WO2022239553A1 - アンダーフィル用樹脂組成物並びに電子部品装置及びその製造方法 - Google Patents
アンダーフィル用樹脂組成物並びに電子部品装置及びその製造方法 Download PDFInfo
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- WO2022239553A1 WO2022239553A1 PCT/JP2022/015659 JP2022015659W WO2022239553A1 WO 2022239553 A1 WO2022239553 A1 WO 2022239553A1 JP 2022015659 W JP2022015659 W JP 2022015659W WO 2022239553 A1 WO2022239553 A1 WO 2022239553A1
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- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- NFACJZMKEDPNKN-UHFFFAOYSA-N trichlorfon Chemical compound COP(=O)(OC)C(O)C(Cl)(Cl)Cl NFACJZMKEDPNKN-UHFFFAOYSA-N 0.000 description 1
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
-
- 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
- H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation
-
- 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
-
- 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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Definitions
- the present invention relates to an underfill resin composition, an electronic component device, and a method for manufacturing the same.
- resins have been mainly used as encapsulants for encapsulating semiconductor elements such as transistors and ICs (Integrated Circuits) from the standpoint of productivity and cost.
- epoxy resins are widely used because of their excellent balance of properties required for encapsulants, such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products. ing.
- an electronic component device in which a semiconductor element is directly bump-connected on a wiring substrate (hereinafter also simply referred to as “substrate”) whose substrate is ceramic, glass/epoxy resin, glass/imide resin, polyimide film, etc.
- a sealing material called an underfill material is used to fill the gap between the bump-connected semiconductor element and the wiring board.
- a resin composition used as an underfill material plays an important role in protecting electronic parts from temperature, humidity and mechanical external force.
- a liquid encapsulating resin composition containing an epoxy resin, a liquid aromatic amine, a filler, and a liquid silicone compound having a carboxy group or an amino group is disclosed in order to improve bleeding defects (for example, Patent Document 1).
- liquid encapsulating resin composition described in Patent Document 1 it is described that bleeding cannot be suppressed when a silicone compound that does not contain a carboxy group or an amino group is used.
- a method for suppressing bleeding of the resin component is desired.
- An object of one aspect of the present invention is to provide an underfill resin composition in which the occurrence of bleeding is suppressed, an electronic component device using this underfill resin composition, and a method for manufacturing the same.
- ⁇ 1> Contains an epoxy resin, a curing agent, an inorganic filler, and a polyether-modified silicone compound having a hydroxyl group on at least one of the terminal of the main chain and the side chain, and the content of the polyether-modified silicone compound is an underfill resin composition greater than 0.1% by mass with respect to the entire underfill resin composition.
- ⁇ 2> The underfill resin composition according to ⁇ 1>, wherein the content of the polyether-modified silicone compound is 0.12% by mass to 0.25% by mass with respect to the entire underfill resin composition.
- An electronic component device comprising: ⁇ 6> The underfilling according to any one of ⁇ 1> to ⁇ 4>, wherein a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer are combined.
- a method for manufacturing an electronic component device comprising a step of sealing using a resin composition.
- an underfill resin composition that suppresses the occurrence of bleeding, an electronic component device using this underfill resin composition, and a method for manufacturing the same.
- each component may contain multiple types of applicable substances.
- the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. means quantity.
- Particles corresponding to each component in the present disclosure may include a plurality of types.
- the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
- the term “layer” or “film” refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.
- the underfill resin composition of the present disclosure comprises an epoxy resin, a curing agent, an inorganic filler, and a polyether-modified silicone compound having a hydroxyl group on at least one of a terminal of a main chain and a side chain, and The content of the polyether-modified silicone compound is greater than 0.1% by mass with respect to the entire underfill resin composition.
- the underfill resin composition of the present disclosure (hereinafter also referred to as "underfill material”) is a polyether-modified silicone compound (hereinafter referred to as "specific modified
- the content of the specific modified silicone compound is greater than 0.1% by mass with respect to the entire underfill material. This suppresses the occurrence of bleeding.
- the underfill material contains a predetermined amount of a specific modified silicone compound having a terminal hydroxy group, thereby suitably reducing the surface tension.
- the terminal hydroxy group contained in the specific modified silicone compound is adsorbed onto the wiring substrate, thereby suppressing wetting and spreading of the preceding liquid film. As described above, the occurrence of bleeding is suppressed.
- the underfill material is preferably liquid at room temperature.
- "normal temperature” means 25 ° C.
- “liquid” means a substance that exhibits fluidity and viscosity and has a viscosity that is a measure of viscosity of 0.0001 Pa s to 100 Pa s. .
- “liquid” means being in a liquid state.
- viscosity is defined as a value obtained by multiplying a measured value obtained by rotating an EHD rotational viscometer at 25°C for 1 minute at a predetermined number of revolutions by a predetermined conversion factor.
- the above measured values are obtained for a liquid maintained at 25 ⁇ 1° C. using an EHD rotational viscometer equipped with a cone rotor having a cone angle of 3° and a cone radius of 14 mm.
- the number of rotations and the conversion factor differ depending on the viscosity of the liquid to be measured. Specifically, the viscosity of the liquid to be measured is roughly estimated in advance, and the rotational speed and the conversion factor are determined according to the estimated value.
- the rotation speed is 10 times per minute, the conversion factor is 0.5, and the estimated viscosity is 1 . If the viscosity is 25 Pa s or more and less than 2.5 Pa s, the rotation speed is 5 times per minute, and the conversion factor is 1. If the estimated viscosity value is 2.5 Pa s or more and less than 6.25 Pa s, the rotation speed is 2.5 times per minute and the conversion factor is 2. When the estimated value of the viscosity is 6.25 Pa ⁇ s or more and less than 12.5 Pa ⁇ s, the rotation speed is 1 time per minute and the conversion factor is 5.
- the viscosity of the underfill material is not particularly limited. Above all, from the viewpoint of high fluidity, the viscosity of the underfill material at 25° C. is preferably 0.1 Pa ⁇ s to 100.0 Pa ⁇ s, more preferably 0.1 Pa ⁇ s to 50.0 Pa ⁇ s. More preferably, it is 0.1 Pa ⁇ s to 30.0 Pa ⁇ s.
- the viscosity of the underfill material at 110° C. can be mentioned. .
- the viscosity of the underfill material at 110° C. is preferably 0.20 Pa ⁇ s or less, more preferably 0.15 Pa ⁇ s or less.
- the viscosity of the underfill material at 110° C. is measured by a rheometer AR2000 (manufactured by TA Instruments, aluminum cone 40 mm, shear rate 32.5/sec).
- the underfill material has a thixotropic index [ (Viscosity at 2.5 revolutions/minute)/(Viscosity at 10 revolutions/minute)] is preferably 0.5 to 1.5, more preferably 0.8 to 1.2.
- the viscosity and thixotropic index of the underfill material can be set within desired ranges by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, and the like.
- the underfill material of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a specific modified silicone compound, and may contain other components as necessary.
- the underfill material of the present disclosure contains epoxy resin.
- the type of epoxy resin is not particularly limited, and can be selected from those commonly used as materials for underfill materials.
- An epoxy resin may be used individually by 1 type, or may use 2 or more types together.
- epoxy resins include phenol novolac epoxy resins, novolac epoxy resins such as cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, N,N-diglycidylaniline, N , N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, aromatic glycidylamine-type epoxy resins such as aminophenol-type glycidylamine, phenol aralkyl-type epoxy resins having at least one of a phenylene skeleton or a biphenylene skeleton, phenylene skeletons or biphenylene skeletons Aralkyl-type epoxy resins such as naphthol aralkyl-type epoxy resins having at least one, hydroquinone-type epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, triphenolmethane-type epoxy resins, triphenolpropane-type epoxy resins,
- epoxy resins may include bisphenol-type epoxy resins, aromatic glycidylamine-type epoxy resins, and naphthalene-type epoxy resins.
- epoxy resins containing a structure in which a glycidyl structure or a glycidylamine structure is bonded to an aromatic ring are preferable from the viewpoint of improving heat resistance, mechanical properties, and moisture resistance.
