WO2021193028A1 - Composition de résine pour moulage et dispositif électronique - Google Patents

Composition de résine pour moulage et dispositif électronique Download PDF

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WO2021193028A1
WO2021193028A1 PCT/JP2021/009335 JP2021009335W WO2021193028A1 WO 2021193028 A1 WO2021193028 A1 WO 2021193028A1 JP 2021009335 W JP2021009335 W JP 2021009335W WO 2021193028 A1 WO2021193028 A1 WO 2021193028A1
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resin composition
boron nitride
molding resin
inorganic filler
composition
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PCT/JP2021/009335
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English (en)
Japanese (ja)
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一 大塚
卓也 浅野
隆宏 明石
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パナソニックＩｐマネジメント株式会社
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Priority to JP2022509541A priority Critical patent/JPWO2021193028A1/ja
Publication of WO2021193028A1 publication Critical patent/WO2021193028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present disclosure relates to a molding resin composition and an electronic device, and more specifically, a molding resin composition containing a reaction-curable resin and an inorganic filler, and a sealing material prepared from the molding resin composition. Regarding electronic devices to be equipped.
  • Patent Document 1 contains an epoxy resin, a curing agent, a curing aid, and an inorganic filler as essential components, and the inorganic filler is a resin composition.
  • the inorganic filler contains 60 Vol% or more of alumina, contains 99.9 Vol% or more of particles having a particle size of 32 ⁇ m or less, and contains particles having a particle size of 0.5 ⁇ m or less.
  • a sealing epoxy resin composition containing 5 Vol% or more and having a particle size distribution having an average particle size in the range of 1 to 10 ⁇ m is disclosed.
  • the problems of the present disclosure are a molding resin which can easily increase the thermal conductivity of the cured product, prevent the elastic modulus of the cured product from becoming excessively high, reduce the thermal expansion coefficient of the cured product, and prevent the moldability from deteriorating. It is an object of the present invention to provide an electronic device including a composition and a sealing material made from the molding resin composition.
  • the molding resin composition according to one aspect of the present disclosure contains a reaction-curable resin (A) and an inorganic filler (B).
  • the inorganic filler (B) contains spherical boron nitride (b1).
  • the inorganic filler (B) does not contain scaly boron nitride (b2), or the inorganic filler (B) contains scaly boron nitride (b2) and said in the inorganic filler (B).
  • the proportion of scaly boron nitride (b2) is more than 0% by mass and less than 3% by mass with respect to the molding resin composition.
  • the electronic device includes a base material, an electronic component mounted on the base material, and a sealing material for sealing the electronic component.
  • the sealing material is a cured product of the molding resin composition.
  • FIG. 5 is a schematic cross-sectional view of an example of an electronic device according to an embodiment of the present disclosure.
  • FIG. 5 is a schematic cross-sectional view of another example of an electronic device according to an embodiment of the present disclosure.
  • the molding resin composition contains alumina as disclosed in Patent Document 1 (Japanese Unexamined Patent Publication No. 2014-31460), the alumina has good thermal conductivity, so that the molding resin is good.
  • the thermal conductivity and heat dissipation of the encapsulant produced from the composition tend to increase.
  • the proportion of alumina in the molding resin composition is increased in order to increase the thermal conductivity, the encapsulant becomes excessively hard, resulting in poor workability or warpage of the encapsulant. do.
  • the inventor can easily increase the thermal conductivity of the cured product, the elastic modulus of the cured product is unlikely to be excessively high, the thermal expansion coefficient of the cured product can be lowered, and the moldability is unlikely to deteriorate.
  • Research and development have been carried out to provide the composition, and the present disclosure has been completed.
  • the molding resin composition (hereinafter, also referred to as composition (X)) contains a reaction curable resin (A) and an inorganic filler (B).
  • the inorganic filler (B) contains spherical boron nitride (b1).
  • the inorganic filler (B) does not contain scaly boron nitride (b2), or the inorganic filler (B) contains scaly boron nitride (b2) and is scaly in the inorganic filler (B).
  • the proportion of boron nitride (b2) is more than 0% by mass and less than 3% by mass with respect to the composition (X).
  • the spherical boron nitride (b1) when the composition (X) is flowed and molded, the spherical boron nitride (b1) does not easily inhibit the flow of the composition (X), so that the moldability of the composition (X) is deteriorated. Hateful. Further, since spherical boron nitride (b1) has higher thermal conductivity than alumina or the like, it is easy to improve the thermal conductivity and heat dissipation of the cured product of the composition (X). Further, since spherical boron nitride (b1) has a lower hardness than alumina or the like, it is difficult to increase the elastic modulus of the cured product.
  • the present embodiment it is easy to increase the thermal conductivity of the cured product of the composition (X), the elastic modulus of the cured product is unlikely to be excessively high, and the moldability of the composition (X) is unlikely to deteriorate. ..
