WO2024089905A1 - Composition de résine, adhésif, agent d'étanchéité, produit durci, dispositif à semi-conducteur et composant électronique - Google Patents

Composition de résine, adhésif, agent d'étanchéité, produit durci, dispositif à semi-conducteur et composant électronique Download PDF

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WO2024089905A1
WO2024089905A1 PCT/JP2022/047359 JP2022047359W WO2024089905A1 WO 2024089905 A1 WO2024089905 A1 WO 2024089905A1 JP 2022047359 W JP2022047359 W JP 2022047359W WO 2024089905 A1 WO2024089905 A1 WO 2024089905A1
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component
group
resin composition
compound
equivalent number
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PCT/JP2022/047359
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Kento MEGURO
Atsushi Saito
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Namics Corporation
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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
    • C08G59/02—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
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/68—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 catalysts used
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds

Definitions

  • the present invention relates to a resin composition, an adhesive or sealant containing the same, a cured product thereof, a semiconductor device and an electronic component containing the cured product.
  • an adhesive, a sealant and the like containing a curable resin composition in particular, an epoxy resin composition
  • a curable resin composition in particular, an epoxy resin composition
  • an adhesive, a sealant and the like containing a curable resin composition are often used for such purposes as maintaining reliability.
  • adhesives and sealants used in the manufacture of such devices or components are required to exhibit sufficient curability even under low temperature conditions.
  • curable compositions using thiol curing agents as curing agents are known (e.g., Patent Literatures 1 and 2).
  • Patent Literature 3 discloses an epoxy resin composition comprising (A) at least one thiol curing agent containing a polyfunctional thiol compound having three or more thiol groups; (B) at least one polyfunctional epoxy resin; (C) a crosslink density modifier containing at least one monofunctional epoxy resin; and (D) a latent curing catalyst, wherein the number (amount) of thiol groups and the number (amount) of epoxy groups possessed by these components are in a specific relationship.
  • the cured product of this epoxy resin composition in Patent Literature 3 is disclosed to be able to follow the deformation caused by thermal expansion of parts in an assembly consisting of multiple parts made of different materials joined together.
  • the object of the present invention is to provide a resin composition that cures under a low temperature condition and gives a cured product with a flexibility enough to follow the deformation of the assembly due to thermal stress of the parts, i.e., an excellent stress relaxation property, and has a low self-exothermic temperature during a curing reaction.
  • the first embodiment of the present invention is the following resin composition.
  • a resin composition comprising (A) a polyfunctional epoxy compound, (B) a polyfunctional thiol compound, (C) a monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in its molecule, and (D) a curing catalyst.
  • the second embodiment of the present invention is (10) an adhesive or sealant comprising the resin composition described in any one of (1) to (9) above.
  • the third embodiment of the present invention is (11) a cured product in which the resin composition described in any one of (1) to (9) above or the adhesive or sealant described in (10) above has been cured.
  • the fourth embodiment of the present invention is (12) a semiconductor device or an electronic component comprising the cured product described in (11) above.
  • One aspect of the resin composition or the adhesive or sealant as mentioned above is (13) the resin composition described in any one of (1) to (9) above or the adhesive or sealant described in (10) above for use in curing by heat alone.
  • Another embodiment of the present invention is (14) use of the resin composition described in any one of (1) to (9) above or the adhesive or sealant described in (10) above in curing by heat alone.
  • the first embodiment of the present invention it is possible to obtain a resin composition that cures under a low temperature condition and gives a cured product with an excellent stress relaxation property. Furthermore, this resin composition has a low self-exothermic temperature during a curing reaction, which can suppress overheating of an adherend and a surrounding component thereof.
  • the second embodiment of the present invention it is possible to obtain an adhesive or sealant that cures under a low temperature condition, gives a cured product with an excellent stress relaxation property, and can suppress overheating of an adherend and a surrounding component thereof.
  • the third embodiment of the present invention it is possible to obtain a cured product with an excellent stress relaxation property and to suppress overheating of an adherend of the cured product and a surrounding component thereof.
  • the fourth embodiment of the present invention it is possible to obtain a semiconductor device and an electronic component containing the cured product with an excellent stress relaxation property and suppressed overheating of an adherend and a surrounding component thereof.
  • Fig.1 shows a dumbbell-shaped specimen used for tensile testing.
  • a cured product with an excellent stress relaxation property refers to a cured product that has a flexibility enough to follow a deformation of an assembly due to a thermal stress of the parts.
  • a self-exothermic temperature of a resin composition refers to the temperature of the resin composition itself during thermal curing.
  • the maximum self-exothermic temperature of the resin composition can be determined as the maximum sample temperature (maximum exothermic temperature) when measured by Simultaneous Thermogravimetry / Differential Thermal Analysis (TG-DTA) under a curing reaction condition at a fixed temperature.
  • maximum sample temperature maximum exothermic temperature
  • TG-DTA Differential Thermal Analysis
  • a resin composition which is the first embodiment of the present invention, contains (A) a polyfunctional epoxy compound, (B) a polyfunctional thiol compound, (C) a monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in its molecule, and (D) a curing catalyst. According to this embodiment, it is possible to obtain a resin composition that cures under a low temperature condition, gives a cured product with an excellent stress relaxation property, and has a low self-exothermic temperature during a curing reaction.
  • the resin composition of this embodiment contains (A) a polyfunctional epoxy compound (hereinafter also referred to as "component (A)").
  • the (A) polyfunctional epoxy compound is not limited as long as it is a compound having at least two epoxy groups, and conventionally used epoxy resins can be used as the component (A).
  • Epoxy resin is a generic term for thermosetting resins that can be cured by cross-linking networks with epoxy groups present in its molecule, including prepolymer compounds before curing. In consideration of ensuring heat resistance, a compound with 2 to 6 epoxy groups is more preferable as the component (A), and a compound with two epoxy groups is even more preferable.
