WO2026023033A1 - Composition durcissable et dispositif à composants électroniques - Google Patents

Composition durcissable et dispositif à composants électroniques

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Publication number
WO2026023033A1
WO2026023033A1 PCT/JP2024/026686 JP2024026686W WO2026023033A1 WO 2026023033 A1 WO2026023033 A1 WO 2026023033A1 JP 2024026686 W JP2024026686 W JP 2024026686W WO 2026023033 A1 WO2026023033 A1 WO 2026023033A1
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WIPO (PCT)
Prior art keywords
curable composition
biomass
derived
mass
resins
Prior art date
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Pending
Application number
PCT/JP2024/026686
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English (en)
Japanese (ja)
Inventor
立欣 陳
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Resonac Corp
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Resonac Corp
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Publication date
Application filed by Resonac Corp filed Critical Resonac Corp
Priority to PCT/JP2024/026686 priority Critical patent/WO2026023033A1/fr
Publication of WO2026023033A1 publication Critical patent/WO2026023033A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • This disclosure relates to a curable composition and an electronic component device.
  • curable compositions containing epoxy resins are widely used.
  • curable compositions containing epoxy resins offer an excellent balance of properties, including electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert parts.
  • Underfill materials are widely used as sealing materials in electronic component devices with bare chips mounted thereon, such as chip on board (COB), chip on glass (COG), and tape carrier package (TCP). Furthermore, in electronic component devices (flip chips) in which electronic components such as semiconductor elements are directly bump-connected to a wiring board made of ceramic, glass epoxy resin, glass imide resin, polyimide film, etc., epoxy resin compositions are used as underfill materials to fill the gaps between the bump-connected electronic components and the wiring board. Underfill materials play an important role in protecting electronic components from temperature, humidity, and external mechanical forces.
  • an encapsulating epoxy resin composition containing (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) rubber particles, and (D) an inorganic filler, as well as an electronic component device with an element encapsulated with this encapsulating epoxy resin composition have been disclosed (see, for example, Patent Document 1).
  • the present disclosure aims to provide a curable composition containing a biomass-derived material and an electronic component device containing the cured product.
  • ⁇ 6> The curable composition according to ⁇ 5>, wherein the content of the inorganic filler is 60% by volume to 90% by volume based on the total amount of the curable composition.
  • ⁇ 7> The curable composition according to any one of ⁇ 1> to ⁇ 6>, which is used for sealing electronic components.
  • An electronic component device comprising: a support member; an electronic component placed on the support member; and a cured product of the curable composition according to ⁇ 7> that seals the electronic component.
  • the present disclosure provides a curable composition containing a biomass-derived material and an electronic component device containing the cured product.
  • FIG. 1A is a schematic plan view showing the electrode structure on one surface of a test piece used in measuring the volume resistivity according to this example
  • FIG. 1B is a schematic plan view showing the electrode structure on the other surface of the test piece used in measuring the volume resistivity according to this example.
  • the term "process” includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.
  • numerical ranges indicated using “to” include the numerical values before and after “to” as the minimum and maximum values, respectively.
  • the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
  • each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
  • the particles corresponding to each component may contain multiple types of particles.
  • the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
  • the curable composition of the present disclosure includes a biomass-derived curable component.
  • the curable composition of the present disclosure includes a biomass-derived material, which can contribute to carbon neutrality.
  • the curable compositions of the present disclosure include biomass-derived curable components.
  • biomass-derived curable components include epoxy resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, vinyl resins, polyimide resins such as maleimide resins, polyamide resins, polyamideimide resins, silicone resins, and (meth)acrylic resins.
  • the curable composition may contain only one type of biomass-derived curable component, or may contain two or more types.
  • the biomass-derived curable component may include a biomass-derived epoxy resin.
  • biomass-derived epoxy resins include epoxy resins obtained by epoxidizing biomass-derived alcohols, biomass-derived phenols, biomass-derived carboxylic acids, and the like.
  • biomass-derived alcohols include glucose, sorbitol, glycerin, polyglycerin, propanediol, butanediol, and isosorbide.
  • biomass-derived phenols include tannic acid, quercetin, cardanol, and lignin-derived substances.
