Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—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
  • C08G59/66—Mercaptans
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present invention relates to an epoxy resin composition, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and electronic component containing the cured product.
• curable resin compositions are often used in the assembly and mounting of semiconductor devices and electronic components, such as semiconductor chips, for the purpose of maintaining reliability.
• compounds having multiple thiol groups in the molecule are useful as curing agents for epoxy resins.
• epoxy resin compositions are known that use a polythiol compound as a curing agent and contain a reaction product of an amine and an epoxy compound as a curing accelerator (e.g., Patent Documents 1 and 2).
• Patent Document 3 describes a compound having the following structural formula: Disclosed is a trithiol compound having the formula:
• Patent Document 3 discloses that when a resin composition containing this trithiol compound is used as an adhesive, it is possible to improve the adhesive strength with an adherend, which has been a problem in the past.
• the present inventors have found that an epoxy resin composition containing this trithiol compound as a curing agent has insufficient curing properties at low temperatures (e.g., 70°C).
• low temperatures e.g. 70°C.
• all of the manufacturing processes must be carried out under low-temperature conditions. Therefore, adhesives and sealants used in the manufacture of such devices and components are required to exhibit sufficient curing properties even under low-temperature conditions.
• the present invention aims to provide an epoxy resin composition that has good low-temperature curing properties even when it contains a specific trithiol compound, an adhesive or sealant containing the same, a cured product, and a semiconductor device or electronic component.
• Embodiments of the present invention include an epoxy resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component having the following aspects.
• A Chemical formula (I): A thiol compound represented by the formula: (B) a thiol compound having an isocyanuric acid skeleton, An epoxy resin composition comprising: (C) an epoxy resin; and (D) a thermal latent curing catalyst.
• the (B) thiol compound having an isocyanuric acid skeleton is represented by the formula (II):
• R 1 , R 2 and R 3 are each independently a C 1-6 alkylene group or -R 4 -Z-(CO) n -R 5 -, R 4 and R 5 are each independently a C 1-6 alkylene group, Z is a sulfur atom or an oxygen atom, n is 0 or 1, and R 4 is bonded to the nitrogen atom of the isocyanuric acid skeleton.
• an epoxy resin composition that has good low-temperature curing properties even when it contains a specific trithiol compound, an adhesive or sealant containing the same, a cured product obtained by curing the same, and a semiconductor device or electronic component containing the cured product.
• resin which normally refers to a polymer (especially a synthetic polymer), may be used to refer to the components that make up a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing.
• the epoxy resin composition according to one embodiment of the present invention comprises: (A) Chemical formula (I): A thiol compound represented by the formula: (B) a thiol compound having an isocyanuric acid skeleton,
• the present embodiment includes an epoxy resin composition having good low-temperature curing properties, even when the epoxy resin composition includes a thiol compound represented by chemical formula (I).
• the epoxy resin composition of the present embodiment comprises (A) a thiol compound represented by chemical formula (I):
• the thiol compound represented by chemical formula (I) acts as a curing agent for epoxy resins.
• the thiol compound represented by chemical formula (I) can be synthesized, for example, by reacting 1,2,3-triallyloxypropane with a thiocarboxylic acid and solvolyzing the resulting thioester according to the method described in Patent Document 3 (JP-A-2022-180364) or the method described in JP-A-2023-126883.
• the thiol compound represented by chemical formula (I) acts as a curing agent for epoxy resin, and the curing agent may contain by-products that are produced during the synthesis of the thiol compound represented by chemical formula (I).
• by-products include, but are not limited to, the compounds represented by the following chemical formulas (I-1) to (I-9) described in JP 2022-180364 A.
• by-products include, but are not limited to, (0) thiol compounds represented by chemical formulas (I-1) to (I-45) described in JP 2023-126883 A, (1) multimers of these thiol compounds (e.g., dimers, trimers, etc.), (2) condensates of two or more selected from these thiol compounds, and (3) condensates of one or more selected from these thiol compounds and one or more selected from the thiol compounds represented by chemical formulas (IV-1) to (IV-6) described in JP 2023-126883 A.
• component (A) contains a by-product of a thiol compound represented by the chemical formula (I), for example, the compounds represented by (I-1) to (I-9) described in JP-A-2022-180364 and the compounds described in JP-A-2023-126883
• the ratio of the content of the by-product of the thiol compound represented by the chemical formula (I) to the content of the thiol compound represented by the chemical formula (I) is preferably 0.02 to 0.3, more preferably 0.02 to 0.25, even more preferably 0.05 to 0.25, and most preferably 0.05 to 0.20.