- the epoxy resin it is preferable to select the epoxy resin so that the entire epoxy resin is liquid at room temperature. That is, when only one kind of epoxy resin is included, it is preferable that the epoxy resin is liquid at room temperature. In the case of a combination of two or more epoxy resins, all of the two or more epoxy resins may be liquid at room temperature, and a part of the epoxy resin may be solid at room temperature, and the two or more epoxy resins are mixed. The combination may sometimes be liquid at room temperature. When an epoxy resin that is solid at room temperature is used as the epoxy resin, the content of the solid epoxy resin is preferably 20% by mass or less relative to the entire epoxy resin from the viewpoint of fluidity.
- the epoxy resins may be mixed in advance and then mixed with the other components, or the epoxy resins may be mixed with the other components without being mixed with each other.
- the content of the epoxy resin in the underfill material is not particularly limited, and is preferably 5% to 60% by mass, more preferably 5% to 50% by mass, based on the entire underfill material.
- the content of the epoxy resin is within the above range, the reactivity during curing, the heat resistance and mechanical strength after curing, and the fluidity during sealing tend to be excellent.
- the epoxy resin preferably contains a bisphenol-type epoxy resin and an aromatic glycidylamine-type epoxy resin.
- the total content of the bisphenol-type epoxy resin and the aromatic glycidylamine-type epoxy resin is preferably, for example, 20% by mass or more relative to the total epoxy resin. , more preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass or more.
- the total content of the bisphenol-type epoxy resin and the aromatic glycidylamine-type epoxy resin may be, for example, 90% by mass or less based on the total epoxy resin.
- bisphenol-type epoxy resin Aromatic glycidylamine-type epoxy is preferably 20:80 to 95:5, and 40:60 to 90:10, from the viewpoint of heat resistance, adhesiveness and fluidity. is more preferred, and 60:40 to 80:20 is even more preferred.
- the epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited, and is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq.
- the epoxy equivalent of the epoxy resin shall be the value measured by the method according to JIS K 7236:2009.
- the purity of the epoxy resin is high.
- the amount of hydrolyzable chlorine is as small as possible because it is related to the corrosion of aluminum wiring on elements such as ICs. From the viewpoint of obtaining an underfill material with excellent moisture resistance, it is preferably, for example, 500 ppm or less.
- the amount of hydrolyzable chlorine is obtained by dissolving 1 g of the sample epoxy resin in 30 mL of dioxane, adding 5 mL of 1 mol / L-KOH (potassium hydroxide) methanol solution and refluxing for 30 minutes, and then by potentiometric titration. The obtained value is used as a scale.
- the underfill material of the present disclosure contains a curing agent.
- the type of curing agent is not particularly limited, and can be selected from those commonly used as materials for underfill materials. Curing agents may be used alone or in combination of two or more. Examples of curing agents include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like. Among these, an amine-based curing agent is preferable as the curing agent.
- amine-based curing agent there are no particular restrictions on the amine-based curing agent, and for example, two or more of one or more selected from the group consisting of primary amino groups and secondary amino groups (hereinafter also simply referred to as "amino groups") per molecule.
- a compound containing the amino group is preferable, a compound having 2 to 4 amino groups in one molecule is more preferable, and a compound having two amino groups in one molecule (diamine compound) is more preferable.
- the curing agent is selected so that the entire curing agent is liquid at room temperature. That is, when only one type of curing agent is included, the curing agent is preferably liquid at room temperature. In the case of a combination of two or more curing agents, all of the two or more curing agents may be liquid at room temperature, and a portion of the curing agents may be solid at room temperature, and the two or more curing agents are mixed. It may be a combination that becomes a liquid at normal temperature when it is mixed. When a curing agent that is solid at room temperature is used as the curing agent, the content of the solid curing agent is preferably 20% by mass or less based on the total curing agent from the viewpoint of fluidity.
- the compound having an amino group is preferably a compound having an aromatic ring (aromatic amine compound), more preferably an aromatic amine compound that is liquid at room temperature, is liquid at room temperature, and contains More preferably, it is an aromatic amine compound having two amino groups.
- diethyltoluenediamines such as 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine
- 1,3,5-triethyl- triethyldiaminobenzene such as 2,6
- diaminodiphenylmethane and diethyltoluenediamine are preferable from the viewpoint of storage stability.
- the total content is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total curing agent. , more preferably 80% by mass or more.
- the upper limit of the total content is not particularly limited, and may be, for example, 100% by mass or less with respect to the entire curing agent.
- the content is preferably 50% by mass or more, preferably 70% by mass or more, based on the total curing agent, from the viewpoint of sufficiently exhibiting its performance. It is more preferable that the content is 80% by mass or more.
- the upper limit of the content is not particularly limited, and may be 100% by mass or less with respect to the entire curing agent.
- the active hydrogen equivalent of the curing agent is not particularly limited. From the viewpoint of further suppressing the occurrence of bleeding, for example, it is preferably 10 g/mol to 200 g/mol, more preferably 20 g/mol to 100 g/mol, and 30 g/mol to 70 g/mol. More preferred.
- the active hydrogen equivalent of the curing agent is a value calculated based on the amine value measured according to JIS K7237:1995.
- the equivalent ratio of the epoxy resin to the curing agent in the underfill material is preferably, for example, 0.7 to 1.6, more preferably 0.8 to 1, from the viewpoint of suppressing each unreacted amount. 0.4 is more preferred, and 0.9 to 1.2 is even more preferred.
- the underfill material of the present disclosure contains an inorganic filler.
- the inorganic filler is not particularly limited in its type.
- inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide. , beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having a flame retardant effect may also be used.
- Inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among them, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
- An inorganic filler may be used individually by 1 type, or may use 2 or more types together. Examples of the state of the inorganic filler include powders, beads obtained by spheroidizing powders, fibers, and the like.
- the content of the inorganic filler in the underfill material is not particularly limited, but from the viewpoint of the thermal expansion coefficient of the cured product and the fluidity of the underfill material, it should be 40% by mass to 70% by mass with respect to the entire underfill material. is preferred, and 50% by mass to 65% by mass is more preferred.
- the inorganic filler may contain silica particles.
- the average particle size of the silica particles is preferably 0.2 ⁇ m to 5 ⁇ m, more preferably 0.2 ⁇ m to 3 ⁇ m, and more preferably 0.3 ⁇ m to 1 ⁇ m, from the viewpoint of the fluidity and filling properties of the underfill material. more preferably 0.4 ⁇ m to 0.8 ⁇ m.
- the inorganic filler may contain large silica particles with a larger average particle size and small silica particles with a smaller average particle size.
- the preferred range of the average particle size of the large silica particles is the same as the preferred range of the average particle size of the silica particles described above.
- the average particle size of the small-diameter silica particles is preferably 7 nm to 100 nm, more preferably 9 nm to 75 nm.
- the average particle size of the small-diameter silica particles is 7 nm or more, the viscosity of the underfill material is less likely to increase, and fluidity tends to be less likely to deteriorate.
- the average particle size of the small-diameter silica particles is 100 nm or less, the viscosity of the underfill material tends to be reduced.
- the proportion of silica particles or large-sized silica particles in the inorganic filler may be 70% by mass or more, or may be 75% by mass or more.
- the proportion of silica particles or large-diameter silica particles in the inorganic filler is not particularly limited as long as it is 100% by mass or less, and may be 99.7% by mass or less, or 99.5% by mass or less.
- the proportion of small-diameter silica particles in the inorganic filler may be 0% by mass, 0.5% by mass or more, or 10% by mass or more. Moreover, the ratio of the small-diameter silica particles in the inorganic filler may be 30% by mass or less, or may be 25% by mass or less.
- the average particle size of the inorganic filler can be measured by the following method.
- a solvent for example, pure water
- a surfactant of 1% to 8% by weight in the range of 1% to 5% by weight of the inorganic filler to be measured.
- About 3 mL of the dispersion liquid is injected into the measurement cell and measured at 25°C.
- a laser diffraction particle size distribution meter (LA920, manufactured by Horiba, Ltd.) is used as a measuring device to measure the volume-based particle size distribution.
- the average particle diameter is obtained as the particle diameter (D50%) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution.