  • composition (X) The components of the composition (X) will be further described.
  • the reaction-curable resin (A) contains, for example, at least one of a thermosetting resin (A1) and a photocurable resin (A2).
  • the curable component (A) preferably contains a thermosetting resin (A1).
  • the composition (X) may have thermosetting properties.
  • the thermosetting resin (A1) can contain at least one thermosetting resin selected from the group consisting of, for example, an epoxy resin (a), a maleimide resin, a phenol resin, a thermosetting polyphenylene ether oligomer, and a cyanate resin.
  • the thermosetting resin (A1) may contain various resins depending on the use of the composition (X) and the like. When the encapsulant 4 is prepared from the composition (X), the thermosetting resin (A1) preferably contains an epoxy resin (a).
  • thermosetting polyphenylene ether oligomer has a structure in which the terminal of the molecular chain of the polyphenylene ether oligomer is modified to bond a functional group having an ethylenic double bond.
  • the structure of the thermocurable polyphenylene ether oligomer is known. For example, it is synthesized by reacting a polyphenylene ether oligomer having phenolic hydroxyl groups at both ends with vinylbenzyl chloride to convert the phenolic hydroxyl group into vinylbenzyl ether. ..
  • the epoxy resin (a) preferably has two or more epoxy groups in one molecule.
  • the epoxy resin (a) can contain various resins such as a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and an olefin oxidation type (alicyclic) epoxy resin.
  • the epoxy resin is, for example, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol S type epoxy resin; a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin.
  • Such as hydrogenated bisphenol type epoxy resin; biphenyl type epoxy resin; naphthalene ring-containing epoxy resin; alicyclic epoxy resin; dicyclopentadiene type epoxy resin; phenol novolac type epoxy resin; cresol novolac type epoxy resin; triphenylmethane type epoxy It contains at least one selected from the group consisting of resins; aliphatic epoxy resins; triglycidyl isocyanurate; and glycidyl group-containing silicone resins.
  • the epoxy resin preferably contains at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthalene ring-containing epoxy resin and alicyclic epoxy resin.
  • the epoxy resin (a) may be solid or liquid at 25 ° C.
  • the epoxy resin (a) is preferably liquid at 25 ° C.
  • the viscosity at 25 ° C. is preferably 0.1 Pa ⁇ s or more and 150 Pa ⁇ s or less, and more preferably 0.1 Pa ⁇ s or more and 100 Pa ⁇ s or less.
  • the viscosity is a value measured with an HB type rotational viscometer (rotation speed 50 rpm) at 25 ° C.
  • the components contained in the epoxy resin (a) are not limited to the above.
  • the epoxy resin (a) preferably contains an epoxy resin (a1) having a mesogen skeleton. That is, the reaction-curable resin (A) preferably contains an epoxy resin (a1) having a mesogen skeleton.
  • the composition (X) tends to have good fluidity, and therefore the composition (X) tends to have high moldability.
  • the mesogen skeleton is a molecular structure capable of expressing crystallinity.
  • the mesogen skeleton in the epoxy resin (a1) is, for example, a phenyl benzoate skeleton, a biphenyl skeleton, a benzophenone skeleton, a phenyl ether skeleton, a benzanilide skeleton, a stillben skeleton, a diazobenzene skeleton and a benzylene aniline skeleton, and a substituent bonded to these skeletons.
  • the phenyl benzoate skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (I) or a structure in which a substituent is bonded to this structure.
  • the biphenyl skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (II), or a structure in which a substituent is bonded to this structure.
  • the benzophenone skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (III) or a structure in which a substituent is bonded to this structure.
  • the phenyl ether skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (IV) or a structure in which a substituent is bonded to this structure.
  • the benzanilide skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (V), or a structure in which a substituent is bonded to this structure.
  • the stilbene skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (VI) or a structure in which a substituent is bonded to this structure.
  • the diazobenzene skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (VII) or a structure in which a substituent is bonded to this structure.
  • the benzylidene aniline skeleton has, for example, a structure in which any two hydrogens are removed from the structure represented by the following formula (VIII), or a structure in which a substituent is bonded to this structure. It is more preferable that no substituent is attached to these skeletons.
  • the epoxy resin (a1) having a mesogen skeleton is, for example, a biphenyl type epoxy resin, a stilbene type epoxy resin, or a modified epoxy resin synthesized by reacting a mixture of hydroquinone and 4,4′-dihydroxybiphenyl with epichlorohydrin. , And at least one selected from the group consisting of phenylbenzoate type epoxy resins.
  • the epoxy resin (a1) having a mesogen skeleton preferably contains a modified epoxy resin (a11) synthesized by reacting a mixture of hydroquinone and 4,4'-dihydroxybiphenyl with epichlorohydrin.