  • biomass-derived carboxylic acids include carboxylic acids obtained by oxidizing the above-mentioned biomass-derived alcohols.
  • Biomass-derived epoxy resins can be obtained by epoxidizing the alcohols, etc. The method for epoxidizing the alcohols, etc. is not particularly limited, and conventionally known methods can be used.
  • biomass-derived epoxy resins include Denacol from Nagase ChemteX Corporation. Other examples include various materials planned for release on the market by Sakata Inx Corporation, Mitsubishi Chemical Corporation, Mitsui Chemicals, Inc., and others.
  • the biomass-derived epoxy resin preferably contains a biphenyl-type epoxy resin.
  • the biomass degree of the biomass-derived curable component preferably the biomass degree of the biomass-derived epoxy resin, is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. There is no particular upper limit to the biomass degree of the biomass-derived curable component, and it may be 80% or less, 60% or less, or 50% or less.
  • the biomass content (%) refers to a value measured by ASTM (American Standard Test Method) D6866-21, Method B. Specifically, it is as follows. The sample to be measured is chemically converted to carbon dioxide, and the resulting carbon dioxide is further reduced to graphite. This graphite is ionized and passed through an accelerator capable of measuring the ratios of 12 C, 13 C, and 14 C, and the ratio of 14 C is measured. From the measurement results obtained, ( 14 C/ 12 C) x 100 is calculated, and this value is taken as the biomass ratio (%). 14 C refers to plant-derived carbon, and 12 C refers to carbon that is not plant-derived (eg, petroleum-derived carbon).
  • the curable composition of the present disclosure may contain a non-biomass-derived curable component (also referred to as "other curable components") in addition to a biomass-derived curable component.
  • the biomass content of the other curable components may be 5% or less, 1% or less, or even 0%.
  • the ratio of the biomass-derived curable component to the total amount of curable components may be 20% by mass to 100% by mass, 30% by mass to 90% by mass, or 50% by mass to 80% by mass.
  • the ratio of the biomass-derived epoxy resin to the total amount of epoxy resins may be 20% by mass to 100% by mass, 30% by mass to 90% by mass, or 50% by mass to 80% by mass.
  • the ratio of the biomass-derived epoxy resin to the total amount of epoxy resins is 20 mass % or more, the curable composition tends to have excellent temperature cycle resistance and moisture absorption properties.
  • curable components include epoxy resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, urethane resins, vinyl resins, polyimide resins such as maleimide resins, polyamide resins, polyamideimide resins, silicone resins, and (meth)acrylic resins.
  • the curable composition may contain only one type of other curable component, or may contain two or more types.
  • the other curable component may contain an epoxy resin other than the biomass-derived epoxy resin (also referred to as other epoxy resin).
  • other epoxy resins include so-called fossil resource-derived epoxy resins.
  • Specific examples of such epoxy resins include novolac epoxy resins obtained by epoxidizing a novolac resin obtained by condensing or co-condensing, under an acidic catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde; triphenylmethane epoxy resins obtained by epoxidizing a triphenylmethane phenolic resin obtained by condens
  • copolymerized epoxy resins obtained by epoxidizing novolak resins obtained by co-condensing a toluic acid compound with an aldehyde compound under an acidic catalyst; diphenylmethane-type epoxy resins which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins which are diglycidyl ethers of bisphenol S, etc.; epoxy resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthal
  • dicyclopentadiene-type epoxy resins in which a co-condensation resin of dicyclopentadiene and a phenol compound is epoxidized; alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane in which an olefin bond in the molecule is epoxidized; paraxylylene-modified epoxy resins which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins which are glycidyl ethers of metaxylylene-modified phenolic resins; and glycid
  • the epoxy resin examples include terpene-modified epoxy resins which are glycidyl ethers of dicyclopentadiene-modified phenolic resins; dicyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins; cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing
  • the curable composition of the present disclosure may contain a biomass-derived epoxy resin and other epoxy resins, or may contain a biomass-derived biphenyl-type epoxy resin and a biphenyl-type epoxy resin other than a biomass-derived epoxy resin (also referred to as an other biphenyl epoxy resin).
