WO2022102489A1 - 樹脂組成物、硬化物、半導体封止材、及び、半導体装置 - Google Patents

樹脂組成物、硬化物、半導体封止材、及び、半導体装置 Download PDF

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WO2022102489A1
WO2022102489A1 PCT/JP2021/040509 JP2021040509W WO2022102489A1 WO 2022102489 A1 WO2022102489 A1 WO 2022102489A1 JP 2021040509 W JP2021040509 W JP 2021040509W WO 2022102489 A1 WO2022102489 A1 WO 2022102489A1
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resin
resin composition
phenol
epoxy resin
compound
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PCT/JP2021/040509
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English (en)
French (fr)
Japanese (ja)
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和久 矢本
和賢 青山
源祐 秋元
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Dic株式会社
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Priority to JP2022544339A priority Critical patent/JP7205673B2/ja
Publication of WO2022102489A1 publication Critical patent/WO2022102489A1/ja

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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
    • C08G59/40—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 curing agents used
    • C08G59/62—Alcohols or 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
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a resin composition, a cured product, a semiconductor encapsulant, and a semiconductor device.
  • Epoxy resins and epoxy resin compositions containing the curing agent as essential components are excellent in various physical properties such as high heat resistance and moisture resistance, and thus are in the field of electronic parts and electronic parts such as semiconductor encapsulants and printed circuit boards.
  • Conductive adhesives such as conductive pastes, other adhesives, matrices for composite materials, paints, photoresist materials, color-developing materials and the like.
  • wafer level packaging technology is one of the mounting technologies that meet these demands.
  • the above-mentioned wafer level packaging technology is a mounting technology for manufacturing a semiconductor package by performing resin encapsulation, rewiring, and electrode formation in the wafer state and disassembling them by dicing. Since the encapsulation resin is used for batch encapsulation, warpage and cracks are likely to occur due to the shrinkage during resin curing and the difference in shrinkage amount due to the linear expansion coefficient of the chip and the linear expansion coefficient of the encapsulating resin. Since the warp and cracks significantly reduce the reliability of the package, it is strongly required to increase the toughness of the sealing resin composition for the purpose of suppressing the warp and to lower the elastic modulus for the purpose of suppressing the cracks. ..
  • Patent Documents As conventionally known resin compositions for encapsulating semiconductors, for example, those using a polyfunctional epoxy compound having a triazine skeleton and a phenol resin having a dicyclopentadiene skeleton are disclosed (for example, Patent Documents). See 1.).
  • Patent Document 1 Although the resin composition for semiconductor encapsulation described in Patent Document 1 has a feature of being excellent in tracking resistance, it does not have the performance such as high toughness and low elasticity in a cured product which is required in recent years. There wasn't.
  • the problem to be solved by the present invention is a resin composition that can contribute to obtaining a cured product having a low elastic modulus and excellent toughness, a cured product obtained by using the resin composition, and the resin composition. It is an object of the present invention to provide a semiconductor device containing a semiconductor encapsulant contained therein and a cured product obtained by using the semiconductor encapsulant.
  • the present inventors have obtained a low cured product by using a phenol novolac resin having a specific structure and a resin composition containing a phenol resin. It has been found that it can exhibit high toughness and elasticity, and can be particularly suitably used for semiconductor encapsulant applications, and has completed the present invention.
  • the present invention relates to a resin composition
  • a resin composition comprising a paratertiary butylphenol novolak resin (A) and a phenol resin (B) having a dicyclopentadiene skeleton.
  • the content ratio of the dikaryon component in the paratertiary butylphenol novolak resin (A) is preferably 30% or more in terms of the area ratio calculated from the GPC chart.
  • the phenol resin (B) having the dicyclopentadiene skeleton contains the compound (b1) represented by the following general formula (1) in an area ratio of 30% or more calculated from the GPC chart. It is preferable to contain it.
  • R 1 is independently represented by a halogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0, 1, or 2.
  • the blending ratio (A) / (B) shown by the mass ratio of the paratertiary butylphenol novolak resin (A) and the phenol resin (B) having a dicyclopentadiene skeleton is It is preferably 15/85 to 85/15.
  • the resin composition of the present invention can contain an epoxy resin.
  • the resin composition of the present invention can contain an inorganic filler.
