・s以上20000Pa・s以下であり、
150℃で1時間熱硬化させた後の常温(20℃)における貯蔵弾性率が1GPa以上20GPa以下であり、
150℃で1時間熱硬化させた後のガラス転移温度以下における線膨張係数が5ppm/K以上15ppm/K以下である。 That is, the hollow sealing resin sheet of the present invention contains an inorganic filler in a content of 70 vol% or more and 90 vol% or less,
The minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement is 2000 Pa · s or more and 20000 Pa · s or less,
The storage elastic modulus at normal temperature (20 ° C.) after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less,
The linear expansion coefficient at the glass transition temperature or lower after thermosetting at 150 ° C. for 1 hour is 5 ppm / K or more and 15 ppm / K or less.
当該中空封止用樹脂シートは、高含有量の無機充填剤により最低溶融粘度を2000Pa・s以上20000Pa・s以下としているので、中空構造への樹脂進入を抑制して信頼性の高い中空パッケージを製造することができる。また、熱硬化後の貯蔵弾性率及び線膨張係数をそれぞれ所定範囲としているので、硬化後のパッケージ強度を確保することができるとともに、はんだリフロー工程等において高温が負荷されてもパッケージの反りを防止し、より信頼性の高いパッケージを製造することができる。なお、最低溶融粘度、貯蔵弾性率、ガラス転移温度及び線膨張係数の測定方法は実施例の記載による。
Since the resin sheet for hollow sealing has a minimum melt viscosity of 2000 Pa · s or more and 20000 Pa · s or less due to a high content of inorganic filler, a highly reliable hollow package can be obtained by suppressing resin intrusion into the hollow structure. Can be manufactured. In addition, since the storage elastic modulus and linear expansion coefficient after thermosetting are in a predetermined range, the package strength after curing can be ensured and package warpage can be prevented even when a high temperature is applied in a solder reflow process. In addition, a more reliable package can be manufactured. In addition, the measuring method of minimum melt viscosity, storage elastic modulus, glass transition temperature, and a linear expansion coefficient is based on description of an Example.
本発明には、被着体上に配置された1又は複数の電子デバイスを覆うように当該中空封止用樹脂シートを前記電子デバイス上に前記被着体と前記電子デバイスとの間の中空部を維持しながら積層する積層工程、及び
前記中空封止用樹脂シートを硬化させて封止体を形成する封止体形成工程
を含む中空パッケージの製造方法も含まれる。 In the present invention, the hollow sealing resin sheet is disposed on the electronic device so as to cover one or a plurality of electronic devices arranged on the adherend. The manufacturing method of the hollow package including the lamination process which laminates | stacks, maintaining the resin, and the sealing body formation process which hardens the said resin sheet for hollow sealing and forms a sealing body is also included.
前記中空封止用樹脂シートを硬化させて封止体を形成する封止体形成工程
を含む中空パッケージの製造方法も含まれる。 In the present invention, the hollow sealing resin sheet is disposed on the electronic device so as to cover one or a plurality of electronic devices arranged on the adherend. The manufacturing method of the hollow package including the lamination process which laminates | stacks, maintaining the resin, and the sealing body formation process which hardens the said resin sheet for hollow sealing and forms a sealing body is also included.
以下に実施形態を掲げ、本発明を詳細に説明するが、本発明はこれらの実施形態のみに限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited only to these embodiments.
《第1実施形態》
[中空封止用樹脂シート] << First Embodiment >>
[Hollow sealing resin sheet]
[中空封止用樹脂シート] << First Embodiment >>
[Hollow sealing resin sheet]
図1は、本発明の一実施形態に係る中空封止用樹脂シート(以下、単に「樹脂シート」ともいう。)11を模式的に示す断面図である。樹脂シート11は、代表的に、ポリエチレンテレフタレート(PET)フィルムなどの支持体11a上に積層された状態で提供される。なお、支持体11aには樹脂シート11の剥離を容易に行うために離型処理が施されていてもよい。
FIG. 1 is a cross-sectional view schematically showing a hollow sealing resin sheet (hereinafter also simply referred to as “resin sheet”) 11 according to an embodiment of the present invention. The resin sheet 11 is typically provided in a state of being laminated on a support 11a such as a polyethylene terephthalate (PET) film. Note that a release treatment may be performed on the support 11a in order to easily peel off the resin sheet 11.
樹脂シート11の硬化前の動的粘弾性測定による60~130℃での最低溶融粘度は2000Pa・s以上20000Pa・s以下であればよく、3000Pa・s以上15000Pa・s以下であることが好ましく、5000Pa・s以上10000Pa・s以下であることがより好ましい。樹脂シート11の最低溶融粘度が上記範囲とすることにより、中空構造への樹脂の進入を効率的に防止し、信頼性の高い中空パッケージを得ることができる。上記最低溶融粘度が下限未満であると、中空構造への樹脂の進入が生じてしまい、パッケージの信頼性が低下するおそれがある。一方、上記上限を超えると、チップの埋まり込み性が低下してボイドが発生するおそれがある。
The minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement before curing of the resin sheet 11 may be 2000 Pa · s or more and 20000 Pa · s or less, and preferably 3000 Pa · s or more and 15000 Pa · s or less, More preferably, it is 5000 Pa · s or more and 10,000 Pa · s or less. By setting the minimum melt viscosity of the resin sheet 11 within the above range, it is possible to efficiently prevent the resin from entering the hollow structure and to obtain a highly reliable hollow package. If the minimum melt viscosity is less than the lower limit, the resin may enter the hollow structure and the reliability of the package may be reduced. On the other hand, when the above upper limit is exceeded, there is a possibility that the embedding property of the chip is lowered and a void is generated.
樹脂シート11では、150℃で1時間熱硬化させた後の20℃における貯蔵弾性率は1GPa以上20GPa以下であり、その下限としては1.5GPa以上が好ましく、2GPa以上がより好ましい。また、該貯蔵弾性率の上限としては10GPa以下が好ましく、5GPa以下がより好ましい。硬化後の貯蔵弾性率を上記範囲とうすることによりパッケージの強度を確保することができる。上記貯蔵弾性率の下限未満であると、パッケージ強度が充分でなくなり信頼性が低下するおそれがある。一方、上記上限を超えた場合には、衝撃に対して脆くなってパッケージ強度が充分でなくなり、この場合も信頼性が低下するおそれがある。
In the resin sheet 11, the storage elastic modulus at 20 ° C. after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less, and the lower limit thereof is preferably 1.5 GPa or more, and more preferably 2 GPa or more. Moreover, as an upper limit of this storage elastic modulus, 10 GPa or less is preferable and 5 GPa or less is more preferable. By setting the storage elastic modulus after curing within the above range, the strength of the package can be ensured. If the storage elastic modulus is less than the lower limit, the package strength may be insufficient and the reliability may be lowered. On the other hand, when the above upper limit is exceeded, the package becomes brittle with respect to impact and the package strength becomes insufficient, and in this case, the reliability may be lowered.
当該封止樹脂シートでは、150℃で1時間熱硬化処理した後のガラス転移温度は70℃以上であることが好ましく、90℃以上であることがより好ましく、110℃以上であることがさらに好ましい。当該封止樹脂シートがこのような構成を備えることにより、耐熱性を向上させることができる。これに対し、上記熱硬化処理後のガラス転移温度の上限は特に限定されないものの、熱硬化の際の硬化収縮低減の観点から、250℃以下が好ましく、200℃以下がより好ましい。
In the sealing resin sheet, the glass transition temperature after thermosetting at 150 ° C. for 1 hour is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 110 ° C. or higher. . When the sealing resin sheet has such a configuration, heat resistance can be improved. On the other hand, although the upper limit of the glass transition temperature after the thermosetting treatment is not particularly limited, it is preferably 250 ° C. or less, and more preferably 200 ° C. or less, from the viewpoint of reducing curing shrinkage during thermosetting.
樹脂シート11を150℃で1時間熱硬化させた後のガラス転移温度以下における線膨張係数は5ppm/K以上15ppm/K以下であればよい。該線膨張係数の下限は6ppm/K以上が好ましく、7ppm/K以上がより好ましい。該線膨張係数の上限は12ppm/K以下であることが好ましく、9ppm/K以下がより好ましい。所定の熱処理後の熱処理物のガラス転移温度以下での線膨張係数を上記範囲とすることより、封止処理後にパッケージ構造に対して高温処理を施しても、樹脂シート11と、特に低線膨張係数を有する基板との線膨張係数の差を小さくすることができ、基板の反り等を防止することができる。上記線膨張係数が上記下限未満であるか、又は上記上限を超えると、樹脂シートと基板との線膨張係数の差が大きくなってパッケージに反りが生じる場合がある。
The linear expansion coefficient below the glass transition temperature after thermosetting the resin sheet 11 at 150 ° C. for 1 hour may be 5 ppm / K or more and 15 ppm / K or less. The lower limit of the linear expansion coefficient is preferably 6 ppm / K or more, more preferably 7 ppm / K or more. The upper limit of the linear expansion coefficient is preferably 12 ppm / K or less, and more preferably 9 ppm / K or less. By setting the linear expansion coefficient below the glass transition temperature of the heat-treated product after a predetermined heat treatment within the above range, even if the package structure is subjected to a high-temperature treatment after the sealing treatment, the resin sheet 11 and particularly low linear expansion. A difference in coefficient of linear expansion from a substrate having a coefficient can be reduced, and warpage of the substrate can be prevented. If the linear expansion coefficient is less than the lower limit or exceeds the upper limit, the difference in the linear expansion coefficient between the resin sheet and the substrate may increase and the package may warp.