• the ratio of the content of each compound in the curing agent is a value calculated using the peak area of each component when the curing agent is analyzed by liquid chromatography.
• the content of component (A) in the epoxy resin composition is preferably 1 to 60% by weight, more preferably 5 to 60% by weight, even more preferably 5 to 55% by weight, and particularly preferably 5 to 50% by weight, based on the total weight of the epoxy resin composition.
• the epoxy resin composition of the present embodiment contains (B) a thiol compound having an isocyanuric acid skeleton (hereinafter also referred to as "component (B)").
• component (B) a thiol compound having an isocyanuric acid skeleton
• an epoxy resin composition containing the thiol compound represented by chemical formula (I) as a curing agent has insufficient curing properties at low temperatures (e.g., 70°C).
• the present inventors thought that the thiol compound represented by chemical formula (I), which has very few polar moieties in its structure, is difficult to extract the protons of the thiol groups, especially at low temperatures.
• an ester-based thiol such as pentaerythritol tetrakis (3-mercaptopropionate
• it is easy to form a six-membered ring structure so that the proton (H) is easily removed.
• the thiol compound (B) having an isocyanuric acid skeleton is preferably a trithiol having an isocyanuric acid skeleton, and has the formula (II):
• R 1 , R 2 and R 3 are each independently a C 1-6 alkylene group or -R 4 -Z-(CO) n -R 5 -
• R 4 and R 5 are each independently a C 1-6 alkylene group
• Z is a sulfur atom or an oxygen atom
• n is 0 or 1
• R 4 is bonded to the nitrogen atom of the isocyanuric acid skeleton.
• the C 1-6 alkylene group may be either linear or branched.
• thiol compounds having an isocyanuric acid skeleton include 2- ⁇ 2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl ⁇ ethyl 3-sulfanylpropionate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, and 1,3,5-tris[3-(2-mercaptoethoxy)propyl]isocyanurate.
• 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione tris(mercaptomethyl)isocyanurate, tris(2-mercaptoethyl)isocyanurate, tris(3-mercaptopropyl)isocyanurate, tris(4-mercaptobutyl)isocyanurate, tris(5-mercaptopentyl)isocyanurate, and the like, but are not limited thereto.
• These thiol compounds having an isocyanuric acid skeleton may be used alone or in combination of two or more.
• the molar ratio of component (A) to component (B) ([component (A)]/[component (B)]) is preferably 0.01 to 100, more preferably 0.05 to 100, even more preferably 0.1 to 95, and particularly preferably 0.4 to 95.
• the weight ratio of component (A) to component (B) ([component (A)]/[component (B)]) is preferably 0.01 to 100, more preferably 0.05 to 90, even more preferably 0.1 to 80, and particularly preferably 0.3 to 70.
• the molar ratio of component (A) to the total amount of component (A) and component (B) ([component (A)]/ ⁇ [component (A)]+[component (B)] ⁇ ) is preferably 0.01 to 0.99, more preferably 0.02 to 0.99, and even more preferably 0.04 to 0.99.
• the weight ratio of component (A) to the total amount of component (A) and component (B) ([component (A)]/ ⁇ [component (A)]+[component (B)] ⁇ ) is preferably 0.01 to 0.99, more preferably 0.02 to 0.99, and even more preferably 0.03 to 0.99.
• the epoxy resin composition of the present embodiment contains (C) an epoxy resin (hereinafter also referred to as “component (C)”).
• the epoxy resin is not particularly limited as long as it has at least two epoxy groups.
• the epoxy resin is a general term for thermosetting resins that can be cured by forming a crosslinked network with epoxy groups present in the molecule, and includes prepolymer compounds before curing. In consideration of ensuring heat resistance, the epoxy resin is more preferably one having 2 to 6 epoxy groups, and even more preferably one having 2 epoxy groups.
• the epoxy resin may be liquid or solid at 25°C, but is preferably liquid at 25°C. Epoxy resins are roughly classified into aromatic epoxy resins and epoxy resins having no aromatic ring.
• aromatic epoxy resin is an epoxy resin having a structure containing an aromatic ring such as a benzene ring.