  • the epoxy resin (a1) having a mesogen skeleton preferably contains an epoxy resin (a12) synthesized by the following method.
  • the compound represented by the formula (1) is reacted with the compound represented by the formula (2) to obtain a phenol compound.
  • This phenol compound is reacted with epihalohydrin in the presence of an alkali metal hydroxide.
  • the product thus obtained is heated to 150 ° C. or higher to melt the crystal components in the product, and then rapidly cooled at 50 ° C. or lower.
  • the epoxy resin (a12) is obtained.
  • each of the plurality of R 1 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group or C Alkoxy groups of numbers 1 to 10 substituted or unsubstituted.
  • l represents the number of R 1 and is an integer from 0 to 4.
  • R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, 6 carbon atoms It is a substituted or unsubstituted aryl group of ⁇ 10, a hydroxyl group, a nitro group, a formyl group, an allyl group or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
  • k represents the number of R 2 and is an integer from 0 to 4.
  • the ratio of the epoxy resin (a1) to the entire epoxy resin (a) is preferably 50% by mass and 100% by mass or less. This ratio is more preferably 70% by mass or more and 100% by mass or less, and further preferably 80% by mass or more and 100% by mass or less.
  • the composition (X) when the composition (X) contains an epoxy resin, the composition (X) preferably contains a curing agent.
  • the curing agent contains at least one selected from the group consisting of, for example, acid anhydrides, amines, imidazoles, phenols, hydrazides, polypeptides, and Lewis acid-amine complexes.
  • Acid anhydrides include, for example, methyltetrahydrophthalic acid anhydride, methylhexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methylhymic acid anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride. , 3,4-Dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, and 1-isopropyl-4-methyl-bicyclo [2.2.2 ] Contains at least one selected from the group consisting of octo-5-ene-2,3-dicarboxylic acid anhydride and the like.
  • Amines contain, for example, a compound having at least one primary or secondary amino group in the molecule.
  • the amines preferably contain aromatic amines.
  • Aromatic amines include, for example, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylsulfide, metaxylene diamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-.
  • the imidazoles are, for example, 2MZ, C11Z, 2PZ, 2E4MZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2MZ-A, C11Z- Selected from the group consisting of A, 2E4MZ-A, 2P4MHZ, 2PHZ, 2MA-OK, 2PZ-OK (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name), and compounds in which these imidazoles are added to epoxy resin. Contains at least one of them.
  • the imidazoles may be microencapsulated.
  • phenols include bisphenol resin, phenol novolac resin, naphthol novolac resin, allylated phenol novolac resin, biphenol resin, cresol novolac resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional phenol resin, and the like. It contains at least one selected from the group consisting of xylylene-modified phenol novolac resin, xylylene-modified naphthol novolac resin, and various polyfunctional phenol resins.
  • the components contained in the curing agent are not limited to the above.
  • the stoichiometric equivalent ratio of the curing agent to the epoxy resin is preferably 0.6 or more and 1.4 or less. In this case, it is possible to set an appropriate amount of the curing agent to the epoxy resin, and it is possible to prevent insufficient curing, a decrease in heat resistance of the cured product, a decrease in the strength of the cured product, an increase in the amount of moisture absorbed by the cured product, and the like.
  • composition (X) may contain a curing accelerator.
  • Curing accelerators include imidazoles such as 2-methylimidazole, 2-ethyl imidazole, 2-phenyl imidazole, 2-ethyl-4-methyl imidazole, 1,8-diazabicyclo [5.4.0] undecene-7, and the like.
  • Cycloamidins such as 1,5-diazabicyclo [4.3.0] nonen-5, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7, 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) )
  • Organic phosphines such as phosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / t
  • the ratio of the curing accelerator is, for example, 0.05% by mass or more and 5% by mass or less with respect to the total amount of the epoxy resin and the curing agent.
  • the composition (X) may have photocurability.
  • the photocurable resin (A2) consists of a group consisting of a monofunctional (meth) acrylate such as 2- (meth) acryloyloxyethyl phthalic acid and a polyfunctional (meth) acrylate such as pentaerythritol tri (meth) acrylate. Contains at least one compound of choice.
  • (meth) acrylic means at least one of "acry” and “methacry”, and for example, (meth) acrylate is one or both of acrylate and methacrylate. be.
  • the inorganic filler (B) contains spherical boron nitride (b1) as described above. It is judged from common general knowledge that the shape of the spherical boron nitride (b1) is spherical.
  • the circularity of the spherical boron nitride (b1) is 0.8 or more.
  • the spherical boron nitride (b1) is particularly unlikely to inhibit the fluidity of the composition (X).
  • the circularity of spherical boron nitride (b1) is defined as follows.