樹脂シート11はエポキシ樹脂、及びフェノール樹脂を含むことが好ましい。これにより、良好な熱硬化性が得られる。
Resin sheet 11 preferably contains an epoxy resin and a phenol resin. Thereby, favorable thermosetting is obtained.
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より好ましい。
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 more preferable.
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℃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。
As the phenolic resin, those having a hydroxyl equivalent weight of 70 to 250 and a softening point of 50 to 110 ° C. are preferably used from the viewpoint of reactivity with the epoxy resin, and in particular, phenol novolak from the viewpoint of high curing reactivity. Resin can be used suitably. From the viewpoint of reliability, low hygroscopic materials such as phenol aralkyl resins and biphenyl aralkyl resins can also be suitably used.
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。
The blending ratio of the epoxy resin and the phenol resin is blended so that the total of hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin from the viewpoint of curing reactivity. It is preferable to use 0.9 to 1.2 equivalents.
樹脂シート11中のエポキシ樹脂及びフェノール樹脂の合計含有量の下限は、2.0重量%以上が好ましく、3.0重量%以上がより好ましい。2.0重量%以上であると、電子デバイス、基板などに対する接着力が良好に得られる。一方、上記合計含有量の上限は20重量%以下が好ましく、10重量%以下がより好ましい。20重量%以下であると、樹脂シートの吸湿性を低減させることができる。
The lower limit of the total content of epoxy resin and phenol resin in the resin sheet 11 is preferably 2.0% by weight or more, and more preferably 3.0% by weight or more. Adhesive force with respect to an electronic device, a board | substrate, etc. is acquired favorably as it is 2.0 weight% or more. On the other hand, the upper limit of the total content is preferably 20% by weight or less, and more preferably 10% by weight or less. The hygroscopicity of a resin sheet can be reduced as it is 20 weight% or less.
樹脂シート11は、熱可塑性樹脂を含むことが好ましい。これにより、得られる中空封止用樹脂シートの耐熱性、可撓性、強度を向上させることができる。
The resin sheet 11 preferably contains a thermoplastic resin. Thereby, the heat resistance of the resin sheet for hollow sealing obtained, flexibility, and intensity | strength can be improved.
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、フッ素樹脂、スチレン-イソブチレン-スチレンブロック共重合体などが挙げられる。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、樹脂シートにおける低応力性、低吸水性という観点から、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. Polyimide resin, polyamide resin such as 6-nylon and 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET and PBT, polyamideimide resin, fluororesin, styrene-isobutylene-styrene block copolymer Can be mentioned. 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 viewpoint of low stress and low water absorption in the resin sheet.
樹脂シート11中の熱可塑性樹脂の含有量は、1.0重量%以上が好ましく、1.5重量%以上がより好ましい。1.0重量%以上であると、樹脂シートに柔軟性、可撓性を好適に付与することができる。樹脂シート11中の熱可塑性樹脂の含有量は、3.5重量%以下が好ましく、3.0重量%以下がより好ましい。3.5重量%以下であると、電子デバイスや基板に対する樹脂シートの接着性を向上させることができる。
The content of the thermoplastic resin in the resin sheet 11 is preferably 1.0% by weight or more, and more preferably 1.5% by weight or more. When it is 1.0% by weight or more, flexibility and flexibility can be suitably imparted to the resin sheet. The content of the thermoplastic resin in the resin sheet 11 is preferably 3.5% by weight or less, and more preferably 3.0% by weight or less. The adhesiveness of the resin sheet with respect to an electronic device or a board | substrate can be improved as it is 3.5 weight% or less.
樹脂シート11は、無機質充填剤を70体積%以上90体積%以下の含有量で含む。上記含有量の下限は74体積%以上が好ましく、78体積%以上がより好ましい。また、上記含有量の上限は、85体積%以下が好ましく、83体積%以下がより好ましい。無機充填剤の含有量を上記範囲とすることにより、中空構造付近における樹脂へのダイラタンシー様作用を好適に付与して中空構造を維持することができるとともに、硬化後の線膨張係数を低下させてパッケージの反りを防止し、高信頼性の中空パッケージを得ることができる。無機充填剤の含有量が上記下限未満であると、充分なダイラタンシー様作用を得られなかったり、パッケージの反りが生じたりする場合があり、上記上限を超えると樹脂シートの流動性や柔軟性が低下して基板やチップへの接着性が低下する場合がある。なお、無機充填剤が複数種の粒子の混合物である場合は、その混合物の含有量が上記範囲を満たす。
Resin sheet 11 contains an inorganic filler in a content of 70% by volume or more and 90% by volume or less. The lower limit of the content is preferably 74% by volume or more, and more preferably 78% by volume or more. Moreover, 85 volume% or less is preferable and the upper limit of the said content has more preferable 83 volume% or less. By setting the content of the inorganic filler in the above range, the dilatancy-like action can be suitably imparted to the resin in the vicinity of the hollow structure to maintain the hollow structure, and the linear expansion coefficient after curing is reduced. Package warpage can be prevented, and a highly reliable hollow package can be obtained. If the content of the inorganic filler is less than the above lower limit, sufficient dilatancy-like action may not be obtained or package warping may occur. If the upper limit is exceeded, the fluidity and flexibility of the resin sheet may be increased. In some cases, the adhesiveness to the substrate or chip may decrease. In addition, when the inorganic filler is a mixture of a plurality of types of particles, the content of the mixture satisfies the above range.
無機質充填剤の含有量は、「重量%」を単位としても説明できる。代表的にシリカの含有量について、「重量%」を単位として説明する。
シリカは通常、比重2.2g/cm3であるので、シリカの含有量(重量%)の好適範囲は以下のとおりである。すなわち、樹脂シート11中のシリカの含有量は、81重量%以上が好ましく、84重量%以上がより好ましい。樹脂シート11中のシリカの含有量は、94重量%以下が好ましく、91重量%以下がより好ましい。 The content of the inorganic filler can be explained by using “wt%” as a unit. Typically, the content of silica will be described in units of “% by weight”.
Since silica usually has a specific gravity of 2.2 g / cm 3 , the preferred range of the silica content (% by weight) is as follows. That is, the content of silica in theresin sheet 11 is preferably 81% by weight or more, and more preferably 84% by weight or more. 94 weight% or less is preferable and, as for content of the silica in the resin sheet 11, 91 weight% or less is more preferable.
シリカは通常、比重2.2g/cm3であるので、シリカの含有量(重量%)の好適範囲は以下のとおりである。すなわち、樹脂シート11中のシリカの含有量は、81重量%以上が好ましく、84重量%以上がより好ましい。樹脂シート11中のシリカの含有量は、94重量%以下が好ましく、91重量%以下がより好ましい。 The content of the inorganic filler can be explained by using “wt%” as a unit. Typically, the content of silica will be described in units of “% by weight”.
Since silica usually has a specific gravity of 2.2 g / cm 3 , the preferred range of the silica content (% by weight) is as follows. That is, the content of silica in the
アルミナは通常、比重3.9g/cm3であるので、アルミナの含有量(重量%)の好適範囲は以下のとおりである。すなわち、樹脂シート11中のアルミナの含有量は、88重量%以上が好ましく、90重量%以上がより好ましい。樹脂シート11中のアルミナの含有量は、97重量%以下が好ましく、95重量%以下がより好ましい。
Since alumina usually has a specific gravity of 3.9 g / cm 3 , the preferred range of the alumina content (% by weight) is as follows. That is, the content of alumina in the resin sheet 11 is preferably 88% by weight or more, and more preferably 90% by weight or more. 97 weight% or less is preferable and, as for content of the alumina in the resin sheet 11, 95 weight% or less is more preferable.
無機充填剤の形状は特に限定されず、球状(楕円体状を含む。)、多面体状、多角柱状、不定形状等の任意の形状であってもよいが、中空構造付近での高充填状態の達成や適度な流動性の観点から、球状が好ましい。
The shape of the inorganic filler is not particularly limited, and may be any shape such as a spherical shape (including an ellipsoidal shape), a polyhedron shape, a polygonal column shape, an indefinite shape, etc., but in a highly filled state near the hollow structure. From the viewpoints of achievement and appropriate fluidity, a spherical shape is preferable.