- the inorganic filler is imaged using an electron microscope or the like, the particle size of each particle is measured, and the particle size of 100 arbitrarily selected particles. may be used as the average particle size of the inorganic filler.
- the measurement sample is a cured product, for example, the ash content obtained as a residue after treating the cured product at a high temperature of 800° C. or higher in a muffle furnace or the like can be measured by the above method.
- the ratio of the average particle size of the small-sized silica particles to the average particle size of the large-sized silica particles is preferably 7-120, more preferably 10-110, even more preferably 20-100.
- the method for determining the ratio of small-diameter silica particles and large-diameter silica particles in the inorganic filler is not particularly limited.
- the volume-based particle size distribution (frequency distribution) of the inorganic filler is obtained, and both are divided between the peak corresponding to the small-diameter silica particles and the peak corresponding to the large-diameter silica particles.
- the ratio of the small-diameter silica particles and the large-diameter silica particles can be obtained.
- the composition of the underfill material When the composition of the underfill material is known, it is possible to obtain the ratio of the small-diameter silica particles and the large-diameter silica particles in the inorganic filler from the composition of the underfill material. Note that the calculation method is not limited to the above method.
- the underfill material of the present disclosure contains a polyether-modified silicone compound (a specific modified silicone compound) having a hydroxyl group on at least one of the terminal of the main chain and the side chain.
- a polyether-modified silicone compound (a specific modified silicone compound) having a hydroxyl group on at least one of the terminal of the main chain and the side chain.
- the type of specific silicone compound is not particularly limited, and one type may be used alone, or two or more types may be used in combination.
- "silicone compound” means a compound having a main chain formed by siloxane bonds.
- the specific silicone compound is preferably a silicone compound that is liquid at 25°C.
- the specific modified silicone compound may have a functional group other than a hydroxy group on at least one of the end of the main chain and the side chain, or may not have a functional group other than the hydroxy group. good.
- the content of the specific modified silicone compound in the underfill material is not particularly limited as long as it is greater than 0.1% by mass with respect to the entire underfill material. From the viewpoint of suppressing the occurrence of creep and the viewpoint of suitably suppressing the occurrence of bleeding, it is preferably 0.12% by mass to 0.5% by mass, and further, from the viewpoint of the adhesive strength of the cured product to a substrate such as a silicon wafer. , more preferably 0.12% by mass to 0.25% by mass, and even more preferably 0.14% by mass to 0.25% by mass.
- "creep” means exudation of a resin component creeping up the semiconductor element at the fillet portion of the semiconductor element sealed with the underfill material.
- the bonding state of the hydroxy groups in the specific modified silicone compound is not particularly limited.
- it may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group such as an ether group, an ester group, an amino group, an alkylene group, or a combination of these linking groups.
- the specific modified silicone compound may contain a polyalkylene glycol-modified silicone compound or may contain a polyethylene glycol-modified silicone compound.
- polyalkylene glycol modification include polyethylene glycol modification, polypropylene glycol modification, combinations thereof, and the like.
- the specific modified silicone compound may be a compound represented by the following general formula (1).
- each R 1 independently represents an organic group having a hydrocarbon group or a hydroxy group, and at least one R 1 is a polyether-modified organic group having a hydroxy group.
- R 1 is a polyether-modified organic group having a hydroxy group
- the organic group may have one hydroxy group or two or more hydroxy groups.
- l represents the number of moles per molecule of the siloxane unit represented by -[Si(R 1 ) 2 O]-, and ranges from 0 to 100;
- the hydrocarbon group represented by R 1 includes aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups.
- the number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, and from the viewpoint of availability, for example, it is preferably 1 to 10, more preferably 1 to 5, and 1 to 3. More preferred.
- Alkyl groups can be straight, cyclic, or branched.
- a vinyl group, an allyl group, etc. are mentioned as an alkenyl group.
- a methyl group or an ethyl group is preferable, and a methyl group is more preferable, from the viewpoint of availability.
- part of R 1 may be an alkyl group other than a methyl group, the remaining R 1 may be a methyl group, or all of the R 1 may be a methyl group.
- the polyether-modified organic group having a hydroxy group represented by R 1 is preferably a polyalkylene glycol-modified organic group having a hydroxy group.
- polyalkylene glycol modification include polyethylene glycol modification, polypropylene glycol modification, combinations thereof, and the like.
- the specific modified silicone compound may be a polyethylene glycol-modified compound, preferably a compound represented by the following general formula (2) or a compound represented by the following general formula (3). .
- each R 1 is independently a hydrocarbon group.
- m is 1-100, n is 1-5, and p is 1-30.
- each R 1 is independently a hydrocarbon group.
- l is 0 to 100, and r and s are each independently 1 to 30.
- the hydrocarbon group represented by R 1 is each independently the same as the hydrocarbon group represented by R 1 in general formula (1) above. be.
- m is preferably 2-60, n is preferably 1-3, and p is preferably 3-20.
- l is preferably 2 to 50, and r and s are each independently preferably 3 to 20.
- the amount of hydroxy groups in the specific modified silicone compound is not particularly limited. From the viewpoint of further suppressing the occurrence of bleeding, for example, the hydroxyl value is preferably 10 mg KOH/g to 100 mg KOH/g, more preferably 20 mg KOH/g to 80 mg KOH/g, and 30 mg KOH/g. g to 60 mg KOH/g is more preferable.
- the weight average molecular weight of the specific modified silicone compound is preferably from 600 to 10,000, more preferably from 1,000 to 8,000, and even more preferably from 1,400 to 6,000.
- the weight average molecular weight is a value determined by conversion using a standard polystyrene calibration curve using gel permeation chromatography.
- Commercially available products may be used as the specific modified silicone compound.
- Commercially available products include KF-6015, KF-6017, KF-6038, etc. manufactured by Shin-Etsu Chemical Co., Ltd., BYK-Siliclean 3720, BYK-377, etc. manufactured by BYK-Chemie Japan Co., Ltd., Dow Toray FZ-2191, FZ-2164, SF-8427, etc. manufactured by Co., Ltd. can be mentioned.
- the underfill material of the present disclosure may contain a coupling agent.
- the coupling agent serves to strengthen the adhesiveness between the resin component and the inorganic filler in the underfill material, or between the resin component and the constituent members of the electronic component device.
- the coupling agent is not particularly limited, and can be selected from those commonly used as components of underfill materials.
- silane compounds such as aminosilanes, epoxysilanes, mercaptosilanes, alkylsilanes, ureidosilanes, and vinylsilanes having one or more selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group.
- titanium-based compounds, aluminum chelates, and aluminum/zirconium-based compounds are preferred, and epoxysilane is more preferred.
- the underfill material contains a coupling agent
- its content is not particularly limited.
- the total amount of the underfill material is 0 It is preferably 0.05% to 10% by mass, more preferably 0.2% to 5% by mass, even more preferably 0.4% to 1% by mass.
- the underfill material contains other additives other than the above components, such as curing accelerators, ion trapping agents, antioxidants, organic solvents, release agents, coloring agents, rubber particles, leveling agents, antifoaming agents, and specific A silicone compound other than the modified silicone compound may be included as necessary.
- the underfill material of the present disclosure may contain a curing accelerator.
- the type of curing accelerator is not particularly limited, and known curing accelerators can be used. Specifically, 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo[5.4.0]undecene-7; cycloamidine compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, and 2,3-dimethyl quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone; Compound
- the content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.
- the underfill material of the present disclosure may contain ion trapping agents.
- the ion trapping agent that can be used in the present disclosure is not particularly limited as long as it is an ion trapping agent commonly used in underfill materials used for manufacturing electronic component devices.
- Examples of ion trapping agents include compounds represented by the following general formula (VI-1) or the following general formula (VI-2).
- the ion trap agent is available as a commercial product.
- a compound represented by general formula (VI-1) for example, "DHT-4A” (manufactured by Kyowa Chemical Industry Co., Ltd., trade name) is commercially available.
- a compound represented by the general formula (VI-2) for example, "IXE500” (manufactured by Toagosei Co., Ltd., trade name) is available as a commercial product.