  • the present invention relates to a cured product obtained by curing the resin composition.
  • the present invention relates to a semiconductor encapsulant comprising the resin composition.
  • the present invention relates to a semiconductor device characterized by containing a cured product of the semiconductor encapsulant.
  • a cured product obtained by using a phenol novolak resin having a specific structure capable of contributing to high toughness and having a low elastic modulus and a resin composition containing the phenol resin has low elastic modulus.
  • Phenol excellent toughness and useful. In particular, it can be suitably used for semiconductor encapsulant applications.
  • 6 is a GPC chart of the paratertiary butylphenol novolak resin (A-1) obtained in Synthesis Example 1.
  • 6 is a GPC chart of the phenol resin (B-1) having a dicyclopentadiene skeleton obtained in Synthesis Example 2.
  • the present invention relates to a paratertiary butylphenol novolak resin (A) (hereinafter, may be simply referred to as “resin (A)”) and a phenol resin (B) having a dicyclopentadiene skeleton (hereinafter, simply “resin”). (B) ”).
  • resin (A) paratertiary butylphenol novolak resin
  • B phenol resin having a dicyclopentadiene skeleton
  • the resin composition can exhibit a low elastic modulus and high toughness in the obtained cured product, and in particular, It is suitable for semiconductor encapsulant applications and is useful.
  • the paratershary butylphenol novolak resin (A) is specifically a novolak-type resin in which paratertiary butylphenol is used as a raw material for a phenol compound and the reaction material is a reaction material thereof. Since the resin (A) obtained by using the paratertiary butylphenol has a bulky structure, the heat shrinkage rate is suppressed to a low level, and when it is made into a cured product, it is less likely to warp or crack, and it is a raw material. Is preferable because it is easily available.
  • the resin (A) uses paratertiary butylphenol as a raw material for the phenol compound, but other phenolic compounds may be used in combination as necessary.
  • the other phenol compounds include phenol, cresol, xylenol, and naphthol.
  • the mass ratio of the paratertiary butyl phenol in the raw material of the phenol compound constituting the resin (A) is preferably 90% by mass or more, more preferably 95% by mass or more. Further, it is particularly preferable that the total amount of the phenol compound raw material is paratertiary butylphenol.
  • the aldehyde compound may be any compound that can form a phenol novolac resin by condensation reaction with paratertiary butylphenol.
  • Formaldehyde may be used as formalin in an aqueous solution state or as paraformaldehyde in a solid state.
  • the paratertiary butylphenol novolak resin (A) preferably contains a dikaryon component.
  • the dinuclear component is, for example, a compound represented by the following general formula (2), that is, two molecules of the phenol compound raw material of the resin (A) via a structural site derived from the aldehyde compound. A bound compound.
  • the content ratio of the dikaryon component in the paratertiary butylphenol novolak resin (A) is preferably 30% or more, more preferably 30% or more in terms of the area ratio calculated from the gel permeation chromatography (GPC) chart. It is 50 to 99%, more preferably 60 to 95%.
  • GPC gel permeation chromatography
  • the content of the monomer component which is the raw material of the phenol compound in the resin (A) is calculated from the chart diagram of gel permeation chromatography (GPC).
  • the area ratio is preferably less than 10%. The GPC was measured under the measurement conditions described in the examples.
  • the softening point of the resin (A) is preferably 50 to 180 ° C, more preferably 50 to 150 ° C. When the softening point is within the above range, the moldability is improved, which is preferable.
  • the softening point can be measured in accordance with JIS K7234.
  • the hydroxyl group equivalent of the resin (A) is preferably 150 to 200 g / equivalent, and more preferably 150 to 180 g / equivalent. When the hydroxyl group equivalent is within the above range, the curability is good, which is preferable.
  • the melt viscosity (150 ° C.) of the resin (A) is preferably 0.1 to 10 dPa ⁇ s, and more preferably 0.1 to 5 dPa ⁇ s. When the melt viscosity is within the above range, the moldability is improved, which is preferable.
  • the melt viscosity (150 ° C.) can be measured with an ICI viscometer in accordance with the melt viscosity measurement method ASTM D4287.
  • the resin (A) can be produced under acidic catalytic conditions like other phenol novolac resins.
  • the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. And so on. These may be used alone or in combination of two or more.