無機質充填剤は、特に限定されるものではなく、従来公知の各種充填剤を用いることができ、例えば、石英ガラス、タルク、シリカ(溶融シリカや結晶性シリカなど)、アルミナ、窒化アルミニウム、窒化珪素、窒化ホウ素の粉末が挙げられる。これらは単独で用いてもよいし、2種以上併用してもよい。なかでも、線膨張係数を良好に低減できるという理由から、シリカ、アルミナが好ましく、シリカがより好ましい。
The inorganic filler is not particularly limited, and various conventionally known fillers can be used. For example, quartz glass, talc, silica (such as fused silica and crystalline silica), alumina, aluminum nitride, silicon nitride And boron nitride powder. These may be used alone or in combination of two or more. Among these, silica and alumina are preferable, and silica is more preferable because the linear expansion coefficient can be satisfactorily reduced.
シリカとしては、シリカ粉末が好ましく、溶融シリカ粉末がより好ましい。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が好ましい。
As silica, silica powder is preferable, and fused silica powder is more preferable. Examples of the fused silica powder include spherical fused silica powder and crushed fused silica powder. From the viewpoint of fluidity, spherical fused silica powder is preferable.
無機充填剤の平均粒径は50μm以下の範囲のものを用いることが好ましく、0.1~30μmの範囲のものを用いることがより好ましく、0.5~25μmの範囲のものを用いることが特に好ましい。なお、平均粒径は、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 the inorganic filler is preferably 50 μm or less, more preferably 0.1 to 30 μm, and particularly preferably 0.5 to 25 μm. preferable. The average particle diameter can be derived by using a sample arbitrarily extracted from the population and measuring it using a laser diffraction / scattering particle size distribution measuring apparatus.
樹脂シート11は、硬化促進剤を含むことが好ましい。
The resin sheet 11 preferably contains a curing accelerator.
硬化促進剤としては、エポキシ樹脂とフェノール樹脂の硬化を進行させるものであれば特に限定されず、例えば、トリフェニルホスフィン、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;2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾールなどのイミダゾール系化合物;などが挙げられる。なかでも、混練時の温度上昇によっても硬化反応が急激に進まず、樹脂シート11を良好に作製できるという理由から、2-フェニル-4,5-ジヒドロキシメチルイミダゾールが好ましい。
The curing accelerator is not particularly limited as long as it can cure the epoxy resin and the phenol resin, and examples thereof include organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; 2-phenyl-4, And imidazole compounds such as 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among these, 2-phenyl-4,5-dihydroxymethylimidazole is preferable because the curing reaction does not rapidly proceed even when the temperature rises during kneading and the resin sheet 11 can be satisfactorily produced.
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.
樹脂シート11は、難燃剤成分を含むことが好ましい。これにより、部品ショートや発熱などにより発火した際の、燃焼拡大を低減できる。難燃剤組成分としては、例えば水酸化アルミニウム、水酸化マグネシウム、水酸化鉄、水酸化カルシウム、水酸化スズ、複合化金属水酸化物などの各種金属水酸化物;ホスファゼン系難燃剤などを用いることができる。なかでも、難燃性、硬化後の強度に優れるという理由から、ホスファゼン系難燃剤が好ましく、式(1)又は式(2)で表される化合物が好ましい。
Resin sheet 11 preferably contains a flame retardant component. This can reduce the expansion of combustion when ignition occurs due to component short-circuiting or heat generation. As the flame retardant composition, for example, various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, complex metal hydroxides; phosphazene flame retardants, etc. should be used. Can do. Of these, phosphazene-based flame retardants are preferred, and compounds represented by formula (1) or formula (2) are preferred because they are excellent in flame retardancy and strength after curing.
(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。)
(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)
(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。)
(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。
(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).
(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.)
(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).
(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 content of the phosphorus element contained in the phosphazene flame retardant is preferably 12% by weight or more.
樹脂シート11中の難燃剤成分の含有量は、全有機成分中の10重量%以上が好ましく、15重量%以上がより好ましい。10重量%以上であると、難燃性が良好に得られる。樹脂シート11中の熱可塑性樹脂の含有量は、全有機成分中の30重量%以下が好ましく、25重量%以下がより好ましい。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)が少ない傾向がある。
The content of the flame retardant component in the resin sheet 11 is preferably 10% by weight or more, more preferably 15% by weight or more in the total organic components. A flame retardance is favorably acquired as it is 10 weight% or more. The content of the thermoplastic resin in the resin sheet 11 is preferably 30% by weight or less, and more preferably 25% by weight or less in the total organic components. When the content is 30% by weight or less, there is a tendency that there is little decrease in physical properties of the cured product (specifically, physical properties such as glass transition temperature and high-temperature resin strength).
樹脂シート11は、シランカップリング剤を含むことが好ましい。シランカップリング剤としては特に限定されず、3-グリシドキシプロピルトリメトキシシランなどが挙げられる。
The resin sheet 11 preferably contains a silane coupling agent. The silane coupling agent is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxysilane.
樹脂シート11中のシランカップリング剤の含有量は、0.1~3重量%が好ましい。上記含有量が0.1重量%以上であると、硬化後の樹脂シートの強度を高めることができるとともに、吸水率を低減させることができる。一方、上記含有量が3重量%以下であると、アウトガスの発生を抑制することができる。
The content of the silane coupling agent in the resin sheet 11 is preferably 0.1 to 3% by weight. When the content is 0.1% by weight or more, the strength of the cured resin sheet can be increased and the water absorption rate can be reduced. On the other hand, generation | occurrence | production of outgas can be suppressed as the said content is 3 weight% or less.
樹脂シート11は、顔料を含むことが好ましい。顔料としては特に限定されず、カーボンブラックなどが挙げられる。
The resin sheet 11 preferably contains a pigment. The pigment is not particularly limited, and examples thereof include carbon black.
樹脂シート11中の顔料の含有量は、0.1~2重量%が好ましい。0.1重量%以上であると、良好なマーキング性が得られる。一方、2重量%以下であると、硬化後の樹脂シートの強度を確保することができる。
The content of the pigment in the resin sheet 11 is preferably 0.1 to 2% by weight. When the content is 0.1% by weight or more, good marking properties can be obtained. On the other hand, the intensity | strength of the resin sheet after hardening can be ensured as it is 2 weight% or less.
なお、樹脂組成物には、上記の各成分以外に必要に応じて、他の添加剤を適宜配合できる。
In addition to the above components, other additives can be appropriately added to the resin composition as necessary.
[中空封止用樹脂シートの製造方法]
樹脂シート11の製造方法は特に限定されないが、混練物を調製し、得られた混練物をシート状に加工する方法が好ましい。具体的には、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、得られた混練物をシート状に加工する。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。 [Method for producing hollow sealing resin sheet]
Although the manufacturing method of theresin sheet 11 is not specifically limited, The method of preparing a kneaded material and processing the obtained kneaded material into a sheet form is preferable. Specifically, a kneaded material is prepared by melt kneading the above-described components with a known kneader such as a mixing roll, a pressure kneader, or an extruder, and the obtained kneaded material is processed into a sheet shape. 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.
樹脂シート11の製造方法は特に限定されないが、混練物を調製し、得られた混練物をシート状に加工する方法が好ましい。具体的には、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、得られた混練物をシート状に加工する。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。 [Method for producing hollow sealing resin sheet]
Although the manufacturing method of the
混練は、減圧条件下(減圧雰囲気下)で行うことが好ましい。減圧条件下の圧力の上限は、好ましくは0.1kg/cm2以下、より好ましくは0.05kg/cm2以下である。減圧条件下の圧力の下限は低いほど好ましいが、生産性や物理的限界から、1×10-4kg/cm2以上であってもよい。これにより、混練物への気体の混入を防止でき、得られる混練物における気孔の発生を抑制することができる。
The kneading is preferably performed under reduced pressure conditions (under reduced pressure atmosphere). The upper limit of the pressure under reduced pressure is preferably 0.1 kg / cm 2 or less, more preferably 0.05 kg / cm 2 or less. Although the lower limit of the pressure under reduced pressure is preferable, it may be 1 × 10 −4 kg / cm 2 or more from the viewpoint of productivity and physical limit. Thereby, mixing of the gas to a kneaded material can be prevented, and generation | occurrence | production of the pore in the kneaded material obtained can be suppressed.
溶融混練後の混練物は、冷却することなく高温状態のままで加工することが好ましい。加工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などが挙げられる。加工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およ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。
The kneaded material after melt kneading is preferably processed in a high temperature state without cooling. The processing 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 processing temperature is preferably higher than the softening point of each component described above, and is, for example, 40 to 150 ° C., preferably 50 to 140 ° C., and more preferably 70 to 120 ° C. in consideration of the thermosetting property and moldability of the epoxy resin. .