  • the content of the biomass-derived biphenyl-type epoxy resin may be 30% by mass to 100% by mass, 50% by mass to 90% by mass, or 60% by mass to 80% by mass relative to the total amount of biphenyl-type epoxy resins (total of biomass-derived biphenyl-type epoxy resins and other biphenyl epoxy resins).
  • the epoxy equivalent (molecular weight/number of epoxy groups) of the biomass-derived epoxy resin or the epoxy equivalent of other epoxy resins is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq. When two or more epoxy resins are used in combination, it is preferable that the epoxy equivalent weight of the mixture of the two or more epoxy resins is within the above range. In the present disclosure, the epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.
  • the curable composition of the present disclosure contains a biomass-derived epoxy resin
  • the curable composition may contain a curing agent, such as an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, or an active ester compound.
  • the hardener may be a biomass-derived hardener, or a non-biomass-derived hardener.
  • the biomass content of biomass-derived curing agents is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. There is no particular upper limit to the biomass content of biomass-derived curing agents, and it may be 80% or less, 60% or less, or 50% or less.
  • the curing agent examples include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and active ester compounds.
  • the curing agent may be used alone or in combination of two or more.
  • all of the curing agents may be biomass-derived curing agents, or a biomass-derived curing agent may be used in combination with a non-biomass-derived curing agent.
  • Hardeners other than those derived from biomass include those derived from fossil resources.
  • the biomass content of hardeners other than those derived from biomass may be 5% or less, 1% or less, or even 0%.
  • amine-based curing agents include aromatic amine curing agents with one aromatic ring, such as m-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, and 2,4-diaminoanisole; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, Examples include aromatic amine curing agents with two aromatic rings, such as 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 3,3',5,5',5
  • Acid anhydride curing agents include phthalic anhydride, maleic anhydride, methyl himic anhydride, himic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrogenated methylnadic anhydride, and various cyclic acid anhydrides such as trialkyltetrahydrophthalic anhydride with multiple alkyl groups obtained by the Diels-Alder reaction of maleic anhydride and a diene compound, and dodecenyl succinic anhydride.
  • phenol-based curing agents include novolak resins obtained by condensing or co-condensing at least one compound selected from the group consisting of phenol compounds (e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F) and naphthol compounds (e.g., ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene) with an aldehyde compound (e.g., formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde) in the presence of an acid catalyst; phenol-aralkyl resins; biphenyl-aralkyl resins; and naphthol-aralkyl resins.
  • examples of the phenol-based curing agent include the above-mentioned biomass-derived phenols.
  • the type of active ester compound is not particularly limited as long as it has one or more ester groups in the molecule that react with an epoxy group.
  • the active ester compound include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds.
  • Examples of active ester compounds include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds using an aliphatic compound as a polycondensation component tend to have excellent compatibility with epoxy resins due to the presence of an aliphatic chain.
  • Ester compounds using an aromatic compound as a polycondensation component tend to have excellent heat resistance due to the presence of an aromatic ring.
  • Specific examples of active ester compounds include aromatic esters obtained by the condensation reaction of an aromatic carboxylic acid with a phenolic hydroxyl group.
  • aromatic esters having structural units derived from the aromatic carboxylic acid component, structural units derived from the monohydric phenol, and structural units derived from the polyhydric phenol are preferred.
  • the content of the curing agent is not particularly limited, and the ratio of the equivalent number of the functional group of the curing agent (e.g., amino group in the case of an amine-based curing agent, phenolic hydroxyl group in the case of a phenol-based curing agent, acid anhydride group in the case of an acid anhydride-based curing agent, or ester group in the case of an active ester compound) to the equivalent number of the epoxy resin (equivalent number of curing agent/equivalent number of epoxy resin) is preferably set in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and even more preferably in the range of 0.8 to 1.2.
  • the equivalent number of the functional group of the curing agent e.g., amino group in the case of an amine-based curing agent, phenolic hydroxyl group in the case of a phenol-based curing agent, acid anhydride group in the case of an acid anhydride-based curing agent, or ester group in the
  • the curable composition of the present disclosure may further contain an inorganic filler.