• aromatic epoxy resins include: - bisphenol A type epoxy resin; - branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyl dimethyl trisbisphenol A diglycidyl ether; - bisphenol F type epoxy resin; - Novolac type epoxy resins; - tetrabromobisphenol A type epoxy resin; - fluorene type epoxy resin; -biphenylaralkyl type epoxy resin; -Diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; Biphenyl-type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; -glycidylamine type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-
• aromatic epoxy resins bisphenol F type epoxy resins, bisphenol A type epoxy resins, and glycidylamine type epoxy resins are preferred, and among them, those having an epoxy equivalent of 90 to 500 g/eq are more preferred, and those having an epoxy equivalent of 90 to 400 g/eq are even more preferred.
• the aromatic epoxy resin may be oxyalkylene-modified, such as EO (ethylene oxide)-modified or PO (propylene oxide)-modified.
• the aromatic epoxy resin is preferably liquid at 25°C.
• the viscosity at 25° C. is preferably from 0.1 to 100 Pa ⁇ s, more preferably from 0.5 to 100 Pa ⁇ s, and particularly preferably from 1 to 100 Pa ⁇ s.
• viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, it can be determined by measuring with an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.
• Epoxy resins that do not have an aromatic ring include, for example, aliphatic epoxy resins and epoxy resins that have a heterocyclic ring.
• aliphatic epoxy resins include: - 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, dicyclopentadiene type diglycidyl ether; - triepoxy compounds such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; - alicyclic epoxy resins such as vinyl(3,4-cyclohex
• the aliphatic epoxy resin preferably has an epoxy equivalent of 90 to 450 g/eq. Also, it is preferable that the resin is liquid at 25° C. Also, it is preferable that the viscosity at 25° C. is 10 to 10,000 mPa ⁇ s, and more preferably 10 to 5,000 mPa ⁇ s.
• Epoxy resins having a heterocycle include isocyanuric acid type epoxy resins and glycoluril type epoxy resins. Epoxy resins having a heterocycle preferably have an epoxy equivalent of 80 to 450 g/eq. From the viewpoint of workability, it is preferable that they are liquid at 25°C. It is also preferable that they have a viscosity at 25°C of 100 to 50,000 mPa ⁇ s, and more preferably 100 to 5,000 mPa ⁇ s. On the other hand, from the viewpoint of adhesion, it is preferable that they are solid at 25°C.
• the content of the epoxy resin (C) in the epoxy resin composition is preferably 30 to 75% by weight, more preferably 30 to 60% by weight, and even more preferably 35 to 60% by weight, based on the total weight of the epoxy resin composition.
• the total content of component (A) and component (B) in the epoxy resin composition is preferably 1 to 70% by weight, more preferably 10 to 65% by weight, and even more preferably 20 to 60% by weight, based on the total weight of the epoxy resin composition.
• the ratio of the number of epoxy group equivalents of the epoxy resin to the sum of the number of thiol group equivalents of component (A) and the number of thiol group equivalents of component (B) is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 6, particularly preferably 0.4 to 2, and most preferably 0.5 to 1.5.
• functional group equivalents such as thiol equivalent and epoxy equivalent refer to the molecular weight of a compound per functional group
• functional group equivalents such as thiol group equivalent number and epoxy group equivalent number refer to the number of functional groups (equivalent number) per compound weight (charge amount).
• the epoxy equivalent of an epoxy resin is the molecular weight of the epoxy resin divided by the number of epoxy groups in one molecule.
• the actual epoxy equivalent can be determined by the method described in JIS K7236.
• the epoxy group equivalent of an epoxy resin is the number of epoxy groups (equivalent number) per weight (charged amount) of epoxy resin, and is the quotient obtained by dividing the weight (g) of the epoxy resin by the epoxy equivalent of that epoxy resin (if multiple epoxy resins are included, the sum of such quotients for each epoxy resin).
• the thiol equivalent of a thiol compound is the molecular weight of the thiol compound divided by the number of thiol groups in one molecule.
• the actual thiol equivalent can be determined, for example, by measuring the thiol value using potential difference. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A.
• the thiol group equivalent number of a thiol compound is the number of thiol groups (equivalent number) per weight (charge amount) of the thiol compound, and is the quotient obtained by dividing the weight (g) of the thiol compound by the thiol equivalent of that thiol compound (when multiple thiol compounds are included, the sum of such quotients for each thiol compound).
• the epoxy resin composition of the present embodiment contains (D) a thermal latent curing catalyst (hereinafter also referred to as "component (D)").