樹脂シート11の厚さは特に限定されないが、100~2000μmであることが好ましい。上記範囲内であると、良好に電子デバイスを封止することができる。また、樹脂シートを薄型にすることで、発熱量を低減でき、硬化収縮が起こりにくくなる。この結果、パッケージ反り量を低減でき、より信頼性の高い中空パッケージが得られる。
The thickness of the resin sheet 11 is not particularly limited, but is preferably 100 to 2000 μm. An electronic device can be favorably sealed as it is in the said range. Further, by making the resin sheet thin, the amount of heat generation can be reduced, and curing shrinkage hardly occurs. As a result, the amount of package warpage can be reduced, and a more reliable hollow package can be obtained.
樹脂シート11は、単層構造であってもよいし、2以上の樹脂シートを積層した多層構造であってもよいが、層間剥離のおそれがなく、シート厚の均一性が高く、低吸湿化し易いという理由から、単層構造が好ましい。
The resin sheet 11 may have a single layer structure or a multilayer structure in which two or more resin sheets are laminated, but there is no fear of delamination, the sheet thickness is highly uniform, and the moisture absorption is reduced. A single layer structure is preferred because it is easy.
樹脂シート11は、SAW(Surface Acoustic Wave)フィルタ;圧力センサ、振動センサなどのMEMS(Micro Electro Mechanical Systems);LSIなどのIC、トランジスタなどの半導体;コンデンサ;抵抗;CMOSセンサなどの電子デバイスの封止に使用される。なかでも、中空封止が必要な電子デバイス(具体的には、SAWフィルタ、MEMS)の封止に好適に使用でき、SAWフィルタの封止に特に好適に使用できる。
The resin sheet 11 is a SAW (Surface Acoustic Wave) filter; MEMS (Micro Electro Mechanical Systems) such as pressure sensors and vibration sensors; ICs such as LSIs; semiconductors such as transistors; capacitors; resistors; sealings of electronic devices such as CMOS sensors. Used for stopping. Especially, it can use suitably for the sealing of the electronic device (specifically SAW filter, MEMS) which needs hollow sealing, and can use it especially suitably for sealing of a SAW filter.
[中空パッケージの製造方法]
図2A~2Cはそれぞれ、本発明の一実施形態に係る中空パッケージの製造方法の一工程を模式的に示す図である。中空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、被着体上の電子デバイスを覆うように未硬化の樹脂シート11を基板上に中空構造を維持しながら積層(載置)し、次いで樹脂シート11を硬化させて封止する方法などが挙げられる。被着体としては特に限定されず、例えば、プリント配線基板、セラミック基板、シリコン基板、金属基板等が挙げられる。本実施形態では、プリント配線基板12上に搭載されたSAWチップ13を樹脂シート11により中空封止して中空パッケージを作製する。 [Method of manufacturing hollow package]
2A to 2C are views schematically showing one step of the method for manufacturing the hollow package according to the embodiment of the present invention. It does not specifically limit as a hollow sealing method, It can seal by a conventionally well-known method. For example, a method of laminating (mounting) anuncured resin sheet 11 on a substrate while maintaining a hollow structure so as to cover an electronic device on an adherend, and then curing and sealing the resin sheet 11 Can be mentioned. The adherend is not particularly limited, and examples thereof include a printed wiring board, a ceramic substrate, a silicon substrate, and a metal substrate. In the present embodiment, the SAW chip 13 mounted on the printed wiring board 12 is hollow-sealed with the resin sheet 11 to produce a hollow package.
図2A~2Cはそれぞれ、本発明の一実施形態に係る中空パッケージの製造方法の一工程を模式的に示す図である。中空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、被着体上の電子デバイスを覆うように未硬化の樹脂シート11を基板上に中空構造を維持しながら積層(載置)し、次いで樹脂シート11を硬化させて封止する方法などが挙げられる。被着体としては特に限定されず、例えば、プリント配線基板、セラミック基板、シリコン基板、金属基板等が挙げられる。本実施形態では、プリント配線基板12上に搭載されたSAWチップ13を樹脂シート11により中空封止して中空パッケージを作製する。 [Method of manufacturing hollow package]
2A to 2C are views schematically showing one step of the method for manufacturing the hollow package according to the embodiment of the present invention. It does not specifically limit as a hollow sealing method, It can seal by a conventionally well-known method. For example, a method of laminating (mounting) an
(SAWチップ搭載基板準備工程)
SAWチップ搭載基板準備工程では、複数のSAWチップ13が搭載されたプリント配線基板12を準備する(図2A参照)。SAWチップ13は、所定の櫛形電極が形成された圧電結晶を公知の方法でダイシングして個片化することにより形成できる。SAWチップ13のプリント配線基板12への搭載には、フリップチップボンダーやダイボンダーなどの公知の装置を用いることができる。SAWチップ13とプリント配線基板12とはバンプなどの突起電極13aを介して電気的に接続されている。また、SAWチップ13とプリント配線基板12との間は、SAWフィルタ表面での表面弾性波の伝播を阻害しないように中空部分14を維持するようになっている。SAWチップ13とプリント配線基板12との間の距離は適宜設定でき、一般的には10~100μm程度である。 (SAW chip mounting substrate preparation process)
In the SAW chip mounting board preparing step, a printedwiring board 12 on which a plurality of SAW chips 13 are mounted is prepared (see FIG. 2A). The SAW chip 13 can be formed by dicing a piezoelectric crystal on which predetermined comb-shaped electrodes are formed by a known method. For mounting the SAW chip 13 on the printed wiring board 12, a known device such as a flip chip bonder or a die bonder can be used. The SAW chip 13 and the printed wiring board 12 are electrically connected via protruding electrodes 13a such as bumps. Further, a hollow portion 14 is maintained between the SAW chip 13 and the printed wiring board 12 so as not to inhibit the propagation of the surface acoustic wave on the surface of the SAW filter. The distance between the SAW chip 13 and the printed wiring board 12 can be set as appropriate, and is generally about 10 to 100 μm.
SAWチップ搭載基板準備工程では、複数のSAWチップ13が搭載されたプリント配線基板12を準備する(図2A参照)。SAWチップ13は、所定の櫛形電極が形成された圧電結晶を公知の方法でダイシングして個片化することにより形成できる。SAWチップ13のプリント配線基板12への搭載には、フリップチップボンダーやダイボンダーなどの公知の装置を用いることができる。SAWチップ13とプリント配線基板12とはバンプなどの突起電極13aを介して電気的に接続されている。また、SAWチップ13とプリント配線基板12との間は、SAWフィルタ表面での表面弾性波の伝播を阻害しないように中空部分14を維持するようになっている。SAWチップ13とプリント配線基板12との間の距離は適宜設定でき、一般的には10~100μm程度である。 (SAW chip mounting substrate preparation process)
In the SAW chip mounting board preparing step, a printed
(封止工程)
封止工程では、SAWチップ13を覆うようにプリント配線基板12へ樹脂シート11を積層し、SAWチップ13を樹脂シート11で樹脂封止する(図2B参照)。樹脂シート11は、SAWチップ13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する。 (Sealing process)
In the sealing step, theresin sheet 11 is laminated on the printed wiring board 12 so as to cover the SAW chip 13, and the SAW chip 13 is resin-sealed with the resin sheet 11 (see FIG. 2B). The resin sheet 11 functions as a sealing resin for protecting the SAW chip 13 and its accompanying elements from the external environment.
封止工程では、SAWチップ13を覆うようにプリント配線基板12へ樹脂シート11を積層し、SAWチップ13を樹脂シート11で樹脂封止する(図2B参照)。樹脂シート11は、SAWチップ13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する。 (Sealing process)
In the sealing step, the
樹脂シート11をプリント配線基板12上に積層する方法は特に限定されず、熱プレスやラミネータなど公知の方法により行うことができる。熱プレス条件としては、温度が、例えば、40~100℃、好ましくは50~90℃であり、圧力が、例えば、0.1~10MPa、好ましくは0.5~8MPaであり、時間が、例えば0.3~10分間、好ましくは0.5~5分間である。また、樹脂シート11のSAWチップ13及びプリント配線基板12への密着性および追従性の向上を考慮すると、減圧条件下(例えば0.1~5kPa)においてプレスすることが好ましい。
The method of laminating the resin sheet 11 on the printed wiring board 12 is not particularly limited, and can be performed by a known method such as hot press or laminator. As hot press conditions, the temperature is, for example, 40 to 100 ° C., preferably 50 to 90 ° C., the pressure is, for example, 0.1 to 10 MPa, preferably 0.5 to 8 MPa, and the time is, for example, 0.3 to 10 minutes, preferably 0.5 to 5 minutes. In view of improving the adhesion and followability of the resin sheet 11 to the SAW chip 13 and the printed wiring board 12, it is preferable to press under reduced pressure conditions (for example, 0.1 to 5 kPa).