  • an inorganic filler there are no particular limitations on the type of inorganic filler. Specific examples include inorganic materials such as silica, such as fused silica and crystalline silica, glass, alumina, aluminum nitride, boron nitride, talc, clay, mica, titanium oxide, calcium titanate, strontium titanate, and barium titanate.
  • Inorganic fillers with flame-retardant properties may also be used. Examples of inorganic fillers with flame-retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides, such as magnesium-zinc composite hydroxide, and zinc borate.
  • inorganic fillers silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. Boron nitride is preferred from the viewpoint of reducing the dielectric loss tangent.
  • silica such as fused silica is preferred from the viewpoint of reducing the linear expansion coefficient
  • alumina is preferred from the viewpoint of high thermal conductivity.
  • Boron nitride is preferred from the viewpoint of reducing the dielectric loss tangent.
  • One type of inorganic filler may be used alone, or two or more types may be used in combination.
  • Inorganic fillers can be in the form of powder, beads made by spheroidizing powder, fibers, etc.
  • the average particle size of the inorganic filler is not particularly limited.
  • the volume average particle size is preferably 0.2 ⁇ m to 50 ⁇ m, and more preferably 0.5 ⁇ m to 30 ⁇ m.
  • the volume average particle diameter is 0.2 ⁇ m or more, an increase in viscosity of the curable composition tends to be further suppressed.
  • the volume average particle diameter is 50 ⁇ m or less, the filling ability into narrow gaps tends to be further improved.
  • the volume average particle diameter of the inorganic filler refers to the value measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution measuring device.
  • the volume-average particle diameter of the inorganic filler in the curable composition or its cured product can be measured by known methods. For example, the inorganic filler is extracted from the curable composition or cured product using an organic solvent, nitric acid, aqua regia, or the like, and then thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume-average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured using a laser diffraction/scattering particle size distribution analyzer.
  • the cured product can be embedded in a transparent epoxy resin or the like, polished, and the resulting cross-section observed using a scanning electron microscope to obtain the volume-based particle size distribution, from which the volume-average particle diameter of the inorganic filler can be measured.
  • the volume-average particle diameter can also be measured by continuously observing two-dimensional cross-sections of the cured product using an FIB device (focused ion beam SEM) or the like, and performing three-dimensional structural analysis.
  • the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably wide.
  • the content of the inorganic filler is not particularly limited and is set appropriately depending on the application of the curable composition.
  • the content of the inorganic filler may be 60% to 90% by volume, or 70% to 85% by volume, relative to the total amount of the curable composition.
  • the curable composition of the present disclosure may contain a release agent from the viewpoint of obtaining good releasability from the mold during molding.
  • the release agent is not particularly limited, and conventionally known ones can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.
  • the release agent may be used alone or in combination of two or more.
  • the release agent may be a biomass-derived release agent or a fossil resource-derived release agent.
  • the content of the release agent is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and even more preferably 7 to 20 parts by mass, per 100 parts by mass of the curable component.
  • the amount of the release agent is 1 part by mass or more per 100 parts by mass of the curable component, sufficient releasability tends to be obtained.
  • the amount is 30 parts by mass or less, better adhesion tends to be obtained.
  • the content of the release agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the epoxy resin and curing agent combined.
  • the amount of the release agent is 0.01 part by mass or more per 100 parts by mass of the epoxy resin and curing agent combined, sufficient release properties tend to be obtained.
  • the amount is 10 parts by mass or less, better adhesion tends to be obtained.
  • the curable composition of the present disclosure may contain a curing accelerator as needed.
  • the type of curing accelerator is not particularly limited and can be selected depending on the type of curable component, the desired properties of the curable composition, etc.
  • the curing accelerator may be a biomass-derived curing accelerator or a fossil resource-derived curing accelerator.
  • curing accelerator examples include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and the combination of these compounds with maleic anhydride, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3
  • Examples of the compound include compounds having intramolecular polarization obtained through a dehydrohalogenation step; tetra-substituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted phosphonium with phenol compounds; salts of tetraalkylphosphonium with partial hydrolysates of aromatic carboxylic acid anhydrides; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds.