  • the (A) polyfunctional epoxy compound may be liquid or solid at 25°C, and it is preferred to be liquid at 25°C.
  • an amount of the polyfunctional epoxy compound that is liquid at 25°C is preferably 50 or more parts by weight, and for example, 60 or more parts by weight, and for example, 70 or more parts by weight, and for example, 80 or more parts by weight, and for example, 90 or more parts by weight, and for example 100 parts by weight, with respect to 100 parts by weight of the total of the (A) polyfunctional epoxy compound.
  • the (A) polyfunctional epoxy compound contains a polyfunctional epoxy compound that is liquid at 25°C and a polyfunctional epoxy compound that is solid at 25°C, and an amount of the polyfunctional epoxy compound that is liquid at 25°C is preferably 50 or more parts by weight, and for example, 60 or more parts by weight, and for example, 70 or more parts by weight, and for example, 80 or more parts by weight, and for example, 90 or more parts by weight, with respect to 100 parts by weight of the total of the (A) polyfunctional epoxy compound.
  • the (A) polyfunctional epoxy compound is broadly classified into an aromatic polyfunctional epoxy compound and a polyfunctional epoxy compound without an aromatic ring.
  • the aromatic polyfunctional epoxy compound is a polyfunctional epoxy compound having a structure containing an aromatic ring such as a benzene ring.
  • epoxy resins of this type that have conventionally been used frequently, such as bisphenol A-type epoxy compounds.
  • examples of the aromatic polyfunctional epoxy compound include, but are not limited to: - bisphenol A-type epoxy compounds; - branched polyfunctional bisphenol A-type epoxy compounds such as p-glycidyloxyphenyldimethyl trisbisphenol A diglycidyl ether; - bisphenol F-type epoxy compounds; - novolac-type epoxy compounds; - tetrabromobisphenol A-type epoxy compounds; - fluorene-type epoxy compounds; - biphenyl aralkyl epoxy compounds; - diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; - biphenyl-type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxy
  • the component (A) contains an aromatic polyfunctional epoxy compound.
  • the aromatic polyfunctional epoxy compound bisphenol F-type epoxy compounds, bisphenol A-type epoxy compounds, and glycidylamine-type epoxy compounds are preferable, and among these, those having an epoxy equivalent weight of 90 to 500 g/eq are particularly preferable, and those having an epoxy equivalent weight of 90 to 400 g/eq are further preferable.
  • the aromatic polyfunctional epoxy compound may be oxyalkylene modified, such as EO (ethylene oxide) modified or PO (propylene oxide) modified.
  • the aromatic polyfunctional epoxy compound is preferably liquid at 25°C.
  • the viscosity of the aromatic polyfunctional epoxy compound at 25°C is preferably from 0.1 to 100 Pa ⁇ s, more preferably 0.5 to 100 Pa ⁇ s, and further preferably 1 to 100 Pa ⁇ s.
  • viscosity is expressed as a value measured according to the Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, viscosity can be observed by measuring viscosity using an E-type viscometer at a rotational speed of 10 rpm. There are no limitations on instruments, rotors or measurement ranges used.
  • the polyfunctional epoxy compound without an aromatic ring includes, for example, an aliphatic polyfunctional epoxy compound and a polyfunctional epoxy compound with a heterocyclic ring.
  • Examples of the aliphatic polyfunctional epoxy compound include, but are not limited to: - diepoxy compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether; - tri-poxy compounds such as trimethylolpropane triglycidyl ether, and glycerin triglycidyl ether; - alicyclic epoxy compounds
  • the aliphatic polyfunctional epoxy compound preferably has an epoxy equivalent weight of 90 to 450 g/eq.
  • the aliphatic polyfunctional epoxy compound is preferably liquid at 25°C.
  • the viscosity of the aliphatic polyfunctional epoxy compound at 25°C is preferably from 10 to 10,000 mPa ⁇ s, and more preferably 10 to 5,000 mPa ⁇ s.
  • polyfunctional epoxy compound having a heterocyclic ring examples include isocyanurate-type epoxy compounds (trade names: TEPIC-S, TEPIC-L, TEPIC-PAS TEPIC-VL TEPIC-VL, TEPIC-FL, and TEPIC-UC; available from Nissan Chemical Corporation) and glycoluril type epoxy compounds (trade name: TG-G available from Shikoku Chemicals Corporation).
  • the polyfunctional epoxy compound having a heterocyclic ring is preferably one having an epoxy equivalent weight of 80 to 450 g/eq.
  • the polyfunctional epoxy compound having a heterocyclic ring is preferably liquid at 25°C from the viewpoint of workability.
  • the polyfunctional epoxy compound having a heterocyclic ring is preferably one having the viscosity at 25°C of from 100 to 50,000 mPa ⁇ s, and more preferably 100 to 5,000 mPa ⁇ s.
  • the polyfunctional epoxy compound having a heterocyclic ring is preferably solid at 25°C.
  • the resin composition of this embodiment contains (B) a polyfunctional thiol compound (hereinafter also referred to as "component (B)").
  • the (B) polyfunctional thiol compound is a compound containing two or more thiol groups, each of which reacts with each of epoxy groups in the (A) polyfunctional epoxy compound and a group (c) in the (C) monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in its molecule.
  • the (B) polyfunctional thiol compound preferably has three or more thiol groups.
  • the (B) polyfunctional thiol compound contains a trifunctional and/or tetrafunctional thiol compound.
  • Trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively.
  • the thiol equivalent weight of the (B) polyfunctional thiol compound is preferably from 90 to 200 g/eq, more preferably from 90 to 150 g/eq, further preferably from 90 to 140 g/eq, and even more preferably from 90 to 130 g/eq.
  • the polyfunctional thiol compound is broadly classified into a thiol compound having a hydrolyzable substructure such as an ester bond in its molecule (i.e., a hydrolyzable thiol compound) and a thiol compound without such a substructure (i.e., a nonhydrolyzable thiol compound).