(封止体形成工程)
封止体形成工程では、樹脂シート11を熱硬化処理して封止体15を形成する(図2B参照)。熱硬化処理の条件として、加熱温度が好ましくは100℃以上、より好ましくは120℃以上である。一方、加熱温度の上限が、好ましくは200℃以下、より好ましくは180℃以下である。加熱時間が、好ましくは10分以上、より好ましくは30分以上である。一方、加熱時間の上限が、好ましくは180分以下、より好ましくは120分以下である。また、必要に応じて加圧してもよく、好ましくは0.1MPa以上、より好ましくは0.5MPa以上である。一方、上限は好ましくは10MPa以下、より好ましくは5MPa以下である。 (Sealing body forming process)
In the sealing body forming step, theresin sheet 11 is thermally cured to form the sealing body 15 (see FIG. 2B). As the conditions for the thermosetting treatment, the heating temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher. On the other hand, the upper limit of the heating temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The heating time is preferably 10 minutes or more, more preferably 30 minutes or more. On the other hand, the upper limit of the heating time is preferably 180 minutes or less, more preferably 120 minutes or less. Moreover, you may pressurize as needed, Preferably it is 0.1 Mpa or more, More preferably, it is 0.5 Mpa or more. On the other hand, the upper limit is preferably 10 MPa or less, more preferably 5 MPa or less.
封止体形成工程では、樹脂シート11を熱硬化処理して封止体15を形成する(図2B参照)。熱硬化処理の条件として、加熱温度が好ましくは100℃以上、より好ましくは120℃以上である。一方、加熱温度の上限が、好ましくは200℃以下、より好ましくは180℃以下である。加熱時間が、好ましくは10分以上、より好ましくは30分以上である。一方、加熱時間の上限が、好ましくは180分以下、より好ましくは120分以下である。また、必要に応じて加圧してもよく、好ましくは0.1MPa以上、より好ましくは0.5MPa以上である。一方、上限は好ましくは10MPa以下、より好ましくは5MPa以下である。 (Sealing body forming process)
In the sealing body forming step, the
(ダイシング工程)
続いて、封止体15のダイシングを行ってもよい(図2C参照)。これにより、SAWチップ13単位での中空パッケージ18を得ることができる。 (Dicing process)
Subsequently, dicing of the sealingbody 15 may be performed (see FIG. 2C). Thereby, the hollow package 18 in the SAW chip 13 unit can be obtained.
続いて、封止体15のダイシングを行ってもよい(図2C参照)。これにより、SAWチップ13単位での中空パッケージ18を得ることができる。 (Dicing process)
Subsequently, dicing of the sealing
(基板実装工程)
必要に応じて、中空パッケージ18に対して再配線及びバンプを形成し、これを別途の基板(図示せず)に実装する基板実装工程を行うことができる。中空パッケージ18の基板への実装には、フリップチップボンダーやダイボンダーなどの公知の装置を用いることができる。 (Board mounting process)
If necessary, a substrate mounting process can be performed in which rewiring and bumps are formed on thehollow package 18 and mounted on a separate substrate (not shown). For mounting the hollow package 18 on the substrate, a known device such as a flip chip bonder or a die bonder can be used.
必要に応じて、中空パッケージ18に対して再配線及びバンプを形成し、これを別途の基板(図示せず)に実装する基板実装工程を行うことができる。中空パッケージ18の基板への実装には、フリップチップボンダーやダイボンダーなどの公知の装置を用いることができる。 (Board mounting process)
If necessary, a substrate mounting process can be performed in which rewiring and bumps are formed on the
《第2実施形態》
第1実施形態では、各配合成分をニーダー等で混練して混練物を調製し、この混練物を押出成形してシート状に形成している。これに対し、本実施形態では、各成分を有機溶剤等に溶解又は分散したワニスを塗工してシート状に形成する。 << Second Embodiment >>
In the first embodiment, each compounding component is kneaded with a kneader or the like to prepare a kneaded product, and the kneaded product is extruded to form a sheet. On the other hand, in this embodiment, the varnish which melt | dissolved or disperse | distributed each component in the organic solvent etc. is applied, and it forms in a sheet form.
第1実施形態では、各配合成分をニーダー等で混練して混練物を調製し、この混練物を押出成形してシート状に形成している。これに対し、本実施形態では、各成分を有機溶剤等に溶解又は分散したワニスを塗工してシート状に形成する。 << Second Embodiment >>
In the first embodiment, each compounding component is kneaded with a kneader or the like to prepare a kneaded product, and the kneaded product is extruded to form a sheet. On the other hand, in this embodiment, the varnish which melt | dissolved or disperse | distributed each component in the organic solvent etc. is applied, and it forms in a sheet form.
ワニスを用いる具体的な作製手順としては、上記成分及び必要に応じて他の添加剤を常法に準じて適宜混合し、有機溶剤に均一に溶解あるいは分散させ、ワニスを調製する。ついで、上記ワニスをポリエステル等の支持体上に塗布し乾燥させることにより中空封止用樹脂シート11を得ることができる。そして必要により、中空封止用樹脂シート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てもよい。剥離シートは封止時に剥離する。
As a specific production procedure using a varnish, the above components and other additives as necessary are mixed as appropriate according to a conventional method, and uniformly dissolved or dispersed in an organic solvent to prepare a varnish. Subsequently, the resin sheet 11 for hollow sealing can be obtained by apply | coating the said varnish on support bodies, such as polyester, and making it dry. And if necessary, in order to protect the surface of the resin sheet for hollow sealing, you may bond together peeling sheets, such as a polyester film. The release sheet peels at the time of sealing.
上記有機溶剤としては、特に限定されるものではなく従来公知の各種有機溶剤、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。これらは単独で用いてもよいし、2種以上併せて用いてもよい。また通常、ワニスの固形分濃度が30~95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。
The organic solvent is not particularly limited, and various conventionally known organic solvents such as methyl ethyl ketone, acetone, cyclohexanone, dioxane, diethyl ketone, toluene, and ethyl acetate can be used. These may be used alone or in combination of two or more. Usually, it is preferable to use an organic solvent so that the solid content concentration of the varnish is in the range of 30 to 95% by weight.
有機溶剤乾燥後のシートの厚みは、特に制限されるものではないが、厚みの均一性と残存溶剤量の観点から、通常、5~100μmに設定することが好ましく、より好ましくは20~70μmである。
The thickness of the sheet after drying the organic solvent is not particularly limited, but is usually preferably set to 5 to 100 μm, more preferably 20 to 70 μm, from the viewpoint of thickness uniformity and the amount of residual solvent. is there.
以下に、この発明の好適な実施例を例示的に詳しく説明する。ただし、この実施例に記載されている材料や配合量などは、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定する趣旨のものではない。
Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to those 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1:新日鐵化学(株)製のYSLV-80XY(ビスフェノールF型エポキシ樹脂、エポキン当量200g/eq.、軟化点80℃)
エポキシ樹脂2:日本化薬社製のEPPN-501HY(エポキシ当量169g/eq.、軟化点60℃)
フェノール樹脂1:明和化成社製のMEH-7851-SS(ビフェニルアラルキル骨格を有するフェノール樹脂、水酸基当量203g/eq.、軟化点67℃)
フェノール樹脂2:明和化成社製のMEH-7500(フェノール当量97g/eq.、軟化点111℃)
熱可塑性樹脂:(株)カネカ製のSIBSTER 072T(スチレン-イソブチレン-スチレンブロック共重合体)
無機充填剤1:電気化学工業社製のFB-9454FC(溶融球状シリカ、平均粒子径20μm)
無機充填剤2:(株)トクヤマ製のSE-40(溶融球状シリカ、平均粒子径38μm)
無機充填剤3:電気化学工業社製のFB-5SDC(溶融球状シリカ、平均粒子径5μm)
無機充填剤4:(株)アドマテックス製のSO-25R(溶融球状シリカ、平均粒子径0.5μm)
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)
カーボンブラック:三菱化学社製の#20
難燃剤: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。)
硬化促進剤:四国化成工業社製の2PHZ-PW(2-フェニル-4,5-ジヒドロキシメチルイミダゾール) The components used in the examples will be described.
Epoxy resin 1: YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin, epkin equivalent 200 g / eq., Softening point 80 ° C.)
Epoxy resin 2: EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 169 g / eq., Softening point 60 ° C.)
Phenol resin 1: MEH-7851-SS manufactured by Meiwa Kasei Co., Ltd. (phenol resin having a biphenylaralkyl skeleton, hydroxyl group equivalent 203 g / eq., Softening point 67 ° C.)
Phenol resin 2: MEH-7500 manufactured by Meiwa Kasei Co., Ltd. (phenol equivalent 97 g / eq., Softening point 111 ° C.)