- ion trapping agents other than those described above include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like.
- An ion trap agent may be used individually by 1 type, or may use 2 or more types together.
- the content of the ion trapping agent is preferably 1 part by mass or more with respect to 100 parts by mass of the epoxy resin from the viewpoint of achieving sufficient moisture resistance reliability. From the viewpoint of sufficiently exhibiting the effects of the other components, the content of the ion trapping agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin, and is 1 to 10 parts by mass. is more preferable, and 2 parts by mass to 5 parts by mass is even more preferable.
- the average particle size of the ion trap agent is preferably 0.1 ⁇ m to 3.0 ⁇ m, and the maximum particle size is preferably 10 ⁇ m or less.
- the average particle size of the ion trapping agent can be measured in the same manner as the inorganic filler.
- the underfill material of the present disclosure may also contain an antioxidant.
- an antioxidant A conventionally well-known thing can be used as an antioxidant.
- phenolic compound antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3,5 -di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis-(4-methyl-6-t-butylphenol), 3,9-bis[2-[3-(3-t-butyl -4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4′-butylidenebis-(6- t-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-t-butyl-4
- Organic sulfur compound antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythrityl.
- Amine compound antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2,4-bis-(n- octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine and the like.
- dicyclohexylamine is commercially available under the trade name of D-CHA-T manufactured by Shin Nippon Rika Co., Ltd., and its derivatives include dicyclohexylamine ammonium nitrite, N, N -di(3-methyl-cyclohexyl)amine, N,N-di(2-methoxy-cyclohexyl)amine, N,N-di(4-bromo-cyclohexyl)amine and the like.
- Phosphorus compound-based antioxidants include trisnonylphenyl phosphite, triphenylphosphite, bis[3,5-di-t-butyl-4-hydroxybenzyl(ethoxy)phosphinate]calcium, tris(2,4-di -t-butylphenyl)phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylether)dibenzo[d,f][1,3,2]dioxaphosphepin- 6-yl]oxy]-N,N-bis[2- ⁇ [2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphos phepin-6-yl]oxy ⁇ -ethyl]ethanamine, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra
- antioxidants may be used alone, or two or more types may be used in combination.
- Specific examples of antioxidants include compounds containing at least one of a phosphorus atom, a sulfur atom and an amine in the same molecule in addition to a phenolic hydroxy group.
- the content of the antioxidant is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass, based on the total epoxy resin. 5% by mass.
- the underfill material of the present disclosure can be blended with an organic solvent as necessary to reduce the viscosity.
- an organic solvent in particular, when using at least one of a solid epoxy resin and a solid curing agent, it is preferable to blend an organic solvent in order to obtain a liquid resin composition.
- the organic solvent is not particularly limited, and alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, Glycol ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate, lactone solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone, dimethylacetamide, dimethyl Amide solvents such as formamide, aromatic solvents such as toluene and xylene, etc.
- alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol
- ketone solvents such as acetone and
- an organic solvent having a boiling point of 170° C. or higher is preferable from the viewpoint of avoiding bubble formation due to rapid volatilization when curing the underfill material.
- the content of volatile matter including organic solvents and the like is not particularly limited as long as it does not form air bubbles when the underfill material is cured, and is preferably 5% by mass or less with respect to the entire underfill material. It is more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.
- the lower limit of the content of volatile matter including organic solvents and the like is not particularly limited as long as it is 0% by mass or more.
- the volatile content of the underfill material is calculated based on the difference in mass before and after heating the underfill material at 180° C. for 30 minutes.
- the underfill material of the present disclosure may contain a release agent.
- the type of release agent is not particularly limited, and known release agents can be used. Specific examples include higher fatty acids, carnauba wax and polyethylene wax.
- the release agent may be used alone or in combination of two or more.
- the content of the release agent is preferably 10% by mass or less with respect to the total amount of the epoxy resin and the curing agent. , 0.5% by mass or more.
- the underfill material of the present disclosure may contain colorants such as dyes and carbon black.
- the colorants may be used singly or in combination of two or more.
- the conductive particles When conductive particles such as carbon black are used as the colorant, the conductive particles preferably contain 1% by mass or less of particles having a particle diameter of 10 ⁇ m or more.
- the content of the conductive particles is preferably 3% by mass or less with respect to the total amount of the epoxy resin and the curing agent, and is 0.01% to 1% by mass. is more preferable.
- the underfill material may contain rubber particles from the viewpoint of low thermal expansion of the cured product.
- One type of rubber particles may be used alone, or two or more types may be used in combination.
- suitable rubber particles include rubber particles of styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), acrylic rubber (AR), and the like.
- SBR styrene-butadiene rubber
- NBR nitrile-butadiene rubber
- BR butadiene rubber
- UR urethane rubber
- AR acrylic rubber
- suitable rubber particles include silicone rubber particles.
- silicone rubber particles include silicone rubber particles obtained by cross-linking linear polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane; surfaces of the silicone rubber particles coated with silicone resin; emulsion polymerization; and core-shell polymer particles containing a core of solid silicone particles obtained by the above method and a shell of an organic polymer such as an acrylic resin.
- the shape of these silicone rubber particles may be amorphous or spherical, and in order to keep the viscosity of the underfill material low, it is preferable to use spherical silicone rubber particles.
- Silicone rubber particles are commercially available from Dow Corning Toray Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., and the like.
- the average particle size of the rubber particles is preferably fine in order to uniformly modify the underfill material.
- the average particle size of the rubber particles is preferably in the range of 0.05 ⁇ m to 10 ⁇ m, more preferably in the range of 0.1 ⁇ m to 5 ⁇ m.
- the average particle size of the rubber particles is 0.05 ⁇ m or more, the dispersibility in the underfill material tends to be further improved.
- the volume average particle diameter of the rubber particles is 10 ⁇ m or less, the effect of reducing stress tends to be further improved, the permeability and fluidity of the underfill material into fine gaps are improved, and voids and unfilling are reduced. It tends to be difficult to invite.
- the average particle size of rubber particles is measured using the same method as for inorganic fillers.
- the rubber particle content is preferably 3% to 30% by mass, more preferably 5% to 28% by mass, based on the total epoxy resin. It is more preferably 10% by mass to 25% by mass.
- the underfill material can be applied, for example, to a semiconductor device on which electronic components to be described later are mounted. Further, in recent years, along with the speeding up of semiconductor devices, there are cases where an interlayer insulating film with a low dielectric constant is formed in semiconductor devices. This interlayer insulating film has a weak mechanical strength and is easily destroyed by external stress, so failures are likely to occur. Since this tendency becomes more conspicuous as the size of the semiconductor element increases, there is a demand for reducing the stress caused by the underfill material.
- a flip chip connection type electronic component device mounted with a semiconductor element having a size of 2 mm or more on the long side and having an interlayer insulating film with a dielectric constant of 3.0 or less can also provide excellent reliability.
- An electronic component device can be provided.
- the underfill material is, for example, an epoxy resin, a curing agent, an inorganic filler, a specific modified silicone compound, and other components that are optionally used, all together or separately, while being subjected to heat treatment if necessary, and stirred. It can be obtained by melting, mixing, dispersing, or the like.
- Equipment for mixing, stirring, dispersing, etc. of these components is not particularly limited, and includes a laikai machine equipped with a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like. mentioned.
- the underfill material can be obtained by mixing and kneading the above components using these devices, and defoaming as necessary.
- silica particles a mixture in which silica particles are mixed in advance with an epoxy resin may be used for the purpose of improving the dispersibility of the particles.
- An electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and a book disposed in a gap between the substrate and the electronic component. and a cured product of the disclosed underfill material.
- the electronic component device of the present disclosure can be obtained by sealing an electronic component with the underfill material of the present disclosure. By sealing the electronic component with the underfill material, the electronic component device of the present disclosure has excellent reliability.
- an electronic component device in which a semiconductor element is flip-chip bonded to wiring formed on a rigid wiring board, a flexible wiring board, or glass by bump connection is one of the targets to which the underfill material of the present disclosure can be applied.
- Specific examples include electronic component devices such as flip chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).