• the thermal latent curing catalyst is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst, and examples of the thermal latent curing catalyst include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct-based latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts). From the viewpoints of pot life and curability, solid-dispersed amine adduct-based latent curing catalysts are preferred as component (D).
• imidazole-isocyanuric acid adducts include, but are not limited to, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.
• Epoxy compounds used as one of the raw materials for manufacturing solid dispersion type amine adduct latent curing catalysts include, for example, polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid; phthalic acid, terephthalic acid, and the like.
• polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol
• glycidyl ether esters obtained by reacting epichlor
• epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting polycarboxylic acids such as glycidyl acid with epichlorohydrin; glycidyl amine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, and epoxidized polyolefin, as well as monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.
• polyglycidyl esters obtained by reacting polycarboxylic acids such as glycidyl acid with epichlorohydrin
• glycidyl amine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol
• the amine compound used as another manufacturing raw material for the solid dispersion type amine adduct latent curing catalyst may be any compound that has at least one active hydrogen atom capable of addition reacting with an epoxy group in the molecule, and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds are shown below, but are not limited to these.
• aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane
• aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline
• heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; and the like, but are not limited to these.
• compounds having a tertiary amino group in the molecule are particularly useful as raw materials that provide latent curing catalysts with excellent curing acceleration capabilities.
• examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.
• Primary or secondary amines having a tertiary amino group in the molecule such as imidazole compounds such as imidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylamin
• Isocyanate compounds used as another manufacturing raw material for solid dispersion type amine adduct latent curing catalysts include, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and further, compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds.
• monofunctional isocyanate compounds such as n-butyl iso
• Examples of such compounds containing terminal isocyanate groups include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.
• urea compounds include, but are not limited to, urea and thiourea.
• the solid dispersion type latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned combination of two components, (a) an amine compound and an epoxy compound, (b) a combination of three components, the above-mentioned two components and an active hydrogen compound, or (c) a combination of two or three components, an amine compound and an isocyanate compound and/or a urea compound.
• Typical examples of commercially available latent curing catalysts include amine-epoxy adducts (amine adducts), such as “Amicure PN-23” (product name of Ajinomoto Fine Techno Co., Ltd.), “Amicure PN-40” (product name of Ajinomoto Fine Techno Co., Ltd.), “Amicure PN-50” (product name of Ajinomoto Fine Techno Co., Ltd.), and “Hardener X-3661S” (product name of ACR Co., Ltd.).
• amine adducts such as "Amicure PN-23" (product name of Ajinomoto Fine Techno Co., Ltd.), “Amicure PN-40” (product name of Ajinomoto Fine Techno Co., Ltd.), “Amicure PN-50" (product name of Ajinomoto Fine Techno Co., Ltd.), and “Hardener X-3661S” (product name of ACR Co., Ltd.).
• Examples of such compounds include, but are not limited to, "Fujicure FXR-1030" (product name of T&K TOKA Corporation), “Fujicure FXR-1121” (product name of T&K TOKA Corporation), “Fujicure FXR-1081” (product name of T&K TOKA Corporation), “Fujicure FXR-1061” (product name of T&K TOKA Corporation), and “Fujicure FXR-1171” (product name of T&K TOKA Corporation).
• Component (D) may be used alone or in combination of two or more types.
• the content of component (D) in the epoxy resin composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 0.5 to 10% by weight, based on the total weight of the resin composition.
• component (D) is provided in the form of a dispersion liquid in which it is dispersed in an epoxy resin.
• the ratio of the number of epoxy group equivalents of the entire epoxy resin to the number of thiol group equivalents of components (A) and (B) is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 6, particularly preferably 0.4 to 2, and most preferably 0.5 to 1.5.
• the epoxy resin composition of this embodiment may contain optional components other than the above components (A) to (D), such as those described below, as necessary, if desired.
• the epoxy resin composition of the present embodiment may contain a thiol compound other than component (A) and component (B) (hereinafter, also referred to as "other thiol compound").
• Examples of the other thiol compound include: Aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; Aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds; Mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6
• thiol compounds include trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl) 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
• the weight ratio of component (A) to other thiol compounds in the epoxy resin composition is preferably set to be 100:0 to 1:99.
• the ratio of the number of epoxy group equivalents of the whole epoxy resin to the number of thiol group equivalents of the whole thiol compounds by combining the number of thiol equivalents of components (A) and (B) with the number of thiol equivalents of the other thiol compounds ([number of epoxy group equivalents of the whole epoxy resin]/[number of thiol group equivalents of the whole thiol compounds]).