  • An image with a resolution of 1280 x 1024 pixels is obtained by photographing particles of spherical boron nitride (b1) at a magnification of 10,000 to 100,000 times with an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Then, the projected area (S) and the peripheral length (L) of the particles are measured by analyzing the image in the manual recognition mode using image analysis software (for example, a trade name MacView manufactured by Mountech Co., Ltd.). From this result, the circularity of the particles is calculated by the following formula.
  • the circularity of the spherical boron nitride (b1) is preferably 0.8 or more, and more preferably 0.9 or more, because it improves the filling property and reduces the influence of orientation.
  • the spherical boron nitride (b1) preferably contains hexagonal boron nitride. In this case, since the hardness of hexagonal boron nitride is low, an excessive increase in elastic modulus of the cured product is particularly unlikely to occur. It is also preferable that all spherical boron nitrides (b1) are hexagonal boron nitrides.
  • Spherical boron nitride (b1) containing hexagonal boron nitride is produced, for example, by a vapor phase synthesis method.
  • boron nitride white powder is obtained by first heating boric acid alkoxide volatilized in an inert gas stream and ammonia at 750 to 1100 ° C. for a time within 30 seconds.
  • the boron nitride white powder is heated at 1000 to 1600 ° C. for 1 hour or more in an atmosphere containing ammonia gas to obtain a fired product.
  • the fired product is heated at 1000 to 3000 ° C. for 0.5 hours or more in a nitrogen atmosphere to obtain spherical boron nitride (b1) containing hexagonal boron nitride.
  • the ratio of spherical boron nitride (b1) is preferably 1% by mass or more and 20% by mass or less with respect to the resin composition for molding. When this ratio is 3% by mass or more, the thermal conductivity of the cured product tends to increase. When this ratio is 20% by mass or less, the fluidity of the composition (X) is not particularly hindered, and therefore the composition (X) tends to have particularly good moldability.
  • the proportion of spherical boron nitride (b1) is more preferably 3% by mass or more and 20% by mass or less, and further preferably 10% by mass or more and 15% by mass or less.
  • the ratio of the spherical boron nitride (b1) is preferably 10% by mass or more and 40% by mass or less with respect to the inorganic filler (B). This ratio is more preferably 15% by mass or more and 30% by mass or less.
  • the median diameter of the spherical boron nitride (b1) is preferably 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the median diameter is more preferably 0.1 ⁇ m or more and 0.8 ⁇ m or less, and further preferably 0.3 ⁇ m or more and 0.6 ⁇ m or less.
  • the median diameter of the spherical boron nitride (b1) is calculated from the volume-based particle size distribution obtained by measuring the spherical boron nitride (b1) by a laser diffraction / scattering method.
  • the inorganic filler (B) preferably further contains a filler (b3) having a median diameter of 0.1 ⁇ m or more and 10 ⁇ m or less in addition to the spherical boron nitride (b1).
  • a filler (b3) having a median diameter of 0.1 ⁇ m or more and 10 ⁇ m or less in addition to the spherical boron nitride (b1).
  • the particles of the spherical boron nitride (b1) are likely to be arranged between the particles of the filler (b3) in the composition (X)
  • the spherical boron nitride (b1) and the particles of the composition (X) are easily arranged. It is easy to be densely filled with the filler (b3). Therefore, even if the amount of the inorganic filler (B) is increased, the fluidity of the composition (X) is less likely to be hindered.
  • the particles of spherical boron nitride (b1) are likely to be arranged between the particles of the filler (b3) even in the cured product, the spherical boron nitride (b1) and the filler (b3) are easily arranged in the composition (X). And are easily filled tightly. Therefore, a path for heat conduction by the inorganic filler (B) is likely to be formed in the cured product, and the heat conductivity of the cured product is likely to be further enhanced.
  • the median diameter of the filler (b3) is more preferably 0.5 ⁇ m or more and 5 ⁇ m or less, and further preferably 1 ⁇ m or more and 3 ⁇ m or less.
  • the filler (b3) contains at least one selected from the group consisting of aluminum hydroxide, boehmite, magnesium oxide, zinc oxide, aluminum nitride, silicon nitride, silicon carbide and diamond. In this case, the thermal conductivity of the cured product is likely to increase further.
  • the filler (b3) may contain alumina. In particular, it is preferable that the filler (b3) contains ⁇ -alumina. In this case, the thermal conductivity of the cured product is likely to increase further. It is more preferable that the pregelatinization rate of ⁇ -alumina is 80% or more. In this case, the thermal conductivity of the cured product tends to increase.
  • the composition (X) contains both the epoxy resin (a1) having a mesogen skeleton and ⁇ -alumina.
  • the fluidity of the composition (X) and the thermal conductivity of the cured product are particularly likely to increase.
  • the molecules of the epoxy resin (a1) having a mesogen skeleton tend to be oriented perpendicularly to the surface of the ⁇ -alumina particles, which improves the fluidity. It is presumed that it is involved in the improvement of thermal conductivity.