- the underfill material of the present disclosure is useful as an underfill material for flip chips that require high reliability.
- the underfill material of the present disclosure is particularly preferably applied, not only the conventional lead-containing solder used as the bump material for connecting the wiring board and the semiconductor element, but also Sn—Ag—Cu A case of lead-free solder such as a system is also included.
- the underfill material of the present disclosure tends to be able to maintain good reliability even for a flip chip in which bump connections are made using lead-free solder, which is physically brittle compared to conventional lead solder.
- a chip scale package such as a wafer level CSP (Chip Size Package) is mounted on a substrate, there is a tendency that reliability can be improved by applying the underfill material of the present disclosure.
- a method of manufacturing an electronic component device includes sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer using the underfill material according to the present disclosure. It has a step of stopping. There is no particular limitation on the process of sealing a substrate having a circuit layer and an electronic component using the underfill material of the present disclosure. For example, after connecting an electronic component and a substrate having a circuit layer, an underfill material is applied to the gap between the electronic component and the substrate using capillary action, and then the underfill material undergoes a curing reaction.
- the underfill material of the present disclosure is applied to the surface of at least one of the substrate having the circuit layer and the electronic component first, and the electronic component is connected to the substrate by thermocompression, the electronic component and the substrate are connected and underfilled.
- a pre-coating method in which the curing reaction of the filler material and the curing reaction of the filler material are performed together can be mentioned.
- Methods for applying the underfill material include a casting method, a dispensing method, a printing method, and the like.
- the curing conditions for the underfill material are not particularly limited, and for example, it is preferable to heat at 80°C to 165°C for 1 minute to 150 minutes.
- underfill material The components shown in Tables 1 and 2 were blended in the amounts (parts by mass) shown in Tables 1 and 2, kneaded and dispersed using a three-roll mill and a vacuum crusher, and the underfills of Examples and Comparative Examples were obtained. material was prepared. Details of each material shown in Table 1 are as follows. A blank (-) in Table 1 indicates that it is not blended.
- Epoxy resin 1 Liquid bifunctional epoxy resin with an epoxy equivalent of 160 g/mol obtained by epoxidizing bisphenol F
- Epoxy resin 2 Trifunctional liquid epoxy resin with an epoxy equivalent of 95 g/mol obtained by epoxidizing aminophenol
- Epoxy Resin 3 Liquid bifunctional epoxy resin with an epoxy equivalent of 143 g/mol obtained by epoxidizing naphthalene
- Curing agent 1 Diethyltoluenediamine with an active hydrogen equivalent of 45 g/mol
- Curing agent 2 Diethyldiamino with an active hydrogen equivalent of 63 g/mol
- Inorganic filler Spherical fused silica with an average particle size of 0.5 ⁇ m Coloring agent: Carbon black Silicone compound 1: KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd., containing hydroxy group) ⁇ Silicone compound 2: KF-6017 (manufactured by Shin-Etsu Chemical Co.
- test electronic component devices for testing were produced, and evaluation of bleeding, evaluation of adhesion to Si, and evaluation of creep were performed. The results are shown in Tables 1 and 2.
- the specifications of the test electronic component device are as follows. In the test electronic component device, 20 mg of the underfill material was applied to the gap between the substrate and the semiconductor element by a dispensing method under the condition of 110 ° C., and then cured in the air at 150 ° C. for 2 hours to fill the gap. It was produced by sealing.
- Exudation (bleed) length on substrate The vicinity of the portion in contact with the fillet in the substrate of the electronic component device after sealing was observed with a digital microscope (manufactured by Keyence Corporation, Digital microscope VHX-500 (trade name)), and the length of the bleeding of the underfill material was observed. was measured. It can be determined that the shorter the length of bleeding (bleed), the more suppressed the occurrence of bleeding. Based on the measurement result of the bleed length in Comparative Example 5, the bleed length in Examples and Comparative Examples was determined. That is, the bleeding ( ⁇ m) in Example or Comparative Example/bleeding ( ⁇ m) in Comparative Example 5 were obtained. Bleed judgment criteria are as follows.