  • the resin (A) for example, a method in which the phenol compound raw material and the aldehyde compound are reacted in the presence of the acidic catalyst under a temperature condition of 50 to 180 ° C. for 1 to 20 hours. Can be mentioned.
  • the reaction ratio between the phenol compound raw material and the aldehyde compound and the amount of the catalyst added can be appropriately adjusted according to the desired resin performance. Above all, the ratio of the aldehyde compound to 1 mol of the phenol compound raw material is preferably in the range of 0.05 to 0.5 mol because the binuclear component is easily generated.
  • the amount of the acidic catalyst added is preferably in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the total mass of the reaction raw material.
  • the reaction between the phenol compound raw material and the aldehyde compound may be carried out in a solvent, if necessary.
  • the solvent used here is, for example, water; methanol, ethanol, propanol, ethyl lactate, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and the like.
  • a step of distilling off unreacted raw materials, a solvent, etc., a step of purifying by washing with water, reprecipitation, etc. may be performed.
  • the resin (B) having a dicyclopentadiene skeleton has an alicyclic structure derived from dicyclopentadiene in the resin structure, it can particularly contribute to the effect of increasing the toughness of the cured product.
  • the resin (B) may be a phenol resin having a dicyclopentadiene skeleton and a phenolic hydroxyl group in the resin structure, and other specific structures are not particularly limited.
  • the phenol resin (B) having the dicyclopentadiene skeleton preferably contains the compound (b1) represented by the following general formula (1).
  • the resin (B) contains the compound (b1), an increase in the viscosity of the resin composition can be suppressed, the resin composition having excellent workability can be obtained, and the toughness of the cured product can be enhanced. Therefore, it is preferable.
  • R 1 independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group and the like. ..
  • n in the formula (1) represents 0, 1, or 2, but it is preferable that n is 0 because it is excellent in curability and the like.
  • the content of the compound (b1) in the resin (B) is preferably 30% or more, more preferably 40 to 99% in terms of the area ratio calculated from the gel permeation chromatography (GPC) chart. It is more preferably 50 to 99%.
  • the GPC was measured under the measurement conditions described in the examples.
  • Examples of the resin (B) include a condensation reaction product of a dicyclopentadiene compound and a phenol compound.
  • the dicyclopentadiene compound is not particularly limited, and is, for example, dicyclopentadiene, 4-vinyl-1-cyclohexene, 5-vinylcyclo [2.2.1] hepta-2-ene, 3a, 4,7,7a-.
  • Tetrahydroindene, ⁇ -pinene, limonene and the like are not mentioned, among which dicyclopentadiene, 4-vinyl-1-cyclohexene, 5-vinylcyclo [2.2.1] hepta-2-ene, and 3a, 4,7,7a-tetrahydroindene is preferred, dicyclopentadiene and 3a, 4,7,7a-tetrahydroindene are more preferred, and dicyclopentadiene is even more preferred. These may be used alone or in combination of two or more.
  • the phenol compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group, but for example, a halogen atom is attached to phenol, naphthalene-1-ol, naphthalene-2-ol, and a hydrogen atom directly bonded to these aromatic rings. And compounds substituted with an alkyl group. From the viewpoint of reactivity with the dicyclopentadiene compound, the number of the substituents is preferably 0, 1, or 2. Further, the number of carbon atoms of the alkyl group is preferably in the range of 1 to 4. Of these, phenol, naphthalene-1-ol, and naphthalene-2-ol are preferable. As the phenol compound, these may be used alone or in combination of two or more.
  • Examples of the condensation reaction between the dicyclopentadiene compound and the phenol compound include a method of reacting the dicyclopentadiene compound with the phenol compound under acidic catalytic conditions.
  • the acidic catalyst is not particularly limited, and Lewis acid, protonic acid and the like can be used.
  • Lewis acid examples include boron trifluoride, boron trifluoride phenol complex, and boron trifluoride ether complex in terms of excellent reaction rate, and among them, boron trifluoride phenol complex and trifluoride. Boron trifluoride ether complexes are preferred, and boron trifluoride phenol complexes are more preferred.
  • Examples of the protonic acid include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like, among which sulfuric acid and p-toluenesulfonic acid are preferable, and p-toluenesulfonic acid is more preferable.