  • the curing accelerators may be used alone or in combination of two or more.
  • the curing accelerator is preferably a curing accelerator containing an organic phosphine, such as the organic phosphines, phosphine compounds such as complexes of the organic phosphines and organic borons, and compounds having intramolecular polarization formed by adding a compound having a ⁇ bond to the organic phosphines or the phosphine compounds.
  • an organic phosphine such as the organic phosphines, phosphine compounds such as complexes of the organic phosphines and organic borons, and compounds having intramolecular polarization formed by adding a compound having a ⁇ bond to the organic phosphines or the phosphine compounds.
  • particularly suitable curing accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound.
  • the amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the curable components (or the total of the epoxy resin and curing agent).
  • the amount of curing accelerator is 0.1 part by mass or more per 100 parts by mass of the curable components (or the total of the epoxy resin and curing agent)
  • good curing tends to occur in a short period of time.
  • the amount of curing accelerator is 30 parts by mass or less per 100 parts by mass of the curable components (or the total of the epoxy resin and curing agent), the curing speed is not too fast, and good molded products tend to be obtained.
  • the curable composition of the present disclosure may contain a stress relief agent.
  • a stress relief agent By including a stress relief agent, warpage of the package and the occurrence of package cracks can be further reduced.
  • stress relief agents include commonly used known stress relief agents (flexibilizers).
  • thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based elastomers; indene-styrene-coumarone copolymers; organic phosphorus compounds such as triphenylphosphine oxide and phosphate esters; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer.
  • MBS methyl methacrylate-styrene-butadiene copolymer
  • MBS methyl methacrylate-silicone cop
  • the stress relief agent may be derived from biomass or fossil resources.
  • the stress relaxation agents may be used alone or in combination of two or more.
  • silicone-based stress relaxation agents include those having an epoxy group, those having an amino group, and polyether-modified versions of these, with silicone compounds such as epoxy-group-containing silicone compounds and polyether-based silicone compounds being more preferred.
  • the stress relaxation agent contain at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide.
  • the amount thereof is, for example, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the curable component (or the total of the epoxy resin and the curing agent).
  • the stress relaxation agent contains at least one of an indene-styrene-coumarone copolymer and triphenylphosphine oxide
  • the amount thereof is, for example, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the curable component (or the total of the epoxy resin and the curing agent).
  • the content of the silicone-based stress relaxation agent is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less, and extremely preferably 0.5% by mass or less, relative to the entire curable composition.
  • the content of the silicone-based stress relaxation agent may be 0% by mass or 0.1% by mass.
  • the curable composition of the present disclosure may contain various additives such as a coupling agent, an ion trapping agent, a flame retardant, a colorant, and an ultraviolet absorber, as exemplified below.
  • the curable composition of the present disclosure may also contain various additives known in the technical field as needed, in addition to the additives exemplified below.
  • the curable composition of the present disclosure may contain a coupling agent.
  • the curable composition preferably contains a coupling agent.
  • the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and disilazane, titanium-based compounds, aluminum chelate-based compounds, and aluminum/zirconium-based compounds.
  • the amount of coupling agent is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2.5 parts by mass, per 100 parts by mass of the inorganic filler.
  • the amount of coupling agent is 0.05 parts by mass or more per 100 parts by mass of the inorganic filler, adhesiveness tends to be further improved.
  • the amount of coupling agent is 5 parts by mass or less per 100 parts by mass of the inorganic filler, moldability of the package tends to be further improved.
  • the curable composition of the present disclosure may contain an ion trapping agent.
  • an ion trapping agent When the curable composition is used to seal electronic components, it is preferable that the curable composition contain an ion trapping agent from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including the sealed electronic components.
  • the ion trapping agent is not particularly limited, and conventionally known ion trapping agents can be used. Specific examples include hydrotalcite compounds and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth.
  • the ion trapping agents may be used alone or in combination of two or more. Among these, hydrotalcites represented by the following general formula (A) are preferred.
  • the curable composition contains an ion trapping agent
  • the content of the ion trapping agent is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 1 part by mass, per 100 parts by mass of the curable component (or the total of the epoxy resin and curing agent).
  • the curable composition of the present disclosure may contain a flame retardant.