• the ratio of the number of epoxy group equivalents of the whole epoxy resin to the number of thiol group equivalents of the whole thiol compounds is preferably 0.1 to 10, more preferably 0.2 to 8, even more preferably 0.3 to 6, particularly preferably 0.4 to 2, and most preferably 0.5 to 1.5.
• the epoxy resin composition of the present embodiment may contain a filler within a range that does not impair the effects of the present invention.
• a filler in the epoxy resin composition, the linear expansion coefficient of the cured product obtained by curing the epoxy resin composition can be reduced, and thermal cycle resistance can be improved.
• the filler has a low elastic modulus, the stress generated in the cured product can be alleviated, and long-term reliability can be improved.
• Fillers are broadly classified into inorganic fillers and organic fillers.
• the inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient by its addition.
• inorganic materials that can be used include 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, and boron nitride. Any one of the inorganic fillers may be used, or two or more of them may be used in combination.
• the inorganic filler it is preferable to use silica filler, since it is possible to increase the loading amount.
• silica amorphous silica is preferable.
• the surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.
• organic fillers examples include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane skeleton, fillers with a butadiene skeleton, and styrene fillers.
• PTFE polytetrafluoroethylene
• silicone fillers acrylic fillers
• fillers with a urethane skeleton fillers with a butadiene skeleton
• styrene fillers examples include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane skeleton, fillers with a butadiene skeleton, and styrene fillers.
• the organic fillers may be surface-treated.
• the shape of the filler is not particularly limited and may be spherical, flaky, needle-like, irregular, etc.
• the average particle size 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 size refers to the volume-based median diameter (d 50 ) measured by a laser diffraction method in accordance with ISO-13320 (2009), unless otherwise specified.
• the lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
• the average particle size of the filler is preferably 0.01 ⁇ m to 5.0 ⁇ m, and more preferably 0.1 ⁇ m to 3.0 ⁇ m.
• Fillers having different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 ⁇ m or more and less than 0.1 ⁇ m and a filler having an average particle size of 0.1 ⁇ m to 6.0 ⁇ m may be used in combination.
• the filler content in the epoxy 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, based on the total weight of the epoxy resin composition.
• the epoxy resin composition of the present embodiment may contain a stabilizer, if desired, within a range that does not impair the effects of the present invention.
• the stabilizer can improve the storage stability of the epoxy resin composition of the present embodiment and extend its pot life.
• Various known stabilizers can be used as the stabilizer, but at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is preferred because of its high effect of improving storage stability.
• liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate,
• the liquid boric acid ester compound is preferred because it is liquid at room temperature (25° C.) and can keep the viscosity of the epoxy resin composition low.
• the aluminum chelate for example, Aluminum Chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used.
• the organic acid for example, barbituric acid can be used.
• the stabilizers may be used alone or in combination of two or more.
• the amount added is preferably 0.01 to 30% by weight, more preferably 0.05 to 25% by weight, and even more preferably 0.1 to 20% by weight, based on the total weight of the epoxy resin composition.
• the epoxy resin composition of the present embodiment may contain a reactive diluent, if desired, within a range that does not impair the effects of the present invention.
• the reactive diluent refers to a compound that has one epoxy group (glycidyl group) and has a relatively low viscosity at room temperature.
• the reactive diluent may have, in addition to the epoxy group, other polymerizable functional groups, for example, alkenyl groups such as vinyl and allyl; and unsaturated carboxylic acid residues such as acryloyl and methacryloyl.
• reactive diluents include monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, styrene oxide, and ⁇ -pinene oxide;
• monoepoxide compounds include those having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.
• a reactive diluent is included, its content is preferably 1 to 150 parts by weight per 100 parts by weight of epoxy resin.
• the epoxy resin composition of the present embodiment may further contain other additives, such as a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a solvent, etc.
• additives such as a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a solvent, etc.
• the type and amount of each additive are the same as in the conventional method, provided that the gist of the present embodiment is not impaired.
• the method for producing the epoxy resin composition of this embodiment is not particularly limited.
• components (A) to (D), and other optional components as necessary can be introduced simultaneously or separately into an appropriate mixer, and stirred and mixed while melting by heating if necessary to obtain a homogeneous composition, thereby obtaining the epoxy resin composition of this embodiment.