  • the reaction ratio between the dicyclopentadiene compound and the phenol compound and the amount of the catalyst added can be appropriately adjusted according to the desired resin performance.
  • the ratio of the phenol compound to 1 mol of the dicyclopentadiene is preferably in the range of 0.05 to 0.5 mol.
  • the amount of the acidic catalyst added is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total mass of the reaction raw material.
  • the acidic catalyst can be neutralized using an alkaline catalyst neutralizer. After neutralizing the acidic catalyst, it is preferable to perform filtration in order to remove the neutralizing agent and the catalyst residue. Further, the purified dicyclopentadienephenol condensate can be recovered by distilling the filtrate under reduced pressure to remove unreacted phenol compounds and the like.
  • the components other than the compound (b1) in the resin are represented by, for example, the following general formula (3). Compounds and the like can be mentioned.
  • R 1 independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0, 1, or 2.
  • m is an integer of 1 or more.
  • R1 and n in the general formula (3) have the same meaning as R1 and n in the general formula (1), and the preferred ones thereof are the same as those in the general formula (1).
  • the resin (B) is a condensation reaction product of the dicyclopentadiene compound and the phenol compound
  • a part of a component having a molecular weight smaller than that of the compound (b1) such as a phenol compound remains in the resin. May be.
  • the content of the component having a molecular weight smaller than that of the compound (b1) in the resin (B) is a chart diagram of gel permeation chromatography (GPC).
  • the area ratio calculated from the above is preferably less than 10%.
  • the GPC was measured under the measurement conditions described in the examples.
  • the softening point of the resin (B) is preferably 50 to 180 ° C, more preferably 50 to 150 ° C. When the softening point is within the above range, the moldability is improved, which is preferable.
  • the softening point can be measured in accordance with JIS K7234.
  • the hydroxyl group equivalent of the resin (B) is preferably 140 to 250 g / equivalent, and more preferably 150 to 200 g / equivalent. When the softening point is within the above range, the curability is good, which is preferable.
  • the melt viscosity (150 ° C.) of the resin (B) is preferably 0.1 to 10 dPa ⁇ s, and more preferably 0.1 to 5 dPa ⁇ s. When the melt viscosity is within the above range, the moldability is improved, which is preferable.
  • the melt viscosity (150 ° C.) can be measured with an ICI viscometer in accordance with the melt viscosity measurement method ASTM D4287.
  • the blending ratio (A) / (B) shown by the mass ratio of the paratertiary butylphenol novolak resin (A) and the phenol resin (B) having a dicyclopentadiene skeleton is It is preferably 15/85 to 85/15, and more preferably 40/60 to 60/40.
  • the above-mentioned compounding ratio is preferable because the elastic modulus of the cured product, which is the effect of the present invention, is lower, and the effect of being more excellent in toughness is more remarkably exhibited.
  • both the resin (A) and the resin (B) contained in the resin composition of the present invention have a phenolic hydroxyl group, they can be cured by using this in combination with a compound capable of causing a curing reaction. It can be used as a sex composition.
  • the compound that can cause a curing reaction with the resin (A) and the resin (B) include an epoxy resin and the like. That is, the resin (A) and the resin (B) of the present invention can be used as a curing agent for an epoxy resin.
  • the epoxy resin is not particularly limited, but is not particularly limited.
  • Novorak type epoxy resin such as resin; Phenolic aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin and other aralkyl type epoxy resins; Bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S Bisphenol type epoxy resin such as type epoxy resin, tetrabromobisphenol A type epoxy resin; Biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, epoxy resin having biphenyl skeleton and diglycidyl oxybenzene skeleton; Naphthalene type epoxy resin; Vinaftor type epoxy resin; Vinaftil type epoxy resin; Dicyclopent
  • epoxy resins phenol novolac type epoxy resin, cresol novolac type epoxy resin, aralkyl type epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are preferable.
  • the epoxy resin may be used alone or in combination of two or more.
  • the number average molecular weight (Mn) of the epoxy resin is preferably 200 to 1500, more preferably 200 to 1000. When it is within the above range, it becomes a low molecular weight epoxy resin and tends to have high fluidity, which is preferable.
  • the number average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions described in Examples.
  • the softening point of the epoxy resin is preferably 50 to 150 ° C, more preferably 50 to 120 ° C. When the softening point is within the above range, the moldability is improved, which is preferable.
