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 inventors found that when an epoxy resin composition containing this trithiol compound was applied to a metal substrate, significant discoloration of the metal substrate was observed in a moisture resistance reliability test, compared to epoxy resin compositions containing other conventional thiol compounds. Discoloration not only reduces commercial value due to poor appearance, but can also lead to corrosion, and once corrosion products are generated, they can progress to the surrounding metal, which can be problematic, particularly in semiconductor devices and electronic components where the distance between components is short.
• the present invention aims to provide an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, 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.
• (1) an epoxy resin having a halogen content of 1,600 ppm or less;
• B Chemical formula (I):
• C a basic curing catalyst.
• (2) The epoxy resin composition according to the above aspect (1), wherein the (C) basic curing catalyst is a thermal latent curing catalyst.
• the adhesive or sealant according to the above aspect (6) which is for use in a semiconductor device or electronic component.
• a semiconductor device or electronic part comprising the cured product according to aspect (8).
• an epoxy resin composition that suppresses discoloration of an adherend to which it is applied, 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.
• Example 1 is a photograph taken from above of a copper substrate used in the discoloration evaluation of Example 1, Comparative Example 2, and Reference Example 1 after being left to stand for 20 hours in an 85° C./85% RH environment.
• 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) an epoxy resin having a halogen content of 1600 ppm or less; (B) Chemical formula (I): and (C) a basic curing catalyst. According to this embodiment, even when the epoxy resin composition contains a thiol compound represented by chemical formula (I), discoloration of an adherend to which the epoxy resin composition is applied is suppressed.
• the epoxy resin composition of the present embodiment contains (A) an epoxy resin having a halogen content of 1600 ppm or less (hereinafter, also referred to as "component (A)").
• component (A) an epoxy resin having a halogen content of 1600 ppm or less
• the present inventors have found that, although an epoxy resin composition containing a thiol compound represented by chemical formula (I) has excellent adhesive strength, when this epoxy resin composition is applied to a metal substrate, a significant discoloration of the metal substrate is observed in a moisture resistance reliability test, compared to epoxy resin compositions containing other conventional thiol compounds. The reason for this discoloration is unclear, but the present inventors speculate as follows. First, the thiol compound represented by chemical formula (I) has very few polar moieties other than the thiol group in its structure compared to other conventional thiol compounds, so that when it comes into contact with a highly polar surface such as a metal surface, the thiol group is relatively likely to approach the metal surface.
• the thiol group of the thiol compound represented by chemical formula (I) is more likely to be present on the metal surface than other conventional thiol compounds. It was believed that, during the moisture resistance reliability test, halogens and water, which have a high affinity for polar metal surfaces, move to the metal surface, causing some kind of reaction between the thiol group on the metal surface, the halogen, water, and the metal, resulting in the discoloration. Therefore, in order to reduce the halogen concentration on the metal surface, the halogen content of the epoxy resin contained in the resin composition was controlled to a certain amount or less, and it was found that discoloration of the metal substrate was suppressed.
• the halogen content of the epoxy resin as component (A) is 1600 ppm or less, preferably 1500 ppm.
• the halogen is at least one selected from fluorine, chlorine, bromine, and iodine. Chlorine may be contained in the epoxy resin during the synthesis process.
• the chlorine content of the epoxy resin as component (A) is 1600 ppm or less, preferably 1500 ppm.
• the halogen content of the epoxy resin is, for example, the total chlorine content when the halogen is chlorine, and can be quantified by a known method, for example, a sample combustion-ion chromatography method in accordance with BS EN 14582:2007.
• oxygen or argon is introduced into a heated quartz combustion tube to combust the sample, the generated combustion gas is absorbed in an absorption liquid, and the absorption liquid is fractionated and quantified by an ion chromatograph to determine the content in the sample.
• this pretreatment method include a flask combustion method, a bomb combustion method, and a combustion tube method.
• the epoxy resin as component (A) is not particularly limited as long as it has a halogen content of 1600 ppm or less and at least two epoxy groups.
• the term "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 resins are epoxy resins that have a structure containing an aromatic ring such as a benzene ring. Many of the epoxy resins that have been used frequently in the past, such as bisphenol A type epoxy resins, are of this type.
• 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
• 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.