Thermoplastic resin: SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka Corporation
Inorganic filler 1: FB-9454FC (fused spherical silica, average particle size 20 μm) manufactured by Denki Kagaku Kogyo Co., Ltd.
Inorganic filler 2: SE-40 (fused spherical silica, average particle size 38 μm) manufactured by Tokuyama Corporation
Inorganic filler 3: FB-5SDC (fused spherical silica, average particle size 5 μm) manufactured by Denki Kagaku Kogyo Co., Ltd.
Inorganic filler 4: SO-25R manufactured by Admatechs Co., Ltd. (fused spherical silica, average particle size 0.5 μm)
Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
Carbon black: # 20 manufactured by Mitsubishi Chemical
Flame retardant: 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.)
Curing accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
エポキシ樹脂1:新日鐵化学(株)製のYSLV-80XY(ビスフェノールF型エポキシ樹脂、エポキン当量200g/eq.、軟化点80℃)
エポキシ樹脂2:日本化薬社製のEPPN-501HY(エポキシ当量169g/eq.、軟化点60℃)
フェノール樹脂1:明和化成社製のMEH-7851-SS(ビフェニルアラルキル骨格を有するフェノール樹脂、水酸基当量203g/eq.、軟化点67℃)
フェノール樹脂2:明和化成社製のMEH-7500(フェノール当量97g/eq.、軟化点111℃)
熱可塑性樹脂:(株)カネカ製のSIBSTER 072T(スチレン-イソブチレン-スチレンブロック共重合体)
無機充填剤1:電気化学工業社製のFB-9454FC(溶融球状シリカ、平均粒子径20μm)
無機充填剤2:(株)トクヤマ製のSE-40(溶融球状シリカ、平均粒子径38μm)
無機充填剤3:電気化学工業社製のFB-5SDC(溶融球状シリカ、平均粒子径5μm)
無機充填剤4:(株)アドマテックス製のSO-25R(溶融球状シリカ、平均粒子径0.5μm)
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)
カーボンブラック:三菱化学社製の#20
難燃剤: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。)
硬化促進剤:四国化成工業社製の2PHZ-PW(2-フェニル-4,5-ジヒドロキシメチルイミダゾール) The components used in the examples will be described.
Epoxy resin 1: YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F type epoxy resin, epkin equivalent 200 g / eq., Softening point 80 ° C.)
Epoxy resin 2: EPPN-501HY manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 169 g / eq., Softening point 60 ° C.)
Phenol resin 1: MEH-7851-SS manufactured by Meiwa Kasei Co., Ltd. (phenol resin having a biphenylaralkyl skeleton, hydroxyl group equivalent 203 g / eq., Softening point 67 ° C.)
Phenol resin 2: MEH-7500 manufactured by Meiwa Kasei Co., Ltd. (phenol equivalent 97 g / eq., Softening point 111 ° C.)
Thermoplastic resin: SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka Corporation
Inorganic filler 1: FB-9454FC (fused spherical silica, average particle size 20 μm) manufactured by Denki Kagaku Kogyo Co., Ltd.
Inorganic filler 2: SE-40 (fused spherical silica, average particle size 38 μm) manufactured by Tokuyama Corporation
Inorganic filler 3: FB-5SDC (fused spherical silica, average particle size 5 μm) manufactured by Denki Kagaku Kogyo Co., Ltd.
Inorganic filler 4: SO-25R manufactured by Admatechs Co., Ltd. (fused spherical silica, average particle size 0.5 μm)
Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
Carbon black: # 20 manufactured by Mitsubishi Chemical
Flame retardant: 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.)
Curing accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.
[実施例1~4及び比較例1~4]
表1に記載の配合比に従い、各成分を配合し、ロール混練機により60~120℃、10分間、減圧条件下(0.01kg/cm2)で溶融混練し、混練物を調製した。次いで、得られた混練物を平板プレス法によりシート状(50mm×50mm)に成形して、表1に示す厚さの中空封止用樹脂シートを作製した。 [Examples 1 to 4 and Comparative Examples 1 to 4]
Each component was blended according to the blending ratio shown in Table 1, and melt-kneaded in a roll kneader at 60 to 120 ° C. for 10 minutes under reduced pressure conditions (0.01 kg / cm 2 ) to prepare a kneaded product. Next, the obtained kneaded material was molded into a sheet (50 mm × 50 mm) by a flat plate pressing method, and a hollow sealing resin sheet having a thickness shown in Table 1 was produced.
表1に記載の配合比に従い、各成分を配合し、ロール混練機により60~120℃、10分間、減圧条件下(0.01kg/cm2)で溶融混練し、混練物を調製した。次いで、得られた混練物を平板プレス法によりシート状(50mm×50mm)に成形して、表1に示す厚さの中空封止用樹脂シートを作製した。 [Examples 1 to 4 and Comparative Examples 1 to 4]
Each component was blended according to the blending ratio shown in Table 1, and melt-kneaded in a roll kneader at 60 to 120 ° C. for 10 minutes under reduced pressure conditions (0.01 kg / cm 2 ) to prepare a kneaded product. Next, the obtained kneaded material was molded into a sheet (50 mm × 50 mm) by a flat plate pressing method, and a hollow sealing resin sheet having a thickness shown in Table 1 was produced.
[実施例5]
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との1:1混合溶剤に溶解ないし分散し、固形分40重量%のワニスを作製した。次に、離型処理を施したPETフィルム上に、溶剤乾燥後の塗膜の厚さが50μmになるようにワニスを塗工し、その後、乾燥条件を120℃、3分として塗膜を乾燥させて、厚さ50μmの樹脂シートを得た。得られた樹脂シートを、ラミネータを用いて厚み200μmになるまで積層し、厚さ200μmの中空封止用樹脂シートを作製した。 [Example 5]
According to the blending ratio shown in Table 1, each component was dissolved or dispersed in a 1: 1 mixed solvent of methyl ethyl ketone and toluene to prepare a varnish having a solid content of 40% by weight. Next, a varnish is applied on the PET film subjected to the release treatment so that the thickness of the coating film after drying the solvent is 50 μm, and then the coating film is dried at 120 ° C. for 3 minutes. Thus, a resin sheet having a thickness of 50 μm was obtained. The obtained resin sheet was laminated using a laminator to a thickness of 200 μm to produce a hollow sealing resin sheet having a thickness of 200 μm.
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との1:1混合溶剤に溶解ないし分散し、固形分40重量%のワニスを作製した。次に、離型処理を施したPETフィルム上に、溶剤乾燥後の塗膜の厚さが50μmになるようにワニスを塗工し、その後、乾燥条件を120℃、3分として塗膜を乾燥させて、厚さ50μmの樹脂シートを得た。得られた樹脂シートを、ラミネータを用いて厚み200μmになるまで積層し、厚さ200μmの中空封止用樹脂シートを作製した。 [Example 5]
According to the blending ratio shown in Table 1, each component was dissolved or dispersed in a 1: 1 mixed solvent of methyl ethyl ketone and toluene to prepare a varnish having a solid content of 40% by weight. Next, a varnish is applied on the PET film subjected to the release treatment so that the thickness of the coating film after drying the solvent is 50 μm, and then the coating film is dried at 120 ° C. for 3 minutes. Thus, a resin sheet having a thickness of 50 μm was obtained. The obtained resin sheet was laminated using a laminator to a thickness of 200 μm to produce a hollow sealing resin sheet having a thickness of 200 μm.
(最低溶融粘度)
各中空封止用樹脂シートの最低溶融粘度を、TAインスツルメント社製の粘弾性測定装置「ARES」(測定条件:測定温度範囲60~130℃、昇温速度10℃/min、周波数0.1Hz)で粘度変化を追跡した際、粘度の最低値を測定した結果を表1に示す。 (Minimum melt viscosity)
The minimum melt viscosity of each hollow sealing resin sheet is determined by measuring the viscoelasticity measuring device “ARES” manufactured by TA Instruments (measuring conditions: measuring temperature range 60 to 130 ° C., heating rate 10 ° C./min, frequency 0. Table 1 shows the result of measuring the minimum value of the viscosity when the viscosity change was traced at 1 Hz).
各中空封止用樹脂シートの最低溶融粘度を、TAインスツルメント社製の粘弾性測定装置「ARES」(測定条件:測定温度範囲60~130℃、昇温速度10℃/min、周波数0.1Hz)で粘度変化を追跡した際、粘度の最低値を測定した結果を表1に示す。 (Minimum melt viscosity)
The minimum melt viscosity of each hollow sealing resin sheet is determined by measuring the viscoelasticity measuring device “ARES” manufactured by TA Instruments (measuring conditions: measuring temperature range 60 to 130 ° C., heating rate 10 ° C./min, frequency 0. Table 1 shows the result of measuring the minimum value of the viscosity when the viscosity change was traced at 1 Hz).