  • hydrolyzable polyfunctional thiol compound examples include trimethylolpropane tris(3-mercaptopropionate) (trade name: TMMP; available from SC Organic Chemical Co., Ltd.), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (trade name: TEMPIC; available from SC Organic Chemical Co., Ltd.), pentaerythritol tetrakis(3-mercaptopropionate) (trade name: PEMP; available from SC Organic Chemical Co., Ltd.), tetraethyleneglycol bis(3-mercaptopropionate) (trade name: EGMP-4; available from SC Organic Chemical Co., Ltd.), dipentaerythritol hexakis(3-mercaptopropionate) (trade name: DPMP; available from SC Organic Chemical Co., Ltd.), pentaerythritol tetrakis(3-mercaptobutyrate) (trade name: Karen
  • non-hydrolyzable polyfunctional thiol compound examples include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, available from Shikoku Chemicals Corporation), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, available from Shikoku Chemicals Corporation), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a, 6a-dimethylglycoluril, 1,3,4,6-tetrakis(
  • the resin composition of this embodiment contains (C) a monofunctional compound (hereinafter referred to simply as "component (C)”) having one group (c) (hereinafter referred to simply as “group (c)”) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in its molecule.
  • component (C) a monofunctional compound having one group (c) (hereinafter referred to simply as “group (c)”) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in its molecule.
  • group (c) in the component (C) more specifically the unsaturated double bond in the group (c) reacts with a thiol group in the (B) polyfunctional thiol compound.
  • the term "monofunctional" is used to mean having one group (c) in its molecule that reacts with a thiol group.
  • the electron-withdrawing group include a carbonyl group and a cyano group, with a carbonyl group being preferred.
  • the inclusion of the component (C) suppresses the increase in self-exothermic temperature during the curing reaction of the resin composition.
  • the reasons for this are, without limitation, considered to be the following.
  • the unsaturated double bond of the group (c) in the component (C) is highly reactive because of the adjacent electron-withdrawing group and reacts with a thiol group in the (B) polyfunctional thiol compound before an epoxy group in the (A) polyfunctional epoxy compound.
  • the exothermic peak associated with the curing reaction is shifted, the reaction heat is dispersed, and the increase in self-exothermic temperature is suppressed.
  • the reaction system of the resin composition described in Patent Literature 3 is primarily an epoxy-thiol reaction, so the reaction heat is not dispersed and the self-exothermic temperature is thought to have increased.
  • the temperature difference between the curing temperature and the maximum self-exothermic temperature is preferably 20°C or less, more preferably 15°C or less, and further preferably 10°C or less.
  • the maximum self-exothermic temperature is preferably 100°C or less, more preferably 95°C or less, and further preferably 90°C or less. Since the component (C) is monofunctional, it does not form a cross-link, and the internal stress increase in the cured product due to too high cross-link density can be suppressed, and flexibility can be given to the resulting cured product of the resin composition.
  • the component (C) is preferably liquid at 25°C from the viewpoint of the viscosity of the resin composition.
  • Examples of the component (C) include a monofunctional maleimide compound, a monofunctional (meth)acrylate compound, and a monofunctional acrylamide compound.
  • Group (c) includes a maleimide group and a (meth)acryloyl group.
  • the component (C) is preferably selected from a monofunctional maleimide compound and a monofunctional (meth)acrylate compound, with monofunctional (meth)acrylate compound being more preferred.
  • the monofunctional maleimide compound is a compound having one maleimide group as the group (c), examples of which include: maleimide; maleimides containing aliphatic hydrocarbon groups such as methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, cyclohexyl maleimide; maleimides containing aromatic rings such as phenyl maleimide; and the like. They may be used alone or in combination of two or more kinds.
  • the monofunctional (meth)acrylate compound is a compound with one (meth)acryloyl group as the group (c).
  • Examples of the monofunctional (meth)acrylate compound include: - esters of monovalent alcohols and (meth)acrylic acids such as ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acryl
  • the molecular weight of the monofunctional (meth)acrylate compound is preferably 450 or less, more preferably 400 or less, even more preferably 380 or less, further preferably 350 or less, and particularly preferably 300 or less.
  • the monofunctional (meth)acrylate compound is preferably of low volatility, and the molecular weight of the monofunctional (meth)acrylate compound is preferably 100 and more, more preferably 120 and more, even more preferably 160 and more, further preferably 190 and more, and particularly preferably 200 and more.
  • the molecular weight of the monofunctional (meth)acrylate compound is preferably from 100 to 450, more preferably 120 to 400, even more preferably 140 to 380, further preferably 180 to 350, and particularly preferably 200 to 320.
  • the component (C) may have a group that can react with a thiol group, such as an epoxy group, in addition to the group (c). From the viewpoint of flexibility of the resulting cured product, there may be a case that it is preferable that the component (C) does not contain a group that can react with a thiol group, such as an epoxy group.
  • a ratio of an equivalent number of the group (c) of the component (C) to an equivalent number of the epoxy group of the component (A) is preferably 0.05 to 2, and more preferably 0.1 to 1.5, further preferably 0.15 to 1.25, and particularly preferably 0.2 to 1.
  • a ratio of an equivalent number of the epoxy group of the component (A) to an equivalent number of the thiol group of the component (B) is preferably 0.4 to 0.95, and more preferably 0.45 to 0.9, further preferably 0.5 to 0.9, and particularly preferably 0.55 to 0.9.
  • a ratio of a total of an equivalent number of the epoxy group of the component (A) and an equivalent number of the group (c) of the component (C) to an equivalent number of the thiol group of the component (B) (([an equivalent number of the epoxy group of the component (A)] + [an equivalent number of the group (c) of the component (C)])/[an equivalent number of the thiol group of the component (B)]) is preferably 0.7 to 1.5, and more preferably 0.75 to 1.4, further preferably 0.8 to 1.3, and particularly preferably 0.8 to 1.1.