• Epoxy resin may be used alone or in combination of two or more types.
• the content of the epoxy resin (A) in the epoxy resin composition is preferably 10 to 90% by weight, more preferably 15 to 85% by weight, and even more preferably 20 to 80% by weight, based on the total weight of the epoxy resin composition.
• the epoxy resin composition does not contain an epoxy resin having a halogen content of more than 1600 ppm.
• the epoxy resin composition contains an epoxy resin having a halogen content of more than 1600 ppm, there may be a portion in the epoxy resin composition where the halogen concentration is locally high, which may cause local discoloration. In applications where the composition is used in a narrow area, such as adhesives and sealants for semiconductor devices and electronic components, even local discoloration may lead to corrosion and may cause electrical failure.
• the epoxy resin composition contains an epoxy resin having a halogen content of more than 1600 ppm, the amount is, for example, 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the entire epoxy resin.
• the halogen content in the entire epoxy resin is 1600 ppm or less, and preferably 1500 ppm or less.
• the halogen content in the entire epoxy resin composition is 1600 ppm or less, and preferably 1500 ppm or less.
• the epoxy resin composition of the present embodiment comprises (B) 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 (B) contains a by-product of the thiol compound represented by the chemical formula (I), for example, the compounds represented by the chemical formulas (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 (B) in the epoxy resin composition is preferably 1 to 70% by weight, more preferably 10 to 60% by weight, and even more preferably 20 to 50% by weight, based on the total weight of the epoxy resin composition. Since component (B) has very few polar moieties other than thiol groups in its structure compared to other conventional thiol compounds, when it comes into contact with a highly polar surface such as a metal surface, the thiol groups are relatively likely to approach the metal surface. Therefore, even if the content of component (B) in the epoxy resin composition is small, discoloration of the metal substrate may occur.
• the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (B) is preferably 0.1 to 10, more preferably 0.2 to 10, 0.3 to 10, 0.4 to 10, or 0.5 to 10.
• functional group equivalents such as thiol equivalent and epoxy equivalent refer to the molecular weight of a compound per functional group
• functional group equivalent numbers 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 (C) a basic curing catalyst (hereinafter also referred to as "component (C)").
• component (C) the epoxy resin composition of the present embodiment can be cured in a short time even under low temperature conditions.
• the basic curing catalyst used in the present embodiment is not particularly limited as long as it is a curing catalyst for epoxy resins, and known basic curing catalysts can be used.
• Component (C) is preferably a latent curing catalyst.
• a latent curing catalyst is a compound that is inactive at room temperature, but is activated by heating to function as a curing catalyst. Examples 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 adduct systems); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adduct systems). From the standpoint of pot life and curability, solid-dispersed amine adduct-based latent curing catalysts are preferred as component (C).
• 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 FXR1121” (product name of T&K TOKA Corporation), “Fujicure FXR1081” (product name of T&K TOKA Corporation), “Fujicure FXR1061” (product name of T&K TOKA Corporation), and “Fujicure FXR1171” (product name of T&K TOKA Corporation).
• Component (C) may be used alone or in combination of two or more types.
• the content of component (C) 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 1 to 10% by weight, based on the total weight of the resin composition.
• component (C) 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 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.
• component (C) contains an epoxy resin
• the halogen content of the epoxy resin is preferably 1600 ppm or less.
• the epoxy resin composition of this embodiment may contain optional components other than the above components (A) to (C), such as those described below, if desired.
• the epoxy resin composition of the present embodiment may contain a thiol compound other than component (B) (hereinafter, also referred to as "other thiol compound").
• a thiol compound other than component (B) hereinafter, also referred to as "other thiol compound”
• 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-xy
• 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 the thiol compound of component (B) to the other thiol compounds in the epoxy resin composition is preferably set to 100:0 to 1:99.
• component (B) has very few polar moieties other than thiol groups in its structure, so that when it comes into contact with a highly polar surface such as a metal surface, the thiol groups tend to come relatively close to the metal surface. Therefore, even if the content of component (B) in the epoxy resin composition is small, discoloration of the metal substrate may occur.