  • the flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.
  • the amount is not particularly limited as long as it is sufficient to achieve the desired flame retardant effect.
  • the amount of flame retardant is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the curable component (or the total of the epoxy resin and curing agent).
  • the curable composition of the present disclosure may contain a colorant.
  • the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide.
  • the content of the colorant can be appropriately selected depending on the purpose, etc.
  • the colorant may be used alone or in combination of two or more.
  • the curable composition of the present disclosure may contain an organic solvent from the viewpoint of reducing viscosity.
  • an organic solvent from the viewpoint of reducing viscosity.
  • the organic solvent is not particularly limited, and examples thereof include alcohol-based solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ketone-based solvents such as acetone and methyl ethyl ketone; glycol ether-based solvents such as ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate; lactone-based solvents such as ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone; amide-based solvents such as dimethylacetamide and dimethylformamide; and aromatic solvents such as toluene and xylene.
  • alcohol-based solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl
  • the organic solvent may be a biomass-derived organic solvent or a fossil resource-derived organic solvent.
  • organic solvents having a boiling point of 170° C. or higher are preferred from the viewpoint of avoiding the formation of bubbles due to sudden evaporation when the curable composition, which is liquid at 25° C., is cured.
  • the content of volatile components including organic solvents and the like is not particularly limited as long as it is to an extent that bubbles are not formed when the liquid curable composition is cured, and is preferably 5 mass % or less, more preferably 1 mass % or less, and even more preferably 0.1 mass % or less, based on the total amount of the liquid curable composition.
  • the volatile content of the curable composition is calculated by heating the curable composition at 180°C for 30 minutes, based on the difference in weight before and after heating.
  • the method for preparing the curable composition is not particularly limited.
  • a common method includes thoroughly mixing predetermined amounts of components using a mixer or the like, melt-kneading the mixture using a mixing roll, extruder, etc., cooling the mixture, and pulverizing it. More specifically, a method includes stirring and mixing predetermined amounts of the components described above, kneading the mixture using a kneader, roll, extruder, etc. that has been preheated to 70° C. to 140° C., cooling the mixture, and pulverizing it.
  • the curable composition When the curable composition is liquid at 25° C., it can be obtained, for example, by stirring, melting, mixing, dispersing, etc., predetermined amounts of components together or separately, while optionally applying heat treatment.
  • the device for mixing, stirring, dispersing, etc., of the components is not particularly limited, and examples thereof include a Raikai mill equipped with a stirrer, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc.
  • the curable composition is not particularly limited.
  • the curable composition may be used for sealing electronic components, for producing adhesive films such as dicing films and die bonding films, or for producing laminates such as copper-clad laminates.
  • the electronic component device of the present disclosure includes a support member, an electronic component placed on the support member, and a cured product of the curable composition that seals the electronic component.
  • electronic component devices include those (e.g., high-frequency devices) in which electronic components (active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, antennas, etc.) are mounted on a support member such as a lead frame, a pre-wired tape carrier, a wiring board, glass, a silicon wafer, or an organic substrate, and the resulting electronic component region is sealed with a curable composition.
  • active elements such as semiconductor chips, transistors, diodes, and thyristors, passive elements such as capacitors, resistors, and coils, antennas, etc.
  • other electronic components may be arranged on the surface of the support member opposite to the surface on which the above-mentioned electronic components are arranged, as necessary.
  • the other electronic components may be encapsulated with the above-mentioned curable composition, or with another resin composition, or may not be encapsulated at all.
  • the method for manufacturing an electronic component device includes the steps of placing an electronic component on a support member and encapsulating the electronic component with the curable composition described above.
  • the method for carrying out each of the above steps is not particularly limited and can be carried out by a general method.
  • the types of support members and electronic components used in manufacturing the electronic component device are not particularly limited and support members and electronic components commonly used in manufacturing electronic component devices can be used.
  • Methods for encapsulating electronic components using a curable composition that is solid at 25° C. include low-pressure transfer molding, injection molding, compression molding, etc. Among these, low-pressure transfer molding is the most common.