  • the softening point can be measured in accordance with JIS K7234.
  • the epoxy equivalent of the epoxy resin is preferably 120 to 400 g / equivalent, and more preferably 130 to 300 g / equivalent.
  • the curability is excellent, and the balance between heat resistance and high toughness of the obtained cured product, low coefficient of thermal expansion, adhesion to the substrate, and the like is excellent. ..
  • the melt viscosity of the epoxy resin is preferably 0.1 to 10 dPa ⁇ s, and more preferably 0.1 to 5 dPa ⁇ s.
  • the melt viscosity (150 ° C.) can be measured with an ICI viscometer in accordance with the melt viscosity measurement method ASTM D4287.
  • a curing agent for epoxy resin may be used.
  • other curing agents for epoxy resins include the resin (A) and other phenolic resins other than the resin (B), amine compounds, acid anhydrides, active ester resins, cyanate ester resins, and amideimides. Examples thereof include a resin, a maleimide resin, and a benzoxazine resin.
  • phenol resins examples include various bisphenol resins, phenol novolac resins, cresol novolak resins, naphthol novolak resins, novolak resins such as bisphenol novolak resins, phenol aralkyl resins (Zyroc resins), naphthol aralkyl resins, and birds.
  • phenol resins examples include phenylol methane resin, polyphenylene ether type resin, and polynaphthylene ether type resin. These may be used alone or in combination of two or more.
  • the resin composition of the present invention contains the other curing agent for epoxy resin, the resin (A) and the resin (A) with respect to the total mass of components (curing agent for epoxy resin) functioning as a curing agent for epoxy resin.
  • the ratio (% by mass) of the total mass of B) is preferably 50% by mass or more because the elastic coefficient of the cured product, which is the effect of the present invention, is lower and the effect of superior toughness is more remarkable. 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable.
  • the resin composition of the present invention can contain an inorganic filler.
  • the thermal expansion property can be suppressed, and the occurrence of warpage and cracks due to the difference in shrinkage amount due to the coefficient of linear expansion can be suppressed, which is preferable.
  • the inorganic filler is not particularly limited, but is silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrided material.
  • silica amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be used.
  • the molten silica is preferable because it is possible to blend a larger amount of the inorganic filler.
  • the molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the resin composition, a spherical one is mainly used. Is preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica.
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler may be surface-treated if necessary.
  • the surface treatment agent that can be used is not particularly limited, but is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based cup. Ring agents and the like can be used.
  • the surface treatment agent examples include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldi. Shirazan and the like can be mentioned.
  • organic filler can be blended in addition to the inorganic filler as long as the characteristics of the present invention are not impaired.
  • examples of the organic filler include polyamide particles and the like.
  • the amount of the inorganic filler used is 100 to 2000 with respect to 100 parts by mass of the total amount of the resin components (the resin (A), the resin (B), the epoxy resin, the curing agent, etc.) in the resin composition. It is preferably parts by mass, more preferably 400 to 1800 parts by mass. When the amount of the inorganic filler used is within the above range, it is preferable because it is excellent in low thermal expansion, flame retardancy, and insulation reliability.
  • the resin composition of the present invention further contains a solvent, an additive, and the like as long as the effects of the present invention are not impaired. It may be included.
  • the resin composition of the present invention may be prepared without a solvent, or may contain a solvent.
  • the solvent are not particularly limited, but are ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate and propylene glycol monomethyl.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • ether solvents such as diethyl ether and tetrahydrofuran
  • Ester-based solvents such as ether acetate and carbitol acetate; carbitol compounds such as cellosolve and butyl carbitol, toluene, xylene, ethylbenzene, mecitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and the like.
  • Examples thereof include amide-based solvents such as aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent used is appropriately adjusted according to the intended use and is not particularly limited. Specifically, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the resin composition.
  • the resin composition of the present invention may contain various additives such as a curing accelerator, a mold release agent, a pigment, a colorant, an emulsifier, and a flame retardant, if necessary.
  • the curing accelerator is not particularly limited, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a urea-based curing accelerator.
  • Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl.
  • organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine
  • organic phosphite compounds such as trimethylphosphine and triethylphosphine
  • ethyltriphenyl ethyltriphenyl.