• a thiol compound other than component (B) When a thiol compound other than component (B) is contained, it is preferable to calculate the ratio of the number of epoxy group equivalents of the entire epoxy resin to the number of thiol group equivalents of the entire thiol compounds ([number of epoxy group equivalents of the entire epoxy resin]/[number of thiol group equivalents of the entire thiol compounds]) by combining the number of thiol equivalents of component (B) and the number of thiol equivalents of the thiol compounds other than component (B).
• the ratio of the number of epoxy group equivalents of the entire epoxy resin to the number of thiol group equivalents of the entire 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 (C) and, if necessary, other optional components can be introduced into an appropriate mixer simultaneously or separately, 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 stirring device and a heating device can be used. These devices may also be used in appropriate combination.
• the epoxy resin composition of the present 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 (C) and other optional components as required can be selected in the same way as for the one-liquid type.
• the components (A) to (C) 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 (C) and other optional components as required may be contained in each liquid, the components (A) to (C) 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 (C) and/or other optional components as required.
• the division may be A liquid: component (A), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (C), A liquid: component (A) and component (B), B liquid: component (A) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (C), B liquid: component (B), A liquid: component (A) and component (C), B liquid: component (B) and component (C).
• the B liquid may contain one or more selected from the components (A) to (C).
• components other than the components (A) to (C) for example, thiol compounds other than the component (B)
• the components (A) to (C) 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 components (A) to (C) are each contained in a separate liquid, the respective liquids can be considered as the resin composition of this embodiment.
• An example of a case in which the components (A) to (C) are each contained in a separate liquid is, for example, a resin composition in which the components (A) to (C) are separated into two or more containers, specifically, a kit composed of multiple liquids containing any of the components (A) to (C).
• 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 that includes 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 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 (C) 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 (C) 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 components selected from the components (A) to (C) 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 division may be A liquid: component (A), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (C), A liquid: component (A) and component (B), B liquid: component (A) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (B), B liquid: component (B) and component (C), A liquid: component (A) and component (C), B liquid: component (B), A liquid: component (A) and component (C), B liquid: component (B) and component (C).
• the B liquid may contain one or more selected from the components (A) to (C).
• components other than the components (A) to (C) for example, thiol compounds other than the component (B)
• the components (A) to (C) 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 (C) are each contained in a different liquid is, for example, an adhesive or sealant in which the components (A) to (C) are separated into two or more containers, specifically, a kit composed of multiple liquids containing any of the components (A) to (C).
• the cured product according to one embodiment of the present invention is a cured product obtained by curing the epoxy resin composition, adhesive, or sealant according to the above-mentioned embodiment.
• the cured product is bonded to an adherend (particularly, a metal) and is prevented from discoloring.
• 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 Epoxy resin with halogen content of 1600 ppm or less
• A-1 YDF-8170 (bisphenol F type liquid epoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd., total chlorine content: 900 ppm, epoxy equivalent: 159 g/eq)
• A' Epoxy resin having a halogen content exceeding 1600 ppm
• A'-1): EP-4003S bisphenol A-PO type, manufactured by ADEKA Corporation, total chlorine content: 1800 ppm, epoxy equivalent: 255 g/eq
• Example 1 is a photograph taken from above of the copper substrate used in the discoloration evaluation of Example 1, Comparative Example 2, and Reference Example 1 after leaving it for 20 hours in an 85° C./85% RH environment. The same evaluation was also performed on the two-component resin composition in Example 1, in which liquid A was component (A), and liquid B was component (B) and component (C). "-": No discoloration of the substrate was observed. “+”: Some discoloration was observed on the board. "++”: Significant discoloration was observed on the substrate.
• the copper substrates coated with the epoxy resin compositions of Examples 1 and 2 containing epoxy resins with a halogen content of 1600 ppm or less showed no discoloration even after being left to stand for 20 hours in an environment of 85° C./85% RH.
• the copper substrates coated with the epoxy resin compositions of Comparative Examples 1 to 3 which did not contain an epoxy resin having a halogen content of 1600 ppm or less and contained an epoxy resin having a halogen content of more than 1600 ppm, were confirmed to have discolored after being left standing in an environment of 85°C/85% RH for 20 hours.
• the nickel substrate also gave similar results to those obtained with the copper substrate.
• Table 1 a similar evaluation was also performed on a two-component resin composition in which the composition of Example 1 was changed from A liquid: component (A) to B liquid: components (B) and (C), 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.

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