- -criterion- A Bleed ( ⁇ m) in Example or Comparative Example/Bleed ( ⁇ m) in Comparative Example 5 is less than 1.00.
- B Bleed ( ⁇ m) in Example or Comparative Example/Bleed ( ⁇ m) in Comparative Example 5 is 1.00.
- C Bleed ( ⁇ m) in Example or Comparative Example/Bleed ( ⁇ m) in Comparative Example 5 is greater than 1.00.
- Examples 5 to 8 and Comparative Example 5 the case where the adhesive force could be measured was evaluated as A, and when the rubber sheet was peeled off, the cured product was peeled off from the rubber sheet, and the adhesive force could not be measured. The case was evaluated as B.
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Abstract
Description
また、半導体素子を、セラミック、ガラス/エポキシ樹脂、ガラス/イミド樹脂、ポリイミドフィルム等を基板とする配線基板(以下、単に「基板」とも称する。)上に直接バンプ接続してなる電子部品装置(フリップチップ)では、バンプ接続した半導体素子と配線基板との間隙(ギャップ)に充填するためのアンダーフィル材と称される封止材が使用されている。
アンダーフィル材として使用される樹脂組成物は、電子部品を温湿度及び機械的な外力から保護する重要な役割を果たしている。
<1> エポキシ樹脂と、硬化剤と、無機充填材と、主鎖の末端及び側鎖の少なくとも一方にヒドロキシ基を有するポリエーテル変性シリコーン化合物と、を含み、前記ポリエーテル変性シリコーン化合物の含有率は、アンダーフィル用樹脂組成物全体に対して0.1質量%よりも大きいアンダーフィル用樹脂組成物。
<2> 前記ポリエーテル変性シリコーン化合物の含有率は、アンダーフィル用樹脂組成物全体に対して0.12質量%~0.25質量%である<1>に記載のアンダーフィル用樹脂組成物。
<3> 前記ポリエーテル変性シリコーン化合物は、ポリエチレングリコール変性シリコーン化合物を含む<1>又は<2>に記載のアンダーフィル用樹脂組成物。
<4> 前記硬化剤が、アミン系硬化剤を含む<1>~<3>のいずれか1つに記載のアンダーフィル用樹脂組成物。
<5> 回路層を有する基板と、
前記基板上に配置され、前記回路層と電気的に接続された電子部品と、
前記基板と前記電子部品との間隙に配置された<1>~<4>のいずれか1つに記載のアンダーフィル用樹脂組成物の硬化物と、
を備える電子部品装置。
<6> 回路層を有する基板と、前記基板上に配置され、前記回路層と電気的に接続された電子部品とを、<1>~<4>のいずれか1つに記載のアンダーフィル用樹脂組成物を用いて封止する工程を有する電子部品装置の製造方法。
本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本開示において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本開示において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本開示のアンダーフィル用樹脂組成物は、エポキシ樹脂と、硬化剤と、無機充填材と、主鎖の末端及び側鎖の少なくとも一方にヒドロキシ基を有するポリエーテル変性シリコーン化合物と、を含み、前記ポリエーテル変性シリコーン化合物の含有率は、アンダーフィル用樹脂組成物全体に対して0.1質量%よりも大きい。
本開示のアンダーフィル材は、エポキシ樹脂を含有する。
エポキシ樹脂の種類は特に制限されず、アンダーフィル材の材料として一般に使用されているものから選択できる。エポキシ樹脂は、1種を単独で用いても2種以上を併用してもよい。
エポキシ樹脂として常温で固形のエポキシ樹脂を使用する場合、固形のエポキシ樹脂の含有率は、流動性の観点から、エポキシ樹脂全体に対して20質量%以下であることが好ましい。
本開示のアンダーフィル材は、硬化剤を含有する。
硬化剤の種類は特に制限されず、アンダーフィル材の材料として一般に使用されているものから選択できる。硬化剤は、1種を単独で用いても2種以上を併用してもよい。硬化剤としては、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤等が挙げられる。これらの中でも、硬化剤としては、アミン系硬化剤が好ましい。
硬化剤として常温で固形の硬化剤を使用する場合、固形の硬化剤の含有率は、流動性の観点から、硬化剤全体に対して20質量%以下であることが好ましい。
本開示のアンダーフィル材は、無機充填材を含有する。
無機充填材は、特にその種類に限定はない。
平均粒子径が20nm以上の無機充填材について測定する場合、溶媒(例えば、純水)に、測定対象の無機充填材を1質量%~5質量%の範囲内で界面活性剤1質量%~8質量%とともに添加し、110Wの超音波洗浄機で30秒~5分間振動し、無機充填材を分散する。分散液の約3mL程度を測定用セルに注入して25℃で測定する。測定装置は、レーザ回折式粒度分布計(株式会社堀場製作所製、LA920)を用い、体積基準の粒度分布を測定する。平均粒子径は、体積基準の粒度分布において小径側からの累積が50%となるときの粒子径(D50%)として求められる。
平均粒子径が20nm未満の無機充填材について測定する場合、電子顕微鏡等を用いて無機充填材を画像化し、粒子1つ1つの粒子径を測定し、任意に選択した100個の粒子の粒子径の算術平均にて得られる粒子径を無機充填材の平均粒子径としてもよい。
測定試料が硬化物である場合は、例えば、マッフル炉等で800℃以上の高温で硬化物を処理した後に残渣として得られる灰分を上記の方法で測定することができる。
本開示のアンダーフィル材は、主鎖の末端及び側鎖の少なくとも一方にヒドロキシ基を有するポリエーテル変性シリコーン化合物(特定の変性シリコーン化合物)を含有する。
特定シリコーン化合物の種類は特に制限されず、1種を単独で用いても、2種以上を併用してもよい。
本開示において「シリコーン化合物」とは、シロキサン結合で形成される主鎖を有する化合物を意味する。
特定シリコーン化合物は、25℃において液状のシリコーン化合物であることが好ましい。
なお、「クリープ」とは、アンダーフィル材で封止された半導体素子のフィレット部において半導体素子を這い上がる樹脂成分の滲み出しを意味する。
lは、-[Si(R1)2O]-で表されるシロキサン単位の1分子中のモル数を示し、0~100である。
また、R1の一部がメチル基以外のアルキル基であり、残りのR1がメチル基であってもよく、全てのR1がメチル基であってもよい。
一般式(3)中、R1は、それぞれ独立に炭化水素基である。lは0~100であり、r及びsはそれぞれ独立に1~30である。
一般式(2)及び一般式(3)において、R1で表される炭化水素基としては、それぞれ独立に、前述の一般式(1)において、R1で表される炭化水素基と同様である。
一般式(3)中、lは2~50であることが好ましく、r及びsはそれぞれ独立に3~20であることが好ましい。
本開示において、重量平均分子量は、ゲルパーミエーションクロマトグラフィーを用いて、標準ポリスチレンの検量線を使用して換算することによって決定した値である。
本開示のアンダーフィル材は、カップリング剤を含有してもよい。
カップリング剤は、アンダーフィル材中の樹脂成分と無機充填材又は樹脂成分と電子部品装置の構成部材との間の接着性を強固にする役割を果たす。カップリング剤は特に制限されず、アンダーフィル材の成分として一般に使用されているものから選択できる。具体的には、1級アミノ基、2級アミノ基及び3級アミノ基からなる群から選ばれる1種以上を有するアミノシラン、エポキシシラン、メルカプトシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシラン系化合物、チタン系化合物、アルミニウムキレート類、アルミニウム/ジルコニウム系化合物などが挙げられる。これらの中でも、充填性の観点からは、シラン系化合物が好ましく、エポキシシランがより好ましい。
アンダーフィル材は、上記した成分以外のその他の添加剤として、硬化促進剤、イオントラップ剤、酸化防止剤、有機溶剤、離型剤、着色剤、ゴム粒子、レベリング剤、消泡剤、特定の変性シリコーン化合物以外のシリコーン化合物などを必要に応じて含んでいてもよい。
本開示のアンダーフィル材は、硬化促進剤を含有してもよい。硬化促進剤の種類は特に制限されず、公知の硬化促進剤を使用することができる。
具体的には、1,8-ジアザ-ビシクロ[5.4.0]ウンデセン-7、1,5-ジアザ-ビシクロ[4.3.0]ノネン、5,6-ジブチルアミノ-1,8-ジアザ-ビシクロ[5.4.0]ウンデセン-7等のシクロアミジン化合物;シクロアミジン化合物に無水マレイン酸、1,4-ベンゾキノン、2,5-トルキノン、1,4-ナフトキノン、2,3-ジメチルベンゾキノン、2,6-ジメチルベンゾキノン、2,3-ジメトキシ-5-メチル-1,4-ベンゾキノン、2,3-ジメトキシ-1,4-ベンゾキノン、フェニル-1,4-ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂などのπ結合をもつ化合物を付加してなる分子内分極を有する化合物;ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の3級アミン化合物;3級アミン化合物の誘導体;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール等のイミダゾール化合物;イミダゾール化合物の誘導体;トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス(4-メチルフェニル)ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物;有機ホスフィン化合物に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物;テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、2-エチル-4-メチルイミダゾールテトラフェニルボレート、N-メチルモルホリンテトラフェニルボレート等のテトラフェニルボロン塩;テトラフェニルボロン塩の誘導体;トリフェニルホスホニウム-トリフェニルボラン、N-メチルモルホリ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等のホスフィン化合物とテトラフェニルボロン塩との付加物などが挙げられる。硬化促進剤は、1種類を単独で使用しても、2種類以上を併用してもよい。