  • bleed refers to a phenomenon in which unreacted components seep out of an adhesive coating or cured product over time when an adhesive containing a curable resin composition is used to fix or bond parts, and the seeping components themselves are sometimes called "bleed".
  • a ratio of an equivalent number of the group (c) of the component (C) to an equivalent number of the thiol group of the component (B) is preferably 0.05 to 0.7 and more preferably 0.1 to 0.6, and further preferably 0.15 to 0.55.
  • the component (C) contains an epoxy group, it is preferable that the above formulae for the equivalent numbers are satisfied on the condition that an equivalent number of the epoxy group of the component (C) is added to an equivalent number of the epoxy group of the component (A).
  • a functional group equivalent weight such as thiol equivalent weight, epoxy equivalent weight, (meth)acryloyl equivalent weight, and the like, refers to the molecular weight of the compound per functional group.
  • the equivalent number of functional group such as equivalent number of thiol group, equivalent number of epoxy group, and equivalent number of (meth)acryloyl group, represents the number (equivalent number) of functional groups per weight (charged amount) of the compound.
  • the epoxy equivalent weight of component (A) is theoretically the number obtained by dividing the molecular weight of component (A) by the number of epoxy groups in one molecule.
  • the actual epoxy equivalent weight can be determined by the method described in JIS K7236.
  • the equivalent number of epoxy group of component (A) is the number (equivalent number) of epoxy groups per weight (charged amount) of component (A), and it is the quotient of the weight (g) of the epoxy compound as component (A) divided by the epoxy equivalent weight of that epoxy compound (the sum of such quotients for each epoxy compound, if more than one epoxy compound is included.).
  • component (C) contains an epoxy group, its epoxy equivalent weight and the equivalent number of epoxy group are determined in the same manner.
  • the thiol equivalent weight of component (B) is theoretically the number obtained by dividing the molecular weight of component (B) by the number of thiol groups in one molecule.
  • the actual thiol equivalent weight can be determined, for example, by determining the thiol value by potentiometry. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A.
  • the equivalent number of thiol group of component (B) is the number of thiol groups (equivalent number) per weight (charged amount) of component (B), and it is the quotient of the weight (g) of the thiol compound as component (B) divided by the thiol equivalent weight of that thiol compound (the sum of such quotients for each thiol compound, if more than one thiol compound is included.).
  • the (meth)acryloyl equivalent weight of component (C) is theoretically equal to the number obtained by dividing the molecular weight of the (meth)acrylate compound by the number of acryloyl groups (or methacryloyl groups) in one molecule.
  • the actual (meth)acryloyl equivalent weight can be measured, for example, by NMR.
  • the equivalent number of (meth)acryloyl group of component (C) is the number of (meth)acryloyl groups (equivalent number) per weight (charged amount) of component (C), and it is the quotient of the weight (g) of the (meth)acrylate compound as component (C) divided by the (meth)acryloyl equivalent weight of that (meth)acrylate compound (the sum of such quotients for each (meth)acrylate compound, if more than one (meth)acrylate compound is included.).
  • the maleimide equivalent weight of component (C) is theoretically equal to the number obtained by dividing the molecular weight of the maleimide compound by the number of maleimide groups in one molecule.
  • the actual maleimide equivalent weight can be measured, for example, by NMR.
  • the equivalent number of maleimide group of component (C) is the number of maleimide groups (equivalent number) per weight (charged amount) of component (C), and it is the quotient of the weight (g) of the maleimide compound as component (C) divided by the maleimide equivalent weightof that maleimide compound (the sum of such quotients for each maleimide compound, if more than one maleimide compound is included.).
  • the resin composition of this embodiment contains (D) a curing catalyst (hereinafter also referred to as "component (D)").
  • component (D) a curing catalyst
  • the resin composition of this embodiment can be cured in a short time even under a low temperature condition.
  • the curing catalyst used in this embodiment is not limited and can be any known catalyst as long as it is a curing catalyst for the (A) polyfunctional epoxy compound.
  • Component (D) is preferably a latent curing catalyst.
  • a latent curing catalyst is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst.
  • the latent curing catalyst include imidazole compounds that are solid at room temperature; solid dispersion type amine adduct latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct type latent curing catalysts); reaction products of amine compounds and isocyanate compounds or urea compounds (urea type adduct type latent curing catalysts).
  • the solid-dispersion amine adduct-type latent curing catalysts are preferred from the viewpoint of pot life and curing performance.
  • epoxy compounds used as one of the raw materials for making solid dispersion type amine adduct latent curing catalysts include, but are not limited to, polyvalent phenols such as bisphenol A, bisphenol F, catechol and resorcinol, or polyglycidyl ether obtained by reacting polyhydric alcohols such as glycerin or polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin;
  • Amine compounds used as another production raw material for solid-dispersion type amine adduct latent curing catalysts can be any as long as it has at least one active hydrogen in its molecule that can additionally react with epoxy groups, and at least one functional group selected from primary, secondary and tertiary amino groups in its molecule.
  • Examples of such amine compounds include, but are not limited to, the following.
  • amine compounds include, but are not limited to, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; heterocyclic compounds containing a nitrogen atom(s) such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine; and the like.
  • aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane
  • compounds with intramolecular tertiary amino group(s) are raw materials that provide latent curing catalysts with excellent curing accelerating ability.
  • examples of such compounds include, but are not limited to, amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine and N-methylpiperazine, and primary or secondary amines with intramolecular tertiary amino group(s), such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and other imidazole compounds; alcohols, phenols, thiols, carboxylic acids, and hydrazides with tertiary amino group(s) in its molecule such as 2-dimethylaminoethanol, 1-methyl-2
  • Examples of the isocyanate compounds used as yet another production raw material for the solid-dispersion type amine adduct latent curing catalysts include, but are not limited to, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, para-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; compounds containing a terminal isocyanate group obtained by the reaction of the above-mentioned polyfunctional isocyanate compounds with active hydrogen compounds; and the like.