  • a curable composition that is liquid at 25°C is used, a post-injection method may be used in which, after the electronic component and the support member are connected, the curable composition penetrates into the gap between the electronic component and the support member by utilizing capillary action, or a pre-application method may be used in which the curable composition is first applied to the support member, and then, when the electronic component is connected to the support member by thermocompression bonding, the connection of the electronic component and the support member and the curing reaction of the curable composition are carried out all at once.
  • Epoxy resin 1 biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g/eq, biomass content 0%
  • Epoxy resin 2 biphenyl type epoxy resin, epoxy equivalent 192 g/eq, biomass content 0%
  • Epoxy resin 3 biphenyl type epoxy resin, epoxy equivalent 192 g/eq, biomass content 27%
  • Curing agent 1 phenol aralkyl type phenol resin, hydroxyl group equivalent 156 g/eq
  • Curing agent 2 melamine-modified phenolic resin, reactive group equivalent 120 g/eq
  • Curing agent 3 Polyaralkylphenol resin, reactive group equivalent 175 g/eq
  • Curing accelerator triphenylphosphine/1,4-benzoquinone adduct
  • Coupling agent 1 N-phenyl-3-aminopropyltrimethoxysilane
  • Coupling agent 2 3-glycidoxypropyltrimethoxysilane
  • Coupling agent 3 tetrasulfideditriethoxysilane
  • Wax Montan acid ester wax
  • Colorant carbon black
  • Ion trapping agent compound represented by the above general formula (A); Stress relaxation agent 1: indene-styrene-coumarone copolymer; Stress relaxation agent 2: triarylphosphine oxide; UV absorber: triazine-based UV absorber
  • Inorganic filler 1 silica particles, volume average particle size: 19.9 ⁇ m
  • Inorganic filler 2 silica particles, volume average particle size: 12 nm
  • the volume average particle size of each of the inorganic fillers is a value obtained by the following measurement. Specifically, first, the inorganic filler was added to a dispersion medium (water) in a range of 0.01% by mass to 0.1% by mass, and the mixture was dispersed in a bath-type ultrasonic cleaner for 5 minutes. 5 ml of the resulting dispersion was poured into a cell, and the particle size distribution was measured at 25° C. using a laser diffraction/scattering particle size distribution measuring device (LA920, manufactured by Horiba Ltd.). The particle size at an integrated value of 50% (volume basis) in the obtained particle size distribution was defined as the volume average particle size.
  • a dispersion medium water
  • LA920 laser diffraction/scattering particle size distribution measuring device
  • the biomass content listed in Table 1 is the biomass content relative to the total amount of the curable composition.
  • melt Viscosity The curable composition was heated to melt, and the melt viscosity ( ⁇ FT, unit: Poise) at 175° C. was measured using a Koka type flow tester with a test force of 10 kgf.
  • the gel time of the curable composition was measured using a Curastometer manufactured by JSR Trading Co., Ltd. Measurement was performed at 180°C using 3 g of the curable composition using a Curastometer manufactured by JSR Trading Co., Ltd., and the time until the torque curve rose was defined as the gel time (seconds).
  • the curable composition was molded in a transfer molding machine under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds to prepare disc-shaped test specimens measuring ⁇ 50 ⁇ 3 mm. Post-curing was performed at 175°C for 5 hours. The test specimens were then subjected to a pressure cooker test (2 atmospheres (0.2 MPa) / 121°C / 100% RH) for 20 hours, after which the water absorption (%) of the test specimens was determined.
  • Mold shrinkage rate ((D-d)/D) x 100
  • the curable composition was molded using a transfer molding machine under conditions of a molding temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds to obtain a plate-shaped molded product (length 127 mm, width 12.7 mm, thickness 6.4 mm).
  • the molded product was post-cured at 175°C for 5 hours to obtain a plate-shaped cured product.
  • the spiral flow was measured by using a spiral flow measurement mold conforming to EMMI-1-66, and determining the flow distance (cm) when the curable composition was molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds.
  • the test piece 10 with the electrode formed thereon was placed in an environment of 25°C, 100°C, or 150°C, and the value of the volume resistivity meter was read 1 minute after application of a voltage of 500 V.