本開示のアンダーフィル材は、イオントラップ剤を含有してもよい。
本開示において使用可能なイオントラップ剤は、電子部品装置の製造用途に用いられるアンダーフィル材において、一般的に使用されているイオントラップ剤であれば特に制限されない。イオントラップ剤としては、例えば、下記一般式(VI-1)又は下記一般式(VI-2)で表される化合物が挙げられる。
(一般式(VI-1)中、aは0<a≦0.5であり、uは正の数である。)
BiOb(OH)c(NO3)d (VI-2)
(一般式(VI-2)中、bは0.9≦b≦1.1、cは0.6≦c≦0.8、dは0.2≦d≦0.4である。)
イオントラップ剤は、1種類を単独で使用しても、2種類以上を併用してもよい。
本開示のアンダーフィル材は、酸化防止剤を含んでもよい。酸化防止剤としては従来公知のものを用いることができる。
フェノール化合物系酸化防止剤としては、フェノール核のオルト位に少なくとも1つのアルキル基を有する化合物として、2,6-ジ-t-ブチル-4-メチルフェノール、n-オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、2,2’-メチレンビス-(4-メチル-6-t-ブチルフェノール)、3,9-ビス[2-〔3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ〕-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン、4,4’-ブチリデンビス-(6-t-ブチル-3-メチルフェノール)、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)、テトラキス[メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、2,2-チオ-ジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、N,N’-ヘキサメチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオンアミド]、イソオクチル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、4,6-ビス(ドデシルチオメチル)-o-クレゾール、ビス[3,5-ジ-t-ブチル-4-ヒドロキシベンジル(エトキシ)ホスフィナート]カルシウム、2,4-ビス(オクチルチオメチル)-6-メチルフェノール、1,6-ヘキサンジオール-ビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン、2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシ-5-メチルベンジル)-4-メチルフェニルアクリレート、2-[1-(2-ヒドロキシ-3,5-ジ-t-ペンチルフェニル)エチル]-4,6-ジ-t-ペンチルフェニルアクリレート、2,2’-メチレンビス-(4-エチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチル-4-エチルフェノール、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、トリエチレングリコール-ビス[3-(3-t-ブチル―4-ヒドロキシ-5-メチルフェニル)プロピオネート]、トリス(3,5-ジ-t-ブチル-4ヒドロキシベンジル)イソシアヌレート、ジエチル[〔3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル〕メチル]ホスホネート、2,5,7,8-テトラメチル-2-(4’,8’,12’-トリメチルトリデシル)クロマン-6-オール、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン等が挙げられる。
有機硫黄化合物系酸化防止剤としては、ジラウリル―3,3’-チオジプロピオネート、ジミリスチル―3,3’-チオジプロピオネート、ジステアリル―3,3’-チオジプロピオネート、ペンタエリスリチルテトラキス(3-ラウリルチオプロピオネート)、ジトリデシル―3,3’-チオジプロピオネート、2-メルカプトベンズイミダゾール、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)、2,2-チオ-ジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、4,6-ビス(ドデシルチオメチル)-o-クレゾール、2,4-ビス(オクチルチオメチル)-6-メチルフェノール、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン等が挙げられる。
アミン化合物系酸化防止剤としては、N,N’-ジアリル-p-フェニレンジアミン、N,N’-ジ-sec-ブチル―p-フェニレンジアミン、オクチル化ジフェニルアミン、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン等が挙げられる。
アミン化合物系酸化防止剤のうち、ジシクロヘキシルアミンとしては、新日本理化株式会社製商品名D-CHA-T等が市販品として入手可能であり、その誘導体としては亜硝酸ジシクロヘキシルアミンアンモニウム、N,N-ジ(3-メチル-シクロヘキシル)アミン、N,N-ジ(2-メトキシ-シクロヘキシル)アミン、N,N-ジ(4-ブロモ-シクロヘキシル)アミン等が挙げられる。
リン化合物系酸化防止剤としては、トリスノニルフェニルフォスファイト、トリフェニルフォスファイト、ビス[3,5-ジ-t-ブチル-4-ヒドロキシベンジル(エトキシ)ホスフィナート]カルシウム、トリス(2,4-ジ-t-ブチルフェニル)フォスファイト、2-[〔2,4,8,10-テトラキス(1,1-ジメチルエ-テル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル〕オキシ]-N,N-ビス[2-{〔2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル〕オキシ}-エチル]エタナミン、6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン、ジエチル[〔3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル〕メチル]ホスホネート等が挙げられる。
酸化防止剤は、1種類を単独で使用しても、2種類以上を併用してもよい。なお、酸化防止剤の具体例としてフェノール性ヒドロキシ基に加え、リン原子、硫黄原子及びアミンのいずれかを少なくとも1つ同一分子中に含む化合物が存在するが、これらの化合物は重複して挙げる場合がある。
本開示のアンダーフィル材には、低粘度化のために必要に応じて有機溶剤を配合することができる。特に、固体のエポキシ樹脂及び固体の硬化剤の少なくとも一方を用いる場合には、液状の樹脂組成物を得るために、有機溶剤を配合することが好ましい。
有機溶剤としては、特に制限はなく、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、エチレングリコールエチルエーテル、エチレングリコールメチルエーテル、エチレングリコールブチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールメチルエーテルアセテート等のグリコールエーテル系溶剤、γ-ブチロラクトン、δ-バレロラクトン、ε-カプロラクトン等のラクトン系溶剤、ジメチルアセトアミド、ジメチルホルムアミド等のアミド系溶剤、トルエン、キシレン等の芳香族系溶剤などが挙げられ、1種類を単独で使用しても、2種類以上を併用してもよい。これらの中では、アンダーフィル材を硬化する際の急激な揮発による気泡形成を避ける観点からは沸点が170℃以上の有機溶剤が好ましい。
本開示において、アンダーフィル材の揮発分は、アンダーフィル材を180℃にて30分の条件で加熱し、加熱前後の質量差に基づいて算出される。
本開示のアンダーフィル材は、離型剤を含有してもよい。離型剤の種類は特に制限されず、公知の離型剤を使用することができる。具体的には、例えば、高級脂肪酸、カルナバワックス及びポリエチレン系ワックスが挙げられる。離型剤は、1種類を単独で使用しても、2種類以上を併用してもよい。
アンダーフィル材が離型剤を含有する場合、離型剤の含有率は、エポキシ樹脂と硬化剤の合計量に対して、10質量%以下であることが好ましく、その効果を発揮させる観点からは、0.5質量%以上であることが好ましい。
本開示のアンダーフィル材は、染料、カーボンブラック等の着色剤を含有してもよい。着色剤は、1種類を単独で使用しても、2種類以上を併用してもよい。
アンダーフィル材が導電性粒子を含有する場合、導電性粒子の含有率は、エポキシ樹脂と硬化剤の合計量に対して3質量%以下であることが好ましく、0.01質量%~1質量%であることがより好ましい。
アンダーフィル材は、硬化物の低熱膨張化の観点から、ゴム粒子を含有してもよい。ゴム粒子は、1種類を単独で使用しても、2種類以上を併用してもよい。
好適なゴム粒子の例としては、スチレン-ブタジエンゴム(SBR)、ニトリル-ブタジエンゴム(NBR)、ブタジエンゴム(BR)、ウレタンゴム(UR)、アクリルゴム(AR)等のゴム粒子が挙げられる。中でも、耐熱性及び耐湿性の観点からは、アクリルゴムを含むゴム粒子が好ましく、コアシェル型アクリルゴム粒子がより好ましい。
シリコーンゴム粒子としては、ポリジメチルシロキサン、ポリメチルフェニルシロキサン、ポリジフェニルシロキサン等の直鎖状のポリオルガノシロキサンを架橋したシリコーンゴム粒子;該シリコーンゴム粒子の表面をシリコーンレジンで被覆したもの、乳化重合等で得られる固形シリコーン粒子のコアとアクリル樹脂等の有機重合体のシェルを含むコア-シェル重合体粒子などが挙げられる。これらのシリコーンゴム粒子の形状は無定形であっても球形であってもよく、アンダーフィル材の粘度を低く抑えるためには、球形のシリコーンゴム粒子を用いることが好ましい。