  • the ratio of the filler (b3) is preferably 70% by mass or more and 97% by mass or less with respect to the entire inorganic filler (B).
  • the proportion of ⁇ -alumina is preferably 70% by mass or more and 97% by mass or less with respect to the entire inorganic filler (B).
  • the total ratio of the spherical boron nitride (b1) and the filler (b3) is determined in the composition (X).
  • it is preferably 75% by mass or more and 95% by mass or less.
  • this ratio is 75% by mass or more, the cured product tends to have particularly high thermal conductivity.
  • this ratio is 95% by mass or less, the fluidity of the composition (X) is not particularly hindered.
  • This ratio is more preferably 80% by mass or more and 93% by mass or less, and further preferably 83% by volume or more and 91% by volume or less.
  • the ratio of the inorganic filler (B) is preferably 75% by mass or more and 95% by mass or less with respect to the composition (X).
  • this ratio is 75% by mass or more, the cured product tends to have particularly high thermal conductivity.
  • this ratio is 95% by mass or less, the fluidity of the composition (X) is not particularly hindered.
  • This ratio is more preferably 80% by mass or more and 93% by mass or less, and further preferably 83% by mass or more and 91% by mass or less.
  • the inorganic filler (B) may further contain a filler (b4) other than the spherical boron nitride (b1) and the filler (b3).
  • the ratio of the filler (b4) is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 10% by mass or less, based on the inorganic filler (B). ..
  • the ratio of scaly boron nitride (b2) in the inorganic filler (B) is 0% by mass or more and less than 3% by mass with respect to the composition (X). That is, the inorganic filler (B) does not contain the scaly boron nitride (b2), or even if it contains the scaly boron nitride (b2), the proportion of the scaly boron nitride (b2) in the inorganic filler (B) is the composition. It is more than 0% by mass and less than 3% by mass with respect to (X).
  • the scaly particles tend to be a factor that hinders the fluidity of the composition (X), but as described above, the inorganic filler (B) does not contain the scaly boron nitride (b2), or the scaly boron nitride ( When the ratio of b2) is more than 0% by mass and less than 3% by mass, the fluidity of the composition (X) is less likely to be inhibited.
  • the proportion of scaly boron nitride (b2) is more preferably 2% by mass or less, and even more preferably 1% by mass or less. It is particularly preferable that the inorganic filler (B) does not contain scaly boron nitride (b2).
  • the proportion of scaly particles in the inorganic filler (B) is preferably 0% by mass or more and less than 3% by mass with respect to the composition (X). That is, the inorganic filler (B) is not limited to the scaly boron nitride (b2), and does not contain scaly particles, or even if it contains scaly particles, the scaly filler in the inorganic filler (B).
  • the proportion of particles is preferably more than 0% by mass and less than 3% by mass with respect to the composition (X). In this case, the fluidity of the composition (X) is less likely to be hindered by the inorganic filler (B).
  • the proportion of scaly particles is more preferably 2% by mass or less, and even more preferably 1% by mass or less. It is particularly preferable that the inorganic filler (B) does not contain scaly particles.
  • the proportion of particles having a particle size of 32 ⁇ m or less in the inorganic filler (B) is preferably 99.9% by volume or more with respect to the inorganic filler (B).
  • the filling property of the composition (X) is less likely to be hindered by the inorganic filler (B), and the composition (X) is particularly easy to fill in a narrow space, for example, smoothly in a space having a width of 1 mm. It becomes easier to fill in.
  • the maximum particle size of the inorganic filler (B) is more preferably 32 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
  • the proportion and maximum particle size of the particles having a particle size of 32 ⁇ m or less in the inorganic filler (B) can be obtained from the volume-based particle size distribution obtained by measuring the inorganic filler (B) by a laser diffraction / scattering method. ..
  • the inorganic filler (B) may be surface-treated with a coupling agent such as a silane coupling agent.
  • a coupling agent such as a silane coupling agent.
  • the composition (X) may contain a coupling agent.
  • composition (X) may further contain components other than the components described above.
  • the composition (X) may contain an appropriate additive.
  • the additive contains at least one selected from the group consisting of, for example, a flux, an ion trapping agent, a viscosity modifier, a surface modifier, a defoaming agent, a leveling agent, a low stress agent, a pigment, and a mold release agent.
  • composition (X) can be obtained, for example, by blending the above components, adding an appropriate solvent as necessary, and mixing them.
  • the composition (X) can be prepared by, for example, the following method. First, a mixture is obtained by simultaneously or sequentially blending the components that can be contained in the composition (X) described above. This mixture is stirred and mixed while performing heat treatment and cooling treatment as necessary. Next, if necessary, an additive is added to this mixture, and the mixture is stirred again and mixed until uniformly dispersed while performing heat treatment and cooling treatment as necessary. Thereby, the composition (X) can be obtained.