  • Examples of the compounds containing a terminal isocyanate group include, but are not limited to, addition compounds with a terminal isocyanate group obtained by the reaction of toluylene diisocyanate with trimethylolpropane, addition compounds with a terminal isocyanate group obtained by the reaction of toluylene diisocyanate with pentaerythritol, and the like.
  • urea compounds include, but are not limited to, urea, thiourea, and the like.
  • Solid-dispersion type latent curing catalysts that can be used in this embodiment are, for example, combinations of (a) two components of the amine compound and the epoxy compound as mentioned above, (b) three components of these two components and the active hydrogen compound, or (c) two or three components of the amine compound and the isocyanate compound and/or the urea compound. They can be easily prepared by taking each component, mixing them, reacting them at temperatures from room temperature to 200°C, cooling and solidifying the reaction product, and then pulverizing it, or reacting the components in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, desolventing the reaction product, and then pulverizing the solid content thereof.
  • a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran
  • Typical examples of commercially available latent curing catalyst products include, but are not limited to, amine-epoxy adduct-type products (amine adducts) such as Ajicure PN-23 (trade name; Ajinomoto Fine-Techno Co., Inc.), Ajicure PN-40 (trade name; Ajinomoto Fine-Techno Co., Inc.), Ajicure PN-50 (trade name; Ajinomoto Fine-Techno Co., Inc.), Hardner X-3661S (trade name; A.C.R.
  • Ajicure PN-23 trade name; Ajinomoto Fine-Techno Co., Inc.
  • Ajicure PN-40 trade name; Ajinomoto Fine-Techno Co., Inc.
  • Ajicure PN-50 trade name; Ajinomoto Fine-Techno Co., Inc.
  • Hardner X-3661S trade name; A.C.R.
  • Component (D) is preferably contained in 0.1 to 30% by weight, more preferably in 0.5 to 20% by weight relative to the total weight of the resin composition.
  • Component (D) may be provided in the form of a dispersion dispersed in a polyfunctional epoxy compound. It should be noted that, when component (D) is used in such form, the amount of the polyfunctional epoxy compound in which component (D) is dispersed is also included in the amount of component (A) above present in the resin composition of the present embodiment.
  • the resin composition of this embodiment may, if desired, contain optional components other than the above components (A) through (D), such as those described below, as needed.
  • thermosetting compound other than the component (A) refers to a polyfunctional thermosetting compound other than the component (A) that can react with the thiol group of the component (B), and does not include the component (B) itself.
  • thermosetting compound other than the component (A) include, (E) a polyfunctional (meth)acrylate compound, a phenol compound, a bismaleimide compound, a cyanate compound, and an episulfide compound.
  • Episulfide compounds are compounds containing thiirane rings, in which all or part of the oxygen atoms of the oxirane rings of the epoxy compounds are replaced by sulfur atoms.
  • Examples of the episulfide compounds include compounds containing two or more thiirane rings in the molecule and compounds containing one or more of both thiirane and oxirane rings in the molecule.
  • the amount of the component (A) is preferably 50 or more parts by weight, and is, for example, 51 or more parts by weight, and for example, 55 or more parts by weight, and for example, 60 or more parts by weight, and for example, 65 or more parts by weight, and for example, 70 or more parts by weight, and for example, 75 or more parts by weight, and for example, 80 or more parts by weight, and for example, 85 or more parts by weight, and for example, 90 or more parts by weight, with respect to 100 parts by weight of the total of the thermosetting compound (excluding the component (B)).
  • the resin composition of this embodiment may contain (E) a polyfunctional (meth)acrylate compound (hereinafter also referred to as "component (E)”) to the extent that the effect of the invention is not impaired.
  • component (E) a polyfunctional (meth)acrylate compound
  • polyfunctional (meth)acrylate compound examples include, but are not limited to, diacrylate and/or dimethacrylate of tris(2-hydroxyethyl)isocyanurate;. triacrylate and/or trimethacrylate of tris(2-hydroxyethyl)isocyanurate; trimethylolpropane triacrylate and/or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and/or trimethacrylate, or oligomers thereof; polyacrylate and/or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and/or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate and/or polymethacrylate
  • polyfunctional (meth)acrylate compounds include, for example, polyester acrylate from DAICEL-ALLNEX LTD. (trade name: EBECRYL810), ditrimethylolpropane tetraacrylate from DAICEL-ALLNEX LTD. (trade name: EBECRYL140), polyester acrylate from Toagosei Co., Ltd. (trade name: M7100), dimethylol tricyclodecane diacrylate from KYOEISHA CHEMICAL Co., LTD (trade name: Light Acrylate DCP-A), neopentylglycol modified trimethylolpropanediacrylate from Nippon Kayaku Co., Ltd. (trade name: Kayarad R-604).
  • the resin composition of this embodiment may contain a (F) filler (hereinafter also referred to as "component (F)”) to the extent that the effect of the present invention is not impaired.
  • component (F) a filler with a low modulus of elasticity can relieve stresses in the cured product, improving long-term reliability.
  • the (F) filler is broadly classified into inorganic and organic fillers.
  • the inorganic filler is not limited as long as it consists of a granular material formed by an inorganic material and has the effect of lowering the coefficient of linear expansion when added.
  • Silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, and the like can be used as the inorganic material. Any one of the inorganic filler may be used alone, or two or more may be used in combination. Silica filler is preferred as the inorganic filler because of its high filling capacity. Amorphous silica is preferred for silica.
  • the inorganic filler may be surface treated with a coupling agent such as a silane coupling agent.
  • organic fillers examples include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, filler with urethane skeleton, filler with butadiene skeleton, styrene filler, and the like. Organic fillers may be surface treated.