シリコーンゴム粒子は、東レ・ダウコーニング・シリコーン株式会社、信越化学工業株式会社等から市販品が入手可能である。
ゴム粒子の平均粒子径は、無機充填材と同様の方法を用いて測定される。
アンダーフィル材がゴム粒子を含む場合、ゴム粒子の含有率は、エポキシ樹脂全体に対して3質量%~30質量%であることが好ましく、5質量%~28質量%であることがより好ましく、10質量%~25質量%であることがさらに好ましい。
アンダーフィル材は、例えば、後述する電子部品を搭載した半導体装置に適用することができる。
また、近年、半導体素子の高速化に伴い、低誘電率の層間絶縁膜が半導体素子に形成される場合がある。この層間絶縁膜は機械強度が弱く、外部からの応力で破壊されやすいため、故障が発生しやすい。この傾向は半導体素子が大きくなる程顕著になるため、アンダーフィル材に起因して発生する応力の低減が求められている。
本開示のアンダーフィル材によると、半導体素子のサイズが長い方の辺で2mm以上であり、誘電率が3.0以下の層間絶縁膜を有する半導体素子を搭載するフリップチップ接続形式の電子部品装置に対しても、優れた信頼性を提供できる。
また、配線基板と半導体素子とのバンプ接続面の距離が200μm以下であるフリップチップ接続に対しても良好な流動性及び充填性を示し、耐湿性、耐熱衝撃性等の信頼性にも優れた電子部品装置を提供することができる。
アンダーフィル材は、例えば、エポキシ樹脂、硬化剤、無機充填材及び特定の変性シリコーン化合物並びに必要に応じて用いられるその他の成分を一括して又は別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散等させることにより得ることができる。これらの成分の混合、撹拌、分散等のための装置としては、特に限定されるものではなく、撹拌装置、加熱装置等を備えたライカイ機、3本ロールミル、ボールミル、プラネタリーミキサー、ビーズミルなどが挙げられる。これらの装置を用いて上記成分を混合し、混練し、必要に応じて脱泡することによってアンダーフィル材を得ることができる。
シリカ粒子としては、粒子の分散性の向上を目的として、予めシリカ粒子がエポキシ樹脂に混合した混合物を用いてもよい。
本開示の電子部品装置は、回路層を有する基板と、前記基板上に配置され、前記回路層と電気的に接続された電子部品と、前記基板と前記電子部品との間隙に配置された本開示のアンダーフィル材の硬化物と、を備える。本開示の電子部品装置は、本開示のアンダーフィル材により電子部品を封止して得ることができる。電子部品がアンダーフィル材によって封止されることで、本開示の電子部品装置は、信頼性に優れる。
特に、リジッド配線板、フレキシブル配線板又はガラス上に形成した配線に、半導体素子をバンプ接続によりフリップチップボンディングした電子部品装置が、本開示のアンダーフィル材を適応しうる対象の1つとして挙げられる。具体的な例としては、フリップチップBGA(Ball Grid Array)、LGA(Land Grid Array)、COF(Chip On Film)等の電子部品装置が挙げられる。
本開示の電子部品装置の製造方法は、回路層を有する基板と、前記基板上に配置され、前記回路層と電気的に接続された電子部品とを、本開示のアンダーフィル材を用いて封止する工程を有する。
本開示のアンダーフィル材を用いて回路層を有する基板と電子部品とを封止する工程に特に限定はない。例えば、電子部品と回路層を有する基板とを接続した後に、電子部品と基板とのギャップに毛細管現象を利用してアンダーフィル材を付与し、次いでアンダーフィル材の硬化反応を行う後入れ方式、並びに、先に回路層を有する基板及び電子部品の少なくとも一方の表面に本開示のアンダーフィル材を付与し、熱圧着して電子部品を基板に接続する際に、電子部品及び基板の接続とアンダーフィル材の硬化反応とを一括して行う先塗布方式が挙げられる。
アンダーフィル材の付与方法としては、注型方式、ディスペンス方式、印刷方式等が挙げられる。
表1及び表2に示す各成分を表1及び表2に示す量(質量部)で配合し、三本ロール及び真空らい潰機にて混練し分散して、実施例及び比較例のアンダーフィル材を調製した。表1に示す各材料の詳細は、下記のとおりである。表1中の空欄(-)は未配合であることを示す。
・エポキシ樹脂2:アミノフェノールをエポキシ化して得られるエポキシ当量95g/molの3官能液状エポキシ樹脂
・エポキシ樹脂3:ナフタレンをエポキシ化して得られるエポキシ当量143g/molの液状2官能エポキシ樹脂
・硬化剤1:活性水素当量45g/molのジエチルトルエンジアミン
・硬化剤2:活性水素当量63g/molのジエチルジアミノジフェニルメタン
・無機充填材:平均粒子径0.5μmの球状溶融シリカ
・着色剤:カーボンブラック
・シリコーン化合物1:KF-6015(信越化学工業株式会社製、ヒドロキシ基含有)
・シリコーン化合物2:KF-6017(信越化学工業株式会社製、ヒドロキシ基含有)
・シリコーン化合物3:KF-6038(信越化学工業株式会社製、ヒドロキシ基含有)
・シリコーン化合物4:BYK-Siliclean3720(ビックケミー・ジャパン株式会社製、ヒドロキシ基含有)
・シリコーン化合物5:BYK-302(ビックケミー・ジャパン株式会社製、ヒドロキシ基未含有)
・シリコーン化合物6:BYK-326(ビックケミー・ジャパン株式会社製、ヒドロキシ基未含有)
・シリコーン化合物7:BYK-333(ビックケミー・ジャパン株式会社製、ヒドロキシ基未含有)
・シリコーン化合物8:BYK-349(ビックケミー・ジャパン株式会社製、ヒドロキシ基未含有)
実施例及び比較例で調製したアンダーフィル材を用いて試験用の電子部品装置を作製し、ブリードの評価、Siに対する接着力の評価及びクリープの評価を行った。結果を表1及び表2に示す。
試験用の電子部品装置の仕様は、以下のとおりである。試験用の電子部品装置は、アンダーフィル材20mgを、110℃の条件下でディスペンス方式により基板と半導体素子との間隙に塗布した後、150℃で2時間、空気中で硬化することで間隙を封止して作製した。
・基板のサイズ:35mm×35mm×1mm厚
・基板(コア)の種類:E-679FG(G)(昭和電工マテリアルズ株式会社製、商品名)
・ソルダーレジストの種類:SR-7300G(昭和電工マテリアルズ株式会社製、商品名)
・基板と半導体素子とのギャップ:50μm
封止後の電子部品装置の基板におけるフィレットと接する部分近傍をデジタルマイクロスコープ(株式会社キーエンス製、Digital microscope VHX-500(商品名))で観察し、アンダーフィル材の滲み出し(ブリード)の長さを測定した。滲み出し(ブリード、Bleed)の長さが短いほど、ブリードの発生が抑制されていると判断できる。
比較例5におけるブリードの長さの測定結果を基準として、実施例及び比較例におけるブリードの長さを求めた。つまり、実施例又は比較例におけるブリード(μm)/比較例5におけるブリード(μm)をそれぞれ求めた。ブリードの判定基準は以下の通りである。
-判定基準-
A:実施例又は比較例におけるブリード(μm)/比較例5におけるブリード(μm)が1.00未満である。
B:実施例又は比較例におけるブリード(μm)/比較例5におけるブリード(μm)が1.00である。
C:実施例又は比較例におけるブリード(μm)/比較例5におけるブリード(μm)が1.00よりも大きい。
実施例5~8及び比較例5において、前述の基板(材質Si)に対するアンダーフィル材の硬化物の接着力を以下のようにして評価した。
中が空洞であるゴムシートを基板上に配置し、ゴム部材内にアンダーフィル材を供給し、次いで、150℃で2時間の条件でアンダーフィル材を硬化させた。アンダーフィル材を硬化させて硬化物(サイズ:直径3mm、高さ1mmである円柱状硬化物)とした後、ゴムシートを剥離した。ゴムシート剥離後に基板上に設けられた硬化物について、万能型ボンドテスタを用いて、ツール高さ50μm、ツール速度50μm/sec、25℃の条件でせん断接着力を測定した。
実施例5~8及び比較例5において、接着力の測定が可能であった場合を評価Aとし、ゴムシート剥離時にゴムシート共に硬化物が剥離してしまい、接着力の測定が不可能であった場合を評価Bとした。
実施例5~8及び比較例5において、封止後の電子部品装置の半導体素子上面における端部近傍をレーザ顕微鏡(オリンパス株式会社製、走査型共焦点レーザ顕微鏡 OLS3000(商品名))で観察し、アンダーフィル材の滲み出し(クリープ)の長さを測定し、以下の判定基準でクリープの評価を行った。
-判定基準-
A:実施例におけるクリープ(μm)/比較例5におけるクリープ(μm)が1.00未満である。
B:実施例におけるクリープ(μm)/比較例5におけるクリープ(μm)が1.00以上である。
一方、表1及び表2に示すように、ヒドロキシ基を含むシリコーン化合物を所定量用いた実施例1~8では、シリコーン化合物を用いていない比較例5よりもブリードの評価が良好であった。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (6)
- エポキシ樹脂と、硬化剤と、無機充填材と、主鎖の末端及び側鎖の少なくとも一方にヒドロキシ基を有するポリエーテル変性シリコーン化合物と、を含み、前記ポリエーテル変性シリコーン化合物の含有率は、アンダーフィル用樹脂組成物全体に対して0.1質量%よりも大きいアンダーフィル用樹脂組成物。
- 前記ポリエーテル変性シリコーン化合物の含有率は、アンダーフィル用樹脂組成物全体に対して0.12質量%~0.25質量%である請求項1に記載のアンダーフィル用樹脂組成物。
- 前記ポリエーテル変性シリコーン化合物は、ポリエチレングリコール変性シリコーン化合物を含む請求項1又は請求項2に記載のアンダーフィル用樹脂組成物。
- 前記硬化剤が、アミン系硬化剤を含む請求項1~請求項3のいずれか1項に記載のアンダーフィル用樹脂組成物。
- 回路層を有する基板と、
前記基板上に配置され、前記回路層と電気的に接続された電子部品と、
前記基板と前記電子部品との間隙に配置された請求項1~請求項4のいずれか1項に記載のアンダーフィル用樹脂組成物の硬化物と、
を備える電子部品装置。 - 回路層を有する基板と、前記基板上に配置され、前記回路層と電気的に接続された電子部品とを、請求項1~請求項4のいずれか1項に記載のアンダーフィル用樹脂組成物を用いて封止する工程を有する電子部品装置の製造方法。
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