  • a disper, a planetary mixer, a ball mill, a three-roll, a bead mill and the like can be applied in an appropriate combination as necessary.
  • the composition (X) can be prepared by, for example, the following method. First, a mixture is obtained by simultaneously or sequentially blending the components that can be contained in the composition (X) described above. This mixture is mixed using a mixer, a blender or the like until it becomes sufficiently uniform, and then melt-kneaded by a kneader such as a hot roll or a kneader. Subsequently, the mixture is cooled to room temperature and then pulverized to obtain a powdery composition (X). Further, the tablet-like composition (X) may be obtained by locking the powder-like composition (X).
  • the composition (X) can have good fluidity as described above.
  • the spiral flow length of the composition (X) is preferably 50 cm or more.
  • the composition (X) can have particularly good moldability.
  • the spiral flow length is more preferably 80 cm or more, and even more preferably 100 cm or more. The details of the method for measuring the spiral flow length will be described in the column of Examples described later.
  • the viscosity of the composition (X) at 25 ° C. is preferably less than 35 Pa ⁇ s. In this case, when molding the composition (X), the coating workability by jet dispense and the discharge stability can be improved.
  • the viscosity of the composition (X) at 25 ° C. is more preferably 25 Pa ⁇ s or less, and even more preferably 20 Pa ⁇ s or less.
  • the lower limit of the viscosity of the composition (X) at 25 ° C. is not particularly limited, but is, for example, 500 mPa ⁇ s or more.
  • the cured product obtained by curing the composition (X) can have high thermal conductivity as described above.
  • the thermal conductivity of the cured product is preferably 2 W / mK or more.
  • the encapsulant 4 produced from the composition (X) can have excellent thermal conductivity and heat dissipation.
  • This thermal conductivity is more preferably 3 W / mK or more, and even more preferably 5 W / mK or more.
  • the thermal conductivity is measured by the xenon flash method. The details of the measurement method will be described in the column of Examples described later.
  • the elastic modulus of the cured product of the composition (X) is unlikely to be excessively high, and therefore the cured product may have a low elastic modulus.
  • the flexural modulus of the cured product according to JIS K6911 is preferably 10 GPa or more and 30 GPa or less. In this case, the processability of the encapsulant 4 produced from the composition (X) tends to be improved, and the encapsulant 4 is less likely to warp.
  • the flexural modulus is more preferably 10 GPa or more and 25 GPa or less, and further preferably 10 GPa or more and 20 GPa or less. The details of the method for measuring the flexural modulus will be described in the column of Examples described later.
  • the sealing material 4 for sealing the electronic component 3 can be produced from the composition (X).
  • the encapsulant 4 and the electronic device 1 including the encapsulant 4 will be described.
  • the electronic device 1 shown in FIG. 1 includes a base material 2, an electronic component 3 flip-chip mounted on the base material 2, and a sealing material 4 for sealing the electronic component 3. There is a gap between the base material 2 and the electronic component 3, and there are a plurality of bumps 5 that electrically connect the base material 2 and the electronic component 3 in this gap.
  • the base material 2 is, for example, a printed wiring board.
  • the configuration of the electronic component 3 is not limited as long as it is flip-chip mounted on the base material 2.
  • the electronic component 3 is, for example, an interposer or a semiconductor element.
  • the semiconductor element may be a bare chip or a semiconductor package.
  • the sealing material 4 covers the entire electronic component 3 and is filled in the gap between the electronic component 3 and the base material 2.
  • the encapsulant 4 is produced, for example, by mounting the electronic component 3 on the base material 2 and then molding the composition (X) by a mold molding method such as a trussfa molding method.
  • the composition (X) can have good fluidity, so that the composition (X) is between the electronic component 3 and the base material 2.
  • the composition (X) is likely to be sufficiently filled in the gap when flowing through the gap.
  • the gap between the adjacent bumps 5 in the gap between the electronic component 3 and the base material 2 also tends to flow. Therefore, the sealing material 4 is less likely to be unfilled.
  • the sealing material 4 can have good thermal conductivity and heat dissipation, the workability of the sealing material 4 is good, and the sealing material 4 is less likely to warp.
  • the electronic device 1 shown in FIG. 2 has a base material 2, an electronic component 3 mounted on the base material 2 with a flip chip, and a sealing material 4 for sealing the electronic component 3. Be prepared. There is a gap between the base material 2 and the electronic component 3, and there are a plurality of bumps 5 that electrically connect the base material 2 and the electronic component 3 in this gap.
  • the sealing material 4 is filled in the gap between the electronic component 3 and the base material 2. That is, the sealing material 4 is an underfill.