(中空封止用樹脂シートの線膨張係数の測定)
線膨張係数の測定は、熱機械分析装置((株)リガク社製:形式:TMA8310)を用いて行った。具体的には、各中空封止用樹脂シートを150℃で1時間加熱して熱硬化させ、この硬化物からサンプルサイズを長さ25mm×幅4.9mm×厚さ200μmとして測定試料を得た後、測定試料をフィルム引っ張り測定用治具にセットし、引張荷重4.9mN、昇温速度10℃/minの条件下で測定し、線膨張係数を得た。結果を表1に示す。 (Measurement of linear expansion coefficient of resin sheet for hollow sealing)
The linear expansion coefficient was measured using a thermomechanical analyzer (manufactured by Rigaku Corporation: model: TMA8310). Specifically, each hollow sealing resin sheet was heated and cured at 150 ° C. for 1 hour, and a measurement sample was obtained from this cured product with a sample size of 25 mm long × 4.9 mm wide × 200 μm thick. Thereafter, the measurement sample was set on a film tensile measurement jig and measured under conditions of a tensile load of 4.9 mN and a temperature increase rate of 10 ° C./min to obtain a linear expansion coefficient. The results are shown in Table 1.
線膨張係数の測定は、熱機械分析装置((株)リガク社製:形式:TMA8310)を用いて行った。具体的には、各中空封止用樹脂シートを150℃で1時間加熱して熱硬化させ、この硬化物からサンプルサイズを長さ25mm×幅4.9mm×厚さ200μmとして測定試料を得た後、測定試料をフィルム引っ張り測定用治具にセットし、引張荷重4.9mN、昇温速度10℃/minの条件下で測定し、線膨張係数を得た。結果を表1に示す。 (Measurement of linear expansion coefficient of resin sheet for hollow sealing)
The linear expansion coefficient was measured using a thermomechanical analyzer (manufactured by Rigaku Corporation: model: TMA8310). Specifically, each hollow sealing resin sheet was heated and cured at 150 ° C. for 1 hour, and a measurement sample was obtained from this cured product with a sample size of 25 mm long × 4.9 mm wide × 200 μm thick. Thereafter, the measurement sample was set on a film tensile measurement jig and measured under conditions of a tensile load of 4.9 mN and a temperature increase rate of 10 ° C./min to obtain a linear expansion coefficient. The results are shown in Table 1.
(中空封止用樹脂シートの貯蔵弾性率及びガラス転移温度(Tg)の測定)
各中空封止用樹脂シートを150℃で1時間加熱して熱硬化させ、この硬化物からサンプルサイズを長さ25mm×幅4.9mm×厚さ200μmとして測定試料を得た。この測定試料の貯蔵弾性率をTAインスツルメント製RSA3で測定した。具体的には、-50~300℃の温度域での貯蔵弾性率及び損失弾性率を、周波数1Hz、昇温速度10℃/minの条件下で測定し、20℃での貯蔵弾性率(E’)を読み取ることにより得た。また、当該測定におけるtanδ(G”(損失弾性率)/G’(貯蔵弾性率))の値を算出することによりガラス転移温度(Tg)を得た。それぞれの結果を表1に示す。 (Measurement of storage elastic modulus and glass transition temperature (Tg) of resin sheet for hollow sealing)
Each hollow sealing resin sheet was heated and cured at 150 ° C. for 1 hour, and a measurement sample was obtained from this cured product with a sample size of 25 mm long × 4.9 mm wide × 200 μm thick. The storage elastic modulus of this measurement sample was measured with RSA3 manufactured by TA Instruments. Specifically, the storage elastic modulus and loss elastic modulus in the temperature range of −50 to 300 ° C. were measured under the conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min, and the storage elastic modulus at 20 ° C. (E Obtained by reading '). Further, the glass transition temperature (Tg) was obtained by calculating the value of tan δ (G ″ (loss elastic modulus) / G ′ (storage elastic modulus)) in this measurement.
各中空封止用樹脂シートを150℃で1時間加熱して熱硬化させ、この硬化物からサンプルサイズを長さ25mm×幅4.9mm×厚さ200μmとして測定試料を得た。この測定試料の貯蔵弾性率をTAインスツルメント製RSA3で測定した。具体的には、-50~300℃の温度域での貯蔵弾性率及び損失弾性率を、周波数1Hz、昇温速度10℃/minの条件下で測定し、20℃での貯蔵弾性率(E’)を読み取ることにより得た。また、当該測定におけるtanδ(G”(損失弾性率)/G’(貯蔵弾性率))の値を算出することによりガラス転移温度(Tg)を得た。それぞれの結果を表1に示す。 (Measurement of storage elastic modulus and glass transition temperature (Tg) of resin sheet for hollow sealing)
Each hollow sealing resin sheet was heated and cured at 150 ° C. for 1 hour, and a measurement sample was obtained from this cured product with a sample size of 25 mm long × 4.9 mm wide × 200 μm thick. The storage elastic modulus of this measurement sample was measured with RSA3 manufactured by TA Instruments. Specifically, the storage elastic modulus and loss elastic modulus in the temperature range of −50 to 300 ° C. were measured under the conditions of a frequency of 1 Hz and a heating rate of 10 ° C./min, and the storage elastic modulus at 20 ° C. (E Obtained by reading '). Further, the glass transition temperature (Tg) was obtained by calculating the value of tan δ (G ″ (loss elastic modulus) / G ′ (storage elastic modulus)) in this measurement.
(パッケージ中空部への樹脂進入性及びパッケージの反りの評価)
アルミニウム櫛形電極が形成された以下の仕様のSAWチップを下記ボンディング条件にて長さ50mm×幅50mm×厚さ0.5mmのガラス基板に実装したSAWチップ実装基板を作製した。実施例1~3、5及び比較例1~4ではSAWチップとガラス基板との間のギャップ幅は30μm、実施例4では90μmであった。 (Evaluation of resin penetration into package hollow and package warpage)
A SAW chip mounting substrate in which a SAW chip having the following specifications on which an aluminum comb-shaped electrode was formed was mounted on a glass substrate having a length of 50 mm, a width of 50 mm, and a thickness of 0.5 mm was produced under the following bonding conditions. In Examples 1 to 3, 5 and Comparative Examples 1 to 4, the gap width between the SAW chip and the glass substrate was 30 μm, and in Example 4, it was 90 μm.
アルミニウム櫛形電極が形成された以下の仕様のSAWチップを下記ボンディング条件にて長さ50mm×幅50mm×厚さ0.5mmのガラス基板に実装したSAWチップ実装基板を作製した。実施例1~3、5及び比較例1~4ではSAWチップとガラス基板との間のギャップ幅は30μm、実施例4では90μmであった。 (Evaluation of resin penetration into package hollow and package warpage)
A SAW chip mounting substrate in which a SAW chip having the following specifications on which an aluminum comb-shaped electrode was formed was mounted on a glass substrate having a length of 50 mm, a width of 50 mm, and a thickness of 0.5 mm was produced under the following bonding conditions. In Examples 1 to 3, 5 and Comparative Examples 1 to 4, the gap width between the SAW chip and the glass substrate was 30 μm, and in Example 4, it was 90 μm.
<SAWチップ>
チップサイズ:1.2mm□(厚さ150μm)
バンプ材質(実施例1~3、5及び比較例1~4):Auバンプ、高さ30μm
バンプ材質(実施例4):半田(鉛フリータイプ)バンプ、高さ90μm
バンプ数:6バンプ
チップ数:100個(10個×10個) <SAW chip>
Chip size: 1.2mm □ (thickness 150μm)
Bump material (Examples 1 to 3, 5 and Comparative Examples 1 to 4): Au bump, height 30 μm
Bump material (Example 4): Solder (lead-free type) bump, height 90 μm
Number of bumps: 6 bumps Number of chips: 100 (10 x 10)
チップサイズ:1.2mm□(厚さ150μm)
バンプ材質(実施例1~3、5及び比較例1~4):Auバンプ、高さ30μm
バンプ材質(実施例4):半田(鉛フリータイプ)バンプ、高さ90μm
バンプ数:6バンプ
チップ数:100個(10個×10個) <SAW chip>
Chip size: 1.2mm □ (thickness 150μm)
Bump material (Examples 1 to 3, 5 and Comparative Examples 1 to 4): Au bump, height 30 μm
Bump material (Example 4): Solder (lead-free type) bump, height 90 μm
Number of bumps: 6 bumps Number of chips: 100 (10 x 10)
<ボンディング条件>
装置:パナソニック電工(株)製
ボンディング条件:200℃、3N、1sec、超音波出力2W <Bonding conditions>
Equipment: manufactured by Panasonic Electric Works Co., Ltd. Bonding conditions: 200 ° C., 3N, 1 sec, ultrasonic output 2W
装置:パナソニック電工(株)製
ボンディング条件:200℃、3N、1sec、超音波出力2W <Bonding conditions>
Equipment: manufactured by Panasonic Electric Works Co., Ltd. Bonding conditions: 200 ° C., 3N, 1 sec, ultrasonic output 2W
得られたSAWチップ実装基板上に、以下に示す加熱加圧条件下、各中空封止用樹脂シートを真空プレスにより貼付けた。
Each hollow sealing resin sheet was stuck on the obtained SAW chip mounting substrate by a vacuum press under the heating and pressurization conditions shown below.