  • PTFE polytetrafluoroethylene
  • the shape of the filler is not limited and can be any of spherical, phosphor, needle, irregularly shaped, and the like.
  • the average particle diameter of the filler is preferably 6.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 4.0 ⁇ m or less.
  • the average particle diameter refers to the volume-based median diameter (d50) measured by the laser diffraction method in accordance with ISO-13320 (2009), unless otherwise noted.
  • the lower limit of the average particle diameter of the filler is not particularly limited, and from the viewpoint of the viscosity of the resin composition, it is preferable to be 0.005 ⁇ m or larger, and more preferable to be 0.1 ⁇ m or larger.
  • the average particle diameter of the (F) filler is preferably from 0.01 ⁇ m to 5.0 ⁇ m, and more preferably from 0.1 ⁇ m to 3.0 ⁇ m. Fillers with different average particle diameters may be used in combination. For example, a filler with an average particle diameter of from 0.005 ⁇ m to less than 0.1 ⁇ m and a filler with an average particle diameter from 0.1 ⁇ m to 6.0 ⁇ m may be used in combination.
  • the filler content in the resin composition of this embodiment is preferably 15 to 50% by weight, more preferably 20 to 45% by weight, and even more preferably 20 to 40% by weight with respect to the total weight of the resin composition.
  • the resin composition of this embodiment may contain (G) photo-radical initiator (hereinafter also referred to as "component (G)”) to the extent that the effect of the present invention is not impaired.
  • component (G) photo-radical initiator
  • the inclusion of the (G) photo-radical initiator promotes the reaction of component (B) with component (C) and an optional component (E) by photoirradiation.
  • Photo-radical initiators include, for example, alkylphenone compounds and acylphosphine oxide compounds.
  • alkylphenone compounds include benzyl dimethyl ketals, such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); ⁇ -aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); ⁇ -hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 379 EG from IGM Resins B.V.), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad
  • acylphosphine oxide compounds examples include 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (commercially available as Omnirad TPO H from IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins B.V.), and the like.
  • the (G) photo-radical initiators include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoate, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenz
  • the content of the (G) photo-radical initiator is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 8 parts by weight, with respect to 100 parts by weight of a total of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound.
  • the resin composition of this embodiment may, if desired, contain (H) a stabilizer (hereinafter also referred to as "component (H)”) to the extent that the effect of the invention is not impaired.
  • the stabilizer can improve the storage stability and lengthen the pot life of the resin composition of this embodiment.
  • Various known stabilizers can be used as the stabilizer, and at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is preferred due to its effectiveness in improving storage stability.
  • liquid boric acid ester compounds examples include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridododecylborate, trihexadecylborate, trioctadecylborate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzylborate, tripheny
  • Liquid boric acid ester compounds are preferred because they are liquid at room temperature (25°C), which keeps the composition viscosity low.
  • Aluminum Chelate A from Kawaken Fine Chemicals Co., Ltd.
  • Barbituric acid for example, may be used as an organic acid. Any one of the stabilizers may be used alone, or two or more may be used in combination.
  • the amount of the stabilizer added is preferably from 0.01 to 30% by weight, more preferably from 0.05 to 25% by weight, and even more preferably from 0.1 to 20% by weight of the total resin composition.
  • the resin composition of this embodiment may, if desired, contain (I) a coupling agent (hereinafter also referred to as "component (I)") to the extent that the effect of the invention is not impaired.
  • the coupling agent has two or more different functional groups in its molecule, one of which is a functional group that chemically bonds to an inorganic material and the other is a functional group that chemically bonds to an organic material.
  • the adhesive strength of the resin composition to substrates and other materials is improved when the resin composition contains a coupling agent.
  • Examples of the (I) coupling agent include, but are not limited to, a silane coupling agent, an aluminum coupling agent, a titanium coupling agent, and the like depending on the type of functional group that chemically bonds with an inorganic material.
  • the coupling agent examples include, but are not limited to, epoxy, amino, vinyl, methacrylic, acrylic, mercapto, and other types of coupling agents, depending on the type of functional group that chemically bonds with an organic material.
  • an epoxy coupling agent containing an epoxy group is preferred from the viewpoint of moisture reliability.
  • epoxy silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane (trade name: KBM403, from Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (trade name: KBE-403, from Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyl methyl diethoxysilane (trade name: KBE-402, from Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyl methyl dimethoxysilane (trade name: KBM402, from Shin-Etsu Chemical Co., Ltd.), 8-glycidoxyoctyltrimethoxysilane (trade name: KBM-4803, from Shin-Etsu Chemical Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane (trade name: KBM-303, from Shin-Etsu Chemical Co., Ltd.), and the like
  • methacrylic silane coupling agent examples include 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, from Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl methyl dimethoxysilane (trade name: KBM502, from Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl methyl diethoxysilane (trade name: KBE502, from Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (trade name: KBE503, from Shin-Etsu Chemical Co., Ltd.), and the like.
  • acrylic silane coupling agent examples include 3-acryloxypropyltrimethoxysilane (trade name: KBM-5103, from Shin-Etsu Chemical Co., Ltd.), and the like.
  • the methacrylic silane coupling agent and acrylic silane coupling agent differ from component (C) in that they have functional groups that chemically bond to the inorganic material, and are not included in component (C).
  • mercaptosilane coupling agent examples include 3-mercaptopropyltrimethoxysilane (trade name: KBM803, from Shin-Etsu Chemical Co., Ltd.), 3-mercaptopropylmethyldimethoxysilane (trade name: KBM802, from Shin-Etsu Chemical Co., Ltd.), and the like.
  • any one of the coupling agent may be used alone, or two or more may be used in combination.
  • the amount of the coupling agent added is preferably 0.01% to 30% by weight, more preferably 0.1% to 10% by weight of the total resin composition from the viewpoint of improving adhesive strength.