  • the sealing material 4 is manufactured by, for example, the capillary flow method after mounting the electronic component 3 on the base material 2. That is, the encapsulant 4 can be produced by injecting the liquid composition (X) into the gap between the base material 2 and the electronic component 3 and then curing the composition (X). Even when the sealing material 4 is produced in this way, the composition (X) can have good fluidity in the present embodiment, so that the composition (X) is placed between the electronic component 3 and the base material 2. When flowing through the gap, the composition (X) is likely to be sufficiently filled in the gap.
  • the gap between the adjacent bumps 5 in the gap between the electronic component 3 and the base material 2 also tends to flow. Therefore, the sealing material 4 is less likely to be unfilled. Further, the sealing material 4 can have good thermal conductivity and heat dissipation, the workability of the sealing material 4 is good, and the sealing material 4 is less likely to warp.
  • the mode of the sealing material 4 is not limited to the above. Further, for example, when the encapsulant 4 shown in FIG. 2 is produced, the encapsulant 4 may be produced by a method other than the capillary flow method.
  • the sealing material 4 can be produced by the NCF (Non Conductive Film) method.
  • NCF Non Conductive Film
  • a film material (NCF) is produced by molding the composition (X) into a sheet and then semi-curing it.
  • the electronic component 3 is superposed on the base material 2 via the film material, and by heating in this state, the film material is melted and then cured to produce the sealing material 4, and the electronic component 3 is bumped 5. It is electrically connected to the base material 2 via. Even in this case, good fluidity can be exhibited when the film material is melted, so that the sealing material 4 is less likely to be unfilled.
  • the composition (X) may be used for producing a molded product or the like other than the sealing material 4.
  • electrically insulating parts or parts of various electronic devices can be made from the composition (X).
  • the composition (X) can have good fluidity, so that the moldability is good, the thermal conductivity of the molded product can be easily increased, and the molded product can be produced. The elastic modulus is unlikely to become excessively high.
  • -Spherical alumina manufactured by Denka Corporation. Part number DAW-0525. Median diameter 5 ⁇ m. -Spherical alumina (0.3 ⁇ m): Made by Admatex Co., Ltd. Product number AO-502. Median diameter 0.3 ⁇ m. -Polyhedral shape ⁇ -alumina (5 ⁇ m): manufactured by Sumitomo Chemical Co., Ltd. Part number AA-5. Median diameter 5 ⁇ m. Pregelatinization rate 100%. -Polyhedral shape ⁇ -alumina (1.5 ⁇ m): manufactured by Sumitomo Chemical Co., Ltd. Part number AA-1.5. Median diameter 1.5 ⁇ m. Pregelatinization rate 100%.
  • -Polyhedral shape ⁇ -alumina (0.3 ⁇ m): manufactured by Sumitomo Chemical Co., Ltd. Part number AA-03F. Median diameter 0.3 ⁇ m. Pregelatinization rate 100%.
  • -Spherical Boron Nitride (0.5 ⁇ m): Hexagonal Spherical Boron Nitride. Median diameter 0.5 ⁇ m. Circularity 0.9.
  • Product number SP-3 Median diameter 6 ⁇ m.
  • -Silane coupling agent N-phenyl-3-aminopropyltrimethoxysilane. Made by Shin-Etsu Chemical Co., Ltd. Part number KBM-573.
  • -Epoxy resin A Biphenyl type epoxy resin. Made by Mitsubishi Chemical Corporation. Product number YX4000H.
  • -Epoxy resin B A stilbene type epoxy resin corresponding to the above epoxy resin (a12). Made by Nippon Kayaku Co., Ltd. Part number TCX-8. Epoxy equivalent 225 g / eq.
  • -Epoxy resin C A modified epoxy resin synthesized by reacting a mixture of hydroquinone and 4,4'-dihydroxybiphenyl with epichlorohydrin.
  • Epoxy equivalent 140 g / eq. -Hardener Phenol novolac resin. Made by Meiwa Kasei Kogyo Co., Ltd. Product number DL-92. OH equivalent 105 g / eq. -Release agent: Carnauba wax. Made by Dainichi Chemical Industry Co., Ltd. Part number F1-100.
  • -Curing accelerator Phosphorus-based curing accelerator. Made by Panasonic Corporation. Part number KXM-J.
  • Tetraphenylphosphonium / tetraphenylborate (product number TPP-K manufactured by Hokuko Chemical Industry Co., Ltd.) and low-viscosity phenol novolac resin (product number H-4 manufactured by Meiwa Kasei Kogyo Co., Ltd.) are mixed in a nitrogen atmosphere at 170 to 180 ° C.
  • -Pigment Carbon black. Made by Mitsubishi Chemical Corporation. # 40.
  • the thermal diffusivity (unit: cm 2 / s) in the thickness direction of this sample at 25 ° C. was measured using a xenon flash method thermal diffusivity measuring device (manufactured by NETZSCH, model number NanoFlash LFA447).