• This mixer is not particularly limited, but a Raikai mixer, Henschel mixer, triple roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirrer and heater can be used. These devices may also be used in appropriate combination.
• the epoxy resin composition of this embodiment can be a one-liquid type resin composition that is configured as being contained in a single container, or a two-liquid type (or multi-liquid type) resin composition that is configured as being divided into two or more containers, depending on the application, etc.
• a two-liquid type (or multi-liquid type) resin composition is used, the components (A) to (D) and other optional components as required can be selected in the same way as for the one-liquid type.
• the components (A) to (D) and other optional components as required can be divided into two or multiple liquids in any manner without particular restrictions.
• one or more selected from the components (A) to (D) and other optional components as required may be contained in each liquid, the components (A) to (D) and other optional components as required may be contained in one liquid, and there may be a liquid consisting only of the components (A) to (D) and/or other optional components as required.
• the division method may be A liquid: component (A), B liquid: component (B) and component (C) and component (D), A liquid: component (A) and component (B), B liquid: component (C) and component (D), A liquid: component (A) and component (C), B liquid: component (B) and component (D), A liquid: component (A) and component (D), B liquid: component (B) and component (C), A liquid: component (B), B liquid: component (A) and component (D), It may be component (C) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (A) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (B) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (B) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (C) and component (D), A liquid: component (A
• the B liquid may contain one or more selected from the components (A) to (D).
• components other than the components (A) to (D) e.g., other thiol compounds
• the components (A) to (D) are contained in liquid A and the other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered as the resin composition of this embodiment.
• the respective liquids can be considered as the resin composition of this embodiment.
• An example of a case in which the components (A) to (D) are each contained in a different liquid is, for example, a resin composition in which the components (A) to (D) are separated into two or more containers, specifically, a kit composed of multiple liquids containing any of the components (A) to (D).
• the epoxy resin composition thus obtained is thermosetting, and preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour at a temperature of 100°C.
• the epoxy resin composition of this embodiment is used to manufacture a semiconductor module containing components that deteriorate under high temperature conditions, it is preferable to thermally cure the composition at a temperature of 50 to 90°C for 30 to 120 minutes.
• the epoxy resin composition of this embodiment has excellent curing properties, particularly at low temperatures (e.g., 70°C).
• the epoxy resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components or components that constitute them, or as a raw material thereof.
• An adhesive or sealant according to one embodiment of the present invention includes the epoxy resin composition according to the above embodiment.
• This adhesive or sealant provides 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 components constituting a semiconductor device or electronic component.
• engineering plastics e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.
• ceramics e.g., copper, nickel, etc.
• metals e.g., copper, nickel, etc.
• semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and TOF sensor modules, semiconductor modules, and integrated circuits.
• the adhesive or sealant of this embodiment can be a one-component adhesive or sealant that is contained in a single container, or a two-component (or multi-component) adhesive or sealant that is divided into two or more containers, depending on the application, etc.
• the components (A) to (D) and other optional components as needed can be selected in the same way as for the one-component type, and the curing method is also the same as for the one-component type.
• the components (A) to (D) and other optional components as needed can be divided into two or multi-component in any way without particular restriction.
• each liquid may contain one or more selected from the components (A) to (D) and other optional components as required, the components (A) to (C) and other optional components as required may be contained in one liquid, or there may be a liquid consisting of only the components (A) to (C) and/or other optional components as required.
• the method of division may be liquid A: component (A), liquid B: component (B), component (C), and component (D), liquid A: component (A) and component (B), liquid B: component (C) and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), liquid A: component (A) and component (D), liquid B: component (B) and component (C), liquid A: component (B), and component (A) and component (D).
• component (C) and component (D A liquid: component (A) and component (B) and component (C), B liquid: component (A) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (B) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (B) and component (D), A liquid: component (A) and component (B) and component (C), B liquid: component (C) and component (D), A liquid: component (A) and component (B) and component (D), B liquid: component (C) and component (D).
• the B liquid may contain one or more selected from the components (A) to (D).
• components other than the components (A) to (D) e.g., other thiol compounds
• the components (A) to (D) are contained in liquid A and the other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered as the adhesive or sealant of this embodiment.
• the respective liquids can be considered as the adhesive or sealant of this embodiment.
• An example of a case in which the components (A) to (D) are each contained in a different liquid is, for example, an adhesive or sealant in which the components (A) to (D) are separated into two or more containers, specifically, a kit composed of multiple liquids containing any of the components (A) to (D).