  • volume resistivity after moisture absorption The same test specimen as that used in the above-mentioned measurement of volume resistivity was used, and this test specimen was treated for 20 hours under pressure cooker test conditions (2 atmospheres (0.2 MPa) / 121°C / 100% RH). After the treatment, water droplets were wiped off the surface of the test specimen, and the specimen was placed in an environment of 25°C. A voltage of 500 V was applied and the value of the volume resistivity meter was read 1 minute later. The volume resistivity after moisture absorption was calculated using the above formula (1).
  • an SOP-8L type package with external dimensions of 3.9 mm length, 4.9 mm width, and 1.5 mm thickness and equipped with a silicon chip (1.5 mm length, 2.6 mm width, 0.37 mm thickness) was produced in a transfer molding machine under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds.
  • Test samples were prepared using four types of packages, namely, A) (1) and (2) and B) (1) and (2). Post-curing was carried out at 175°C for 5 hours.
  • the prepared samples were subjected to a 1000-hour temperature cycle test, with one cycle consisting of holding at -55°C for 5 minutes, holding at 150°C for 5 minutes, and holding at 55°C for 5 minutes. After 100 hours (h), 250 hours, 500 hours, 750 hours, and 1000 hours, the presence or absence of cracks was observed using an ultrasonic microscope (device name: Nordson Sonoscan). The results are shown in Table 3.
  • an SOP-8L type package with external dimensions of 3.9 mm length, 4.9 mm width, and 1.5 mm thickness and equipped with a silicon chip (1.5 mm length, 2.6 mm width, 0.37 mm thickness) was produced in a transfer molding machine under conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 150 seconds.
  • Test samples were prepared using four types of packages, namely, A) (1) and (2) and B) (1) and (2). Post-curing was carried out at 175°C for 5 hours.
  • the prepared samples were heat-treated in a heating furnace at 125°C for 24 hours, then left at 60°C and 60% RH for 40 hours or at 85°C and 60% RH for 168 hours, and then heated three times in a reflow furnace at a furnace temperature of 260°C for a heating time of 15 minutes, and the presence or absence of cracks was observed using an ultrasonic microscope (device name: Nordson Sonoscan). The results are shown in Table 4.
  • B/A indicates the number of packages tested, and B indicates the number of packages in which cracks were observed. The smaller the B value, the better the temperature cycle characteristics. "-" in the tables indicates no data available.
  • Examples 1 and 2 tended to have fewer packages in which cracks were observed in the temperature cycle test and moisture absorption test than Comparative Example 1. Therefore, Examples 1 and 2 had better cycle characteristics and moisture absorption properties than Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

[Problème] Fournir une composition durcissable contenant un matériau dérivé d'une biomasse. [Solution] Une composition durcissable contenant un constituant durcissable dérivé d'une biomasse.
PCT/JP2024/026686 2024-07-25 2024-07-25 Composition durcissable et dispositif à composants électroniques Pending WO2026023033A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008195843A (ja) * 2007-02-14 2008-08-28 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物
JP2010150298A (ja) * 2008-12-23 2010-07-08 Hitachi Ltd バイオマス由来エポキシ化合物及びその製造方法
KR102197405B1 (ko) * 2019-12-05 2020-12-31 주식회사 제일화성 친환경 바이오매스 기반의 아이소소바이드 에폭시 원료를 이용한 고체상 에폭시 수지의 제조 방법
WO2023162975A1 (fr) * 2022-02-28 2023-08-31 住友ベークライト株式会社 Composition de résine d'étanchéité et dispositif à semi-conducteur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008195843A (ja) * 2007-02-14 2008-08-28 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物
JP2010150298A (ja) * 2008-12-23 2010-07-08 Hitachi Ltd バイオマス由来エポキシ化合物及びその製造方法
KR102197405B1 (ko) * 2019-12-05 2020-12-31 주식회사 제일화성 친환경 바이오매스 기반의 아이소소바이드 에폭시 원료를 이용한 고체상 에폭시 수지의 제조 방법
WO2023162975A1 (fr) * 2022-02-28 2023-08-31 住友ベークライト株式会社 Composition de résine d'étanchéité et dispositif à semi-conducteur

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