  • Phosphornium bromide benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylboran, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.
  • Examples of the amine-based curing accelerator include triethylamine, tributylamine, N, N-dimethyl-4-aminopyridine (4-dimethylaminopyridine, DMAP), 2,4,6-tris (dimethylaminomethyl) phenol, 1, Examples thereof include 8-diazabicyclo [5.4.0] -undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] -Nonen-5 (DBN).
  • DBU 8-diazabicyclo [5.4.0] -undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] -Nonen-5
  • imidazole-based curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl.
  • Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-Triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.
  • urea-based curing accelerator examples include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.
  • a phosphorus-based curing accelerator or an imidazole-based curing accelerator from the viewpoint of curability, and a phosphorus-based curing accelerator is preferable from the viewpoint of insulation reliability.
  • the curing accelerator may be used alone or in combination of two or more.
  • the amount of the curing accelerator used can be appropriately adjusted in order to obtain the desired curability, and the resin components in the resin composition (epoxy resin, the resin (A) as a curing agent, the resin (B), etc.) can be adjusted.
  • the resin components in the resin composition epoxy resin, the resin (A) as a curing agent, the resin (B), etc.
  • the amount of the curing accelerator used is within the above range, it is preferable because the curing property and the insulation reliability are excellent.
  • the flame retardant is not particularly limited, and examples thereof include an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, and a halogen flame retardant. These flame retardants may be used alone or in combination of two or more.
  • the resin composition can be obtained by uniformly mixing each component such as the above-mentioned curing agent in addition to the epoxy resin, and can be easily made into a cured product by the same method as a conventionally known method. can.
  • the present invention relates to a cured product obtained by curing the resin composition. Since the cured product is obtained by using the resin composition, it is useful because it has a low elastic modulus and excellent toughness. In particular, since the resin composition contains the resin (A) and the resin (B), the viscosity is low and the workability is excellent. Therefore, the cured product is suitably used for semiconductor encapsulant applications and the like. Can be done.
  • Examples of the cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.
  • the curing reaction examples include thermal curing and ultraviolet curing reaction.
  • the thermal curing reaction is easily carried out even under a non-catalyst, but if a faster reaction is desired, an organic peroxide or an azo compound is used.
  • a polymerization initiator such as, a phosphine compound, or a basic catalyst such as a tertiary amine.
  • benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazole compound and the like can be mentioned.
  • the heating temperature at the time of heat curing is not particularly limited, but is usually 100 to 300 ° C., and the heating time is 1 to 1 to 1. 24 hours.
  • the cured product of the present invention preferably has an elastic modulus (storage elastic modulus) at 40 ° C. of 3200 MPa or less, more preferably 3000 MPa or less, and particularly preferably 2800 MPa or less. Further, the elastic modulus (storage elastic modulus) at 260 ° C. is preferably 20 MPa or less, and more preferably 10 MPa or less.
  • the method for measuring the elastic modulus is the same as the evaluation method in the examples.
  • the cured product of the present invention preferably has a Charpy impact strength of 2 J / cm 2 or more, more preferably 2.5 J / cm 2 or more, and particularly preferably 3 J / cm 2 or more. ..
  • the method for measuring the Charpy impact strength is the same as the evaluation method in the examples.
  • the present invention relates to a semiconductor encapsulant containing the resin composition.
  • the semiconductor encapsulant obtained by using the resin composition is preferably used for semiconductor encapsulant applications because it is excellent in low elastic modulus and high toughness in the obtained cured product by using the resin composition. Can be done.
  • the resin composition is sufficiently melt-mixed with an additive, which is an optional component, by using an extruder, a kneader, a roll or the like until it becomes uniform.
  • an additive which is an optional component
  • the present invention relates to a semiconductor device containing a cured product of the semiconductor encapsulant.
  • the cured product of the semiconductor encapsulant has a low elastic modulus and excellent toughness, and is preferable because it can suppress the occurrence of warpage and cracks due to the difference in shrinkage amount due to the linear expansion coefficient.
  • the semiconductor encapsulant is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further, in a temperature range of room temperature (20 ° C.) to 250 ° C., 1 to 1 to Examples thereof include a method of heat-curing for 10 hours.