  • the resin composition of this embodiment may, if desired, further contain other additives, such as carbon black, titanium black, an ion trap agent, a leveling agent, an antioxidant, a defoaming agent, a viscosity adjuster, a flame retardant, a colorant, a solvent, and the like, to the extent that the purpose of this embodiment is not compromised.
  • additives such as carbon black, titanium black, an ion trap agent, a leveling agent, an antioxidant, a defoaming agent, a viscosity adjuster, a flame retardant, a colorant, a solvent, and the like.
  • the type and amount of each additive is as usual.
  • the method of producing the resin composition of this embodiment is not limited.
  • components (A) to (D), components (E), (F), (G), (H), (I), and (J) other additives, and the like, if necessary, can be introduced simultaneously or separately into an appropriate mixing machine and mixed by stirring while melting by heating if necessary, to obtain a uniform composition as the resin composition of this embodiment.
  • the mixing machine is not limited, and can be a ricer, Henschel mixer, 3-roll mill, ball mill, planetary mixer, bead mill, and the like, equipped with an agitator and heating device. A combination of these devices may also be used as appropriate.
  • the resin composition thus obtained is thermosetting, and under a temperature of 80°C, it preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour.
  • the curable composition of this embodiment is used in the manufacture of a semiconductor module containing components that deteriorate under a high temperature condition, it is preferred that the composition be thermally cured at a temperature of 50 to 90°C for 30 to 120 minutes.
  • the resin composition of this embodiment is of low volatility. Volatility can be determined from the weight loss on heating. The weight loss on heating is preferably 1% or less, more preferably 0.7% or less, and even more preferably 0.5% or less.
  • the resin composition of this embodiment is the resin composition as mentioned above for use in curing by heat alone. Use of the resin composition as mentioned above in curing by heat alone is also one embodiment of the present invention.
  • the resin composition of this embodiment contains the component (E) and the component (G)
  • the resin composition can also be cured by light (UV).
  • UV light
  • the resin composition can be cured preliminarily by light (UV) curing, and then cured mainly by heat curing.
  • the resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, bonding, or protecting parts comprising a semiconductor device or an electronic component, or as a raw material thereof.
  • An adhesive or sealant which is the second embodiment of the invention, contains the resin composition of the first embodiment described above.
  • the adhesive or sealant enables good fixation, bonding, or protection for engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.) and can be used to fix, bond, or protect parts comprising a semiconductor device or an electronic component.
  • the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, integrated circuits, and the like.
  • the adhesive or sealant of this embodiment can cure under a low temperature condition and give a cured product with an excellent stress relaxation property, making it highly productive and suitable for use in the manufacture of semiconductor devices and electronic components, for example, where multiple parts made of different materials are joined and assembled.
  • the adhesive or sealant of this embodiment is suitable for use in the manufacture of semiconductor modules with miniaturized electronic components, for example, because of low self-exothermic temperature during curing reaction.
  • the adhesive or sealant of this embodiment is the adhesive or sealant as mentioned above for use in curing by heat alone. Use of the adhesive or sealant as mentioned above in curing by heat alone is also one embodiment of the present invention.
  • the cured product of the third embodiment of the present invention is a cured product in which the resin composition of the first embodiment or the adhesive or sealant of the second embodiment described above has been cured.
  • the cured product has an excellent stress relaxation property.
  • the semiconductor device or electronic component of the fourth embodiment of the present invention has high reliability, especially in a semiconductor device or electronic component assembled by joining multiple parts made of different materials, because it contains the cured product of the third embodiment described above.
  • semiconductor device refers to all devices that can function by utilizing semiconductor characteristics and includes electronic components, semiconductor circuits, modules incorporating these components, and electronic equipment. Examples of the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, integrated circuits, and the like.
  • Examples 1 to 24 and Comparative Examples 1 to 2 Each of resin compositions was prepared by mixing each of the components in the amounts according to the formulations shown in Table 1 using a three-roll mill. In Table 1, the amount of each component is expressed in parts by weight (unit: g). The ingredients used in the examples and comparative examples are as follows.
  • A Polyfunctional epoxy compound (Component (A))
  • A-1 Bisphenol F epoxy resin and bisphenol A epoxy resin mixture (trade name: EXA-835LV, available from DIC Corporation, epoxy equivalent weight: 165 g/eq)
  • A-2 Liquid epoxy compound (trade name: jER YX7400, available from Mitsubishi Chemical Corporation; epoxy equivalent weight: 450 g/eq)
  • A-3 PO-modified bisphenol liquid epoxy resin (trade name: AER9000, available from Asahi Kasei Corporation, epoxy equivalent weight: 380 g/eq)
  • A-4) Bisphenol F epoxy resin (trade name: jER4005P, available from Mitsubishi Chemical Corporation, epoxy equivalent weight: 1004 g/eq)
  • A-5 Epoxy resin in component (D-1) (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent weight: 180 g/eq)
  • B Polyfunctional thiol compound (Component (B))
  • B-1 Pentaerythritol tetrakis(3-mercaptopropionate) (trade name: PEMP, available from SC Organic Chemical Co., Ltd., thiol equivalent weight: 122 g/eq)
  • B-2 1,3,4,6-Tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, available from Shikoku Chemicals Corporation, thiol equivalent weight: 100 g/eq)
  • B-3) 1,3,4,6-Tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, available from Shikoku Chemicals Corporation, thiol equivalent weight: 114 g/eq)
  • B-4) Trimethylolpropane tris(3-mercaptopropionate) (trade name: TMMP, available from SC Organic Chemical Co., Ltd., thiol equivalent
  • (C) Monofunctional compound having one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule
  • Component (C)) (C-1): Dicyclopentanyl acrylate (trade name: FA513AS, available from Showa Denko Materials Co., Ltd., (meth)acryloyl equivalent weight: 206 g/eq)
  • C-2) Isobornyl acrylate (trade name: IBXA, available from Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent weight: 208 g/eq)
  • C-3) 2-(o-phenylphenoxy)ethyl acrylate (trade name: HRD-01, available from Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl equivalent weight: 268 g/eq)
  • C-4) (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name
  • (D) Curing catalyst Component (D) (D-1): Amine-epoxy adduct-type latent curing catalyst (trade name: Novacure HXA9322HP, available from Asahi Kasei Corporation) (D-2): Urea adduct-type latent curing catalyst (trade name: Fujicure FXR1121, available from T & K TOKA Co., Ltd.)