<貼り付け条件>
温度:60℃
加圧力:4MPa
真空度:1.6kPa
プレス時間:1分 <Paste conditions>
Temperature: 60 ° C
Applied pressure: 4 MPa
Degree of vacuum: 1.6 kPa
Press time: 1 minute
温度:60℃
加圧力:4MPa
真空度:1.6kPa
プレス時間:1分 <Paste conditions>
Temperature: 60 ° C
Applied pressure: 4 MPa
Degree of vacuum: 1.6 kPa
Press time: 1 minute
大気圧に開放した後、熱風乾燥機中、150℃、1時間の条件で中空封止用樹脂シートを熱硬化させ、封止体を得た。封止体を常温まで冷却した後、ガラス基板側から電子顕微鏡(KEYENCE社製、商品名「デジタルマイクロスコープ」、200倍)により、SAWチップとガラス基板との間の中空部への樹脂の進入量を測定した。樹脂進入量は、中空封止用樹脂シートによる封止前にガラス基板側から電子顕微鏡でSAWチップの端部の位置を確認及び記憶しておき、封止後に再度ガラス基板側から電子顕微鏡で観察し、封止前後での観察像を比較して、封止前に確認しておいたSAWチップの端部から中空部へ進入した樹脂の最大到達距離を測定し、これを樹脂進入量とした。樹脂進入量が20μm以下であった場合を「○」、20μmを超えていた場合を「×」として評価した。結果を表1に示す。
After releasing to atmospheric pressure, the resin sheet for hollow sealing was thermoset in a hot air dryer at 150 ° C. for 1 hour to obtain a sealed body. After the sealing body is cooled to room temperature, the resin enters the hollow portion between the SAW chip and the glass substrate from the glass substrate side using an electron microscope (trade name “Digital Microscope”, 200 ×, manufactured by KEYENCE). The amount was measured. The amount of resin penetration is confirmed and memorized by the electron microscope from the glass substrate side before sealing with the hollow sealing resin sheet, and observed again from the glass substrate side with the electron microscope after sealing. Then, the observation images before and after sealing were compared, and the maximum reach distance of the resin that entered the hollow portion from the end of the SAW chip that had been confirmed before sealing was measured, and this was defined as the resin penetration amount . The case where the resin penetration amount was 20 μm or less was evaluated as “◯”, and the case where it exceeded 20 μm was evaluated as “×”. The results are shown in Table 1.
また、常温まで冷却した封止体の最大反り量をレーザー3次元測定装置(ティーテック社製、「LS-220-MT50」)を用い、樹脂シート側の表面を走査して計測し、反り量が1mm以下の場合を「○」、1mmを超えた場合を「×」として評価した。
In addition, the amount of warpage of the sealed body cooled to room temperature is measured by scanning the surface on the resin sheet side using a laser three-dimensional measuring device ("LS-220-MT50" manufactured by TETECH Co., Ltd.). Was evaluated as “◯” when 1 mm or less, and “X” when exceeding 1 mm.
表1から分かるように、実施例1~5のSAWチップパッケージでは、中空封止用樹脂シートの樹脂成分の中空部への進入及び反りが抑制されており、中空部が拡大しても高品質かつ高信頼性の中空パッケージを作製可能であることが分かる。比較例1~4では中空部への樹脂進入量がいずれも20μmを超えており、また比較例1、3及び4では封止体の反りも発生していた。
As can be seen from Table 1, in the SAW chip packages of Examples 1 to 5, the resin components of the hollow sealing resin sheet are prevented from entering and warping into the hollow part, and even if the hollow part is enlarged, high quality It can also be seen that a highly reliable hollow package can be produced. In Comparative Examples 1 to 4, the amount of resin entering the hollow portion exceeded 20 μm, and in Comparative Examples 1, 3, and 4, warpage of the sealing body occurred.
11 中空封止用樹脂シート
11a 支持体
13 SAWチップ
15 封止体
18 中空パッケージ
DESCRIPTION OFSYMBOLS 11 Resin sheet | seat for hollow sealing 11a Support body 13 SAW chip 15 Sealing body 18 Hollow package
11a 支持体
13 SAWチップ
15 封止体
18 中空パッケージ
DESCRIPTION OF
Claims (2)
- 無機充填剤を70体積%以上90体積%以下の含有量で含み、
動的粘弾性測定による60~130℃での最低溶融粘度が2000Pa・s以上20000Pa・s以下であり、
150℃で1時間熱硬化させた後の20℃における貯蔵弾性率が1GPa以上20GPa以下であり、
150℃で1時間熱硬化させた後のガラス転移温度以下における線膨張係数が5ppm/K以上15ppm/K以下である中空封止用樹脂シート。 Containing an inorganic filler in a content of 70 vol% or more and 90 vol% or less,
The minimum melt viscosity at 60 to 130 ° C. by dynamic viscoelasticity measurement is 2000 Pa · s or more and 20000 Pa · s or less,
The storage elastic modulus at 20 ° C. after thermosetting at 150 ° C. for 1 hour is 1 GPa or more and 20 GPa or less,
A resin sheet for hollow sealing, having a linear expansion coefficient of 5 ppm / K or more and 15 ppm / K or less after the glass transition temperature after thermosetting at 150 ° C. for 1 hour. - 被着体上に配置された1又は複数の電子デバイスを覆うように請求項1に記載の中空封止用樹脂シートを前記電子デバイス上に前記被着体と前記電子デバイスとの間の中空部を維持しながら積層する積層工程、及び
前記中空封止用樹脂シートを硬化させて封止体を形成する封止体形成工程
を含む中空パッケージの製造方法。
A hollow portion between the adherend and the electronic device, wherein the resin sheet for hollow sealing according to claim 1 is covered on the electronic device so as to cover one or more electronic devices arranged on the adherend. The manufacturing method of the hollow package including the lamination process which laminates | stacks, maintaining the resin, and the sealing body formation process which hardens the said resin sheet for hollow sealing, and forms a sealing body.
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CN201480019057.4A CN105074906B (en) | 2013-03-28 | 2014-03-18 | The manufacturing method of hollow sealing resin sheet and hollow package body |
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JP2014-022313 | 2014-02-07 |
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Cited By (4)
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CN106206470A (en) * | 2015-05-28 | 2016-12-07 | 日东电工株式会社 | Hollow type electronic component encapsulation sheet, the manufacture method of hollow type electron device package body and hollow type electron device package body |
CN109148680A (en) * | 2018-09-26 | 2019-01-04 | 深圳市麦捷微电子科技股份有限公司 | Epoxy resin packaging ceramic substrate warp degree supplementally takes process and supplementally takes fixture |
WO2019098078A1 (en) * | 2017-11-17 | 2019-05-23 | リンテック株式会社 | Resin sheet |
US20210031433A1 (en) * | 2017-11-08 | 2021-02-04 | Hytech Worldwide, Inc. | Three Dimensional Thermoforming and Lamination |
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JP6379051B2 (en) * | 2015-01-23 | 2018-08-22 | 日東電工株式会社 | Hollow electronic device sealing sheet |
JP6422370B2 (en) * | 2015-03-03 | 2018-11-14 | 日東電工株式会社 | Hollow type electronic device sealing sheet and method for manufacturing hollow type electronic device package |
JP6883937B2 (en) * | 2015-03-19 | 2021-06-09 | 日東電工株式会社 | Manufacturing method of sealing sheet and hollow package |
JP6174292B1 (en) * | 2016-04-05 | 2017-08-02 | リンテック株式会社 | Sheet for manufacturing three-dimensional integrated multilayer circuit and method for manufacturing three-dimensional integrated multilayer circuit |
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CN106206470A (en) * | 2015-05-28 | 2016-12-07 | 日东电工株式会社 | Hollow type electronic component encapsulation sheet, the manufacture method of hollow type electron device package body and hollow type electron device package body |
CN106206470B (en) * | 2015-05-28 | 2021-04-06 | 日东电工株式会社 | Sheet for sealing hollow electronic device, package, and method for manufacturing package |
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TWI621225B (en) | 2018-04-11 |
CN105074906A (en) | 2015-11-18 |
JP6643791B2 (en) | 2020-02-12 |
SG11201507891RA (en) | 2015-10-29 |
TW201448135A (en) | 2014-12-16 |
JP2014209568A (en) | 2014-11-06 |
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