  • the cured product obtained by the resin composition of the present invention is excellent in low elastic modulus and high toughness, it is not only a semiconductor encapsulant and a semiconductor device, but also a prepreg, a circuit board, a build-up film, and a build-up board. , Can be suitably used for adhesives, resist materials and the like. Further, it can be suitably used for various uses such as a matrix resin of a fiber reinforced resin, and the use is not limited to these.
  • the mixture was aged at 140 ° C. for 2 hours.
  • 10.0 g of hydrotalcite was added to the contents of the reaction vessel, and the mixture was stirred for 30 minutes to neutralize and adsorb the catalyst.
  • the reaction mixture in the reaction vessel was filtered to remove the neutralized product, and the filtrate was collected.
  • the recovered filtrate was placed in a flask, heated to 220 ° C., subjected to atmospheric distillation and vacuum distillation, and unreacted phenol was distilled off to remove the unreacted phenol.
  • ⁇ Elastic modulus (storage elastic modulus)> The resin composition obtained above is cured in a normal pressure press at 150 ° C. for 10 minutes so that the thickness of the cured product is 2.4 mm, and then aftercure is performed at 175 ° C. for 5 hours. As a result, a cured product for evaluation was obtained.
  • the obtained cured product was cut into a size of 5 mm ⁇ 54 mm to obtain a test piece, and 40 by DMA (dynamic viscoelastic) measurement by a rectangular tension method using a “solid viscoelastic modulus measuring device RSAII” manufactured by Leometric Co., Ltd.
  • the storage elastic modulus (MPa) at ° C. and 260 ° C. was measured, and the elastic modulus was evaluated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)
PCT/JP2021/040509 2020-11-16 2021-11-04 樹脂組成物、硬化物、半導体封止材、及び、半導体装置 WO2022102489A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022151177A (ja) * 2021-03-26 2022-10-07 住友ベークライト株式会社 封止用樹脂組成物および半導体素子の製造方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07196767A (ja) * 1993-12-28 1995-08-01 Nippon Kayaku Co Ltd エポキシ樹脂組成物およびその硬化物
JPH11199648A (ja) * 1998-01-19 1999-07-27 Dainippon Ink & Chem Inc エポキシ樹脂組成物
WO2005019299A1 (ja) * 2003-08-21 2005-03-03 Asahi Kasei Chemicals Corporation 感光性組成物およびその硬化物
JP2010222390A (ja) * 2009-03-19 2010-10-07 Lintec Corp 接着剤組成物、接着シートおよび半導体装置の製造方法
US20140228483A1 (en) * 2013-02-13 2014-08-14 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith
WO2015152037A1 (ja) * 2014-03-31 2015-10-08 明和化成株式会社 フェノール樹脂、該フェノール樹脂を含むエポキシ樹脂組成物、該エポキシ樹脂組成物の硬化物、及び該硬化物を有する半導体装置
WO2018003513A1 (ja) * 2016-06-29 2018-01-04 Dic株式会社 フェノールノボラック樹脂、硬化性樹脂組成物及びその硬化物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07196767A (ja) * 1993-12-28 1995-08-01 Nippon Kayaku Co Ltd エポキシ樹脂組成物およびその硬化物
JPH11199648A (ja) * 1998-01-19 1999-07-27 Dainippon Ink & Chem Inc エポキシ樹脂組成物
WO2005019299A1 (ja) * 2003-08-21 2005-03-03 Asahi Kasei Chemicals Corporation 感光性組成物およびその硬化物
JP2010222390A (ja) * 2009-03-19 2010-10-07 Lintec Corp 接着剤組成物、接着シートおよび半導体装置の製造方法
US20140228483A1 (en) * 2013-02-13 2014-08-14 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith
WO2015152037A1 (ja) * 2014-03-31 2015-10-08 明和化成株式会社 フェノール樹脂、該フェノール樹脂を含むエポキシ樹脂組成物、該エポキシ樹脂組成物の硬化物、及び該硬化物を有する半導体装置
WO2018003513A1 (ja) * 2016-06-29 2018-01-04 Dic株式会社 フェノールノボラック樹脂、硬化性樹脂組成物及びその硬化物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022151177A (ja) * 2021-03-26 2022-10-07 住友ベークライト株式会社 封止用樹脂組成物および半導体素子の製造方法

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