  • the epoxy resins constituting this dispersion are treated as forming part of component (A).
  • Table 1 therefore, the amount of the latent curing catalyst only in (D-1) is shown in a row for component (D), and the amount of epoxy resin in (D-1) is shown in a row for component (A) as component (A-5).
  • F Filler (Component (F))
  • F-1 Silica filler 1 (trade name: SE2300, available from Admatechs Company Limited, average particle diameter: 0.6 ⁇ m)
  • F-2) Silica filler 2 (trade name: Admanano YA050C-SM1, available from Admatechs Company Limited, average particle diameter: 50 nm)
  • F-3 Monodisperse cross-linked styrene particles (trade name: SX350H, available from Soken Chemical & Engineering Co., Ltd., average particle diameter: 3.5 ⁇ m)
  • H Stabilizer (Component (H))
  • H-1 Triisopropylborate (available from Tokyo Chemical Industry Co., Ltd.)
  • H-2) N-nitroso-N-phenylhydroxylamine aluminum salt (trade name: Q1301, available from FUJIFILM Wako Pure Chemical Corporation)
  • the "((A)+(C)+(E)+(Z))/(B)” represents a ratio of a total of an equivalent number of the epoxy group of the component (A), an equivalent number of the group (c) of the component (C), an equivalent number of the (meth)acryloyl group of the component (E) and an equivalent number of the epoxy group of the component (Z) to an equivalent number of the thiol group of the component (B) (([an equivalent number of the epoxy group of the component (A)] + [an equivalent number of the group (c) of the component (C)] + [an equivalent number of the (meth)acryloyl group of the component (E)] + [an equivalent number of the epoxy group of the component (Z)])/[an equivalent number of the thiol group of the component (B)]).
  • the "(A)/(B)” represents a ratio of an equivalent number of the epoxy group of the component (A) to an equivalent number of the thiol group of the component (B) ([an equivalent number of the epoxy group of the component (A)] /[an equivalent number of the thiol group of the component (B)]).
  • the "(C)/(B)” represents a ratio of an equivalent number of the group (c) of the component (C) to an equivalent number of the thiol group of the component (B) ([an equivalent number of the group (c) of the component (C)] /[an equivalent number of the thiol group of the component (B)]).
  • the "(E)/(B)” represents a ratio of an equivalent number of the (meth)acryloyl group of the component (E) to an equivalent number of the thiol group of the component (B) ([an equivalent number of the (meth)acryloyl group of the component (E)] /[an equivalent number of the thiol group of the component (B)]).
  • the "(Z)/(B)” represents a ratio of an equivalent number of the epoxy group of the component (Z) to an equivalent number of the thiol group of the component (B) ([an equivalent number of the epoxy group of the component (Z)] /[an equivalent number of the thiol group of the component (B)]).
  • the elongation at break obtained from the above test shows that the each elongation at break of Examples 1 to 24 containing component (C) is greater than that of Comparative Example 1, which does not contain component (C).
  • the elongation at break is preferably 40% or more, more preferably 70% or more, and even more preferably 100% or more.
  • Volatilization amount (%)] 100 x ⁇ [Weight of the entire container containing the resin composition before thermal curing process (g)] - [Weight of the entire container after thermal curing process (g)] ⁇ / [Weight of the initial resin composition (g)] --- Formula (1) Volatilization amount during thermal curing process obtained by the above test is preferably 1.0% or less, more preferably 0.7% or less, and even more preferably 0.5% or less.
  • the cured products of the resin compositions of Examples 1 to 24 all have high elongation at break and excellent flexibility (stress relaxation property).
  • the resin compositions of Examples 1 to 24 had low self-exothermic temperatures during the curing reaction.
  • the resin compositions of Examples 1 to 24 had low volatilization amounts during the thermal curing process.
  • the cured product of the resin composition of Comparative Example 1 which did not contain component (C), had a low elongation at break and did not meet the required stress relaxation property criteria.
  • the resin composition of Comparative Example 1 had a high self-exothermic temperature during the curing reaction.
  • the resin composition of Comparative Example 2 containing (Z) monofunctional epoxy compound instead of component (C) had a high self-exothermic temperature during the curing reaction.
  • the present invention is a resin composition that cures under a low temperature condition, gives a cured product with excellent stress relaxation properties, and has a low self-exothermic temperature during the curing reaction.
  • the resin composition is very useful as an adhesives or sealant suitable for use in the manufacture of a semiconductor device and an electronic component that are assembled by joining multiple parts made of different materials.

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Abstract

L'objet de la présente invention est de fournir une composition de résine et un adhésif qui durcissent dans des conditions de basse température, donnent un produit durci ayant une excellente propriété de relaxation de contrainte, et ont une faible température auto-exothermique pendant une réaction de durcissement. La présente invention concerne une composition de résine comprenant (A) un composé époxy polyfonctionnel, (B) un composé thiol polyfonctionnel, (C) un composé monofonctionnel ayant un groupe (c) contenant une double liaison insaturée et un groupe attracteur d'électrons adjacent à celui-ci dans sa molécule, et (D) un catalyseur de durcissement.
PCT/JP2022/047359 2022-10-28 2022-12-22 Composition de résine, adhésif, agent d'étanchéité, produit durci, dispositif à semi-conducteur et composant électronique WO2024089905A1 (fr)

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