  • the density of the test piece (unit: g / cm 3 ) is measured by the Archimedes method, and the specific heat (unit: J / (g ⁇ K)) of the test piece is measured by the method using a differential scanning calorimeter (DSC method). bottom. From these results, the thermal conductivity (unit: W / mK) in the thickness direction of the sample was calculated by the following formula.
  • (Thermal conductivity) (Density) x (Thermal diffusivity) x (Specific heat)
  • the composition is molded by a transfer molding method under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 180 seconds, and then heated at 175 ° C. for 6 hours.
  • a test piece having a size of 10 mm ⁇ 80 mm ⁇ 3 mm was produced.
  • This test piece was subjected to a three-point bending test using a universal tensile compression tester at room temperature (25 ° C.), and the flexural modulus was measured.
  • the measurement conditions were a test speed of 2 mm / min and a distance between fulcrums: 48 mm.
  • test piece was prepared by the same method as in the case of "(2) Flexural modulus" above. Using a thermomechanical analyzer (manufactured by TA Instruments), the temperature of the test piece was raised from 40 ° C to 280 ° C at 5 ° C per minute, and the average linear expansion coefficient of this test piece in the thickness direction from 50 ° C to 80 ° C. was measured.
  • Spiral flow length A mold for spiral flow manufactured based on ASRM D 3123 using a transfer molding machine (manufactured by Shinto Metal Industry Co., Ltd.) with a mold temperature of 175 ° C. and an injection pressure of 6.9 MPa. The composition was injected under the condition of a curing time of 180 seconds, and the length of flow of the composition was measured.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La présente invention concerne une composition de résine pour moulage, ladite composition de résine augmentant facilement la conductivité thermique d'un produit durci associé et éliminant la dilatation thermique, tout en évitant que le produit durci présente un module d'élasticité extrêmement élevé, et ladite composition de résine étant insensible à la détérioration de l'aptitude au moulage. Cette composition de résine pour moulage contient une résine durcissable de réaction (A) et une charge minérale (B). La charge minérale (B) contient du nitrure de bore sphérique (b1). La charge minérale (B) ne contient pas de nitrure de bore sous forme de paillettes (b2), ou en variante, la charge minérale (B) contient du nitrure de bore lamellaire (b2) et le rapport du nitrure de bore sous forme de paillettes (b2) dans la charge minérale (B) relativement à la composition de résine pour moulage est supérieur à 0 % en masse, mais inférieur à 3 % en masse.
PCT/JP2021/009335 2020-03-27 2021-03-09 Composition de résine pour moulage et dispositif électronique WO2021193028A1 (fr)

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Cited By (2)

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CN113912914A (zh) * 2021-12-07 2022-01-11 北京石墨烯技术研究院有限公司 聚合物基复合导热材料及其制备方法和应用
CN115403743A (zh) * 2022-09-27 2022-11-29 重庆大学 一种高导热球形氮化硼复合环氧树脂的固化方法

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JP2014208818A (ja) * 2013-03-28 2014-11-06 三菱化学株式会社 積層型半導体装置の層間充填材用の組成物、積層型半導体装置、および積層型半導体装置の製造方法
WO2015122379A1 (fr) * 2014-02-12 2015-08-20 電気化学工業株式会社 Particules sphériques de nitrure de bore et leur procédé de production
WO2018163367A1 (fr) * 2017-03-09 2018-09-13 日立化成株式会社 Polymère époxy, résine époxy, composition de résine époxy, feuille de résine, feuille de stade b, produit durci, feuille de stade c, feuille métallique comprenant de la résine, substrat métallique et procédé pour la fabrication de résine époxy

Patent Citations (3)

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JP2014208818A (ja) * 2013-03-28 2014-11-06 三菱化学株式会社 積層型半導体装置の層間充填材用の組成物、積層型半導体装置、および積層型半導体装置の製造方法
WO2015122379A1 (fr) * 2014-02-12 2015-08-20 電気化学工業株式会社 Particules sphériques de nitrure de bore et leur procédé de production
WO2018163367A1 (fr) * 2017-03-09 2018-09-13 日立化成株式会社 Polymère époxy, résine époxy, composition de résine époxy, feuille de résine, feuille de stade b, produit durci, feuille de stade c, feuille métallique comprenant de la résine, substrat métallique et procédé pour la fabrication de résine époxy

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912914A (zh) * 2021-12-07 2022-01-11 北京石墨烯技术研究院有限公司 聚合物基复合导热材料及其制备方法和应用
CN113912914B (zh) * 2021-12-07 2022-02-18 北京石墨烯技术研究院有限公司 聚合物基复合导热材料及其制备方法和应用
CN115403743A (zh) * 2022-09-27 2022-11-29 重庆大学 一种高导热球形氮化硼复合环氧树脂的固化方法

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