• the cured product of one embodiment of the present invention is a cured product obtained by curing the epoxy resin composition, adhesive, or sealant of the above-mentioned embodiment.
• the cured product of this embodiment has good extensibility.
• the semiconductor device or electronic component of one embodiment of the present invention includes the cured product of the above-mentioned embodiment.
• the semiconductor device refers to a device in general that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc.
• Examples of the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, integrated circuits, etc.
• Epoxy resin compositions were prepared by mixing the prescribed amounts of each component using a three-roll mill according to the formulation shown in Table 1.
• Table 1 the amount of each component is expressed in parts by weight (unit: g).
• the components used in the examples and comparative examples are as follows.
• A Thiol compound represented by chemical formula (I)
• A-1 Thiol compound represented by chemical formula (I) (1,2,3-(3-mercaptopropyloxy)propane) (obtained from Shikoku Chemical Industry Co., Ltd., thiol equivalent: 106 g/eq). Note that this thiol equivalent is an average value of values actually measured by a known method, for example, the method disclosed in paragraph 0079 of JP-A-2012-153794.
• B Thiol compound having an isocyanuric acid skeleton
• B-1 2- ⁇ 2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl ⁇ ethyl 3-sulfanylpropionate represented by the following formula (product name: TEMPIC, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 175 g/eq)
• B-2) 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate represented by the following formula (product name: ACTOCURE (registered trademark) SS32, manufactured by Kawaguchi Chemical Industry Co., Ltd., thiol equivalent: 183 g/eq)
• Epoxy resin (C-1) Bisphenol F type epoxy resin/bisphenol A type epoxy resin mixture (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 163 g/eq)
• (D) Thermal Latent Curing Catalyst (D-1): Amine-epoxy adduct-based latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)
• D-2) Modified amine compound that is solid at room temperature (product name: Fujicure FXR-1020, manufactured by T&K Toka Corporation)
• molar ratio (A/(A+B)) is the molar ratio of component (A) to the total amount of component (A) and component (B) ([component (A)]/ ⁇ [component (A)]+[component (B)] ⁇ ).
• the "weight ratio (A/(A+B))” is the weight ratio of component (A) to the total amount of component (A) and component (B) ([component (A)]/ ⁇ [component (A)]+[component (B)] ⁇ ).
• Molar ratio (A/B) is the molar ratio of component (A) to component (B) ([component (A)]/[component (B)]).
• Weight ratio (A/B) is the weight ratio of component (A) to component (B) ([component (A)]/[component (B)]).
• the properties of the resin composition and the cured product obtained by curing the resin composition were measured as follows.
• Liquid A was component (C)
• Liquid B was component (A), component (B), and component (D).
• the epoxy resin compositions of Comparative Examples 1 and 2 which contained only the thiol compound represented by chemical formula (I) of component (A) as a curing agent for an epoxy resin, exhibited good curing properties at 120°C but poor curing properties at 70°C.
• the cured products obtained by curing the resin compositions of these Examples exhibited good elongation properties compared to the cured products obtained by curing the resin compositions of Comparative Examples 3 and 4, which contain only the thiol compound having an isocyanuric acid skeleton of component (B) as a curing agent for an epoxy resin.
• the cured products of Examples 3 to 6 exhibited good elongation properties compared to the cured products of the resin compositions of Comparative Examples 1 and 2, which contain only the component (A) as a curing agent.
• similar evaluations were also performed on a two-component resin composition in which the composition of Example 1 was changed to A liquid: component (C), and B liquid: component (A), component (B), and component (D), and similar results were obtained.
• the epoxy resin composition of the present invention is extremely useful, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components or the components that constitute them, or as a raw material for such adhesives or sealants.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Epoxy Resins (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=94374962

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (11)

• 2024
  • 2024-07-11 JP JP2025535729A patent/JPWO2025023051A1/ja active Pending
  • 2024-07-11 CN CN202480042250.3A patent/CN121399182A/zh active Pending
  • 2024-07-11 TW TW113126053A patent/TW202506798A/zh unknown
  • 2024-07-11 WO PCT/JP2024/025149 patent/WO2025023051A1/ja active Pending
  • 2024-07-11 KR KR1020257043339A patent/KR20260038862A/ko active Pending

Patent Citations (11)

Also Published As

Similar Documents

Legal Events