WO2023181831A1 - 樹脂組成物、接着剤又は封止材、硬化物、半導体装置及び電子部品 - Google Patents

樹脂組成物、接着剤又は封止材、硬化物、半導体装置及び電子部品 Download PDF

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WO2023181831A1
WO2023181831A1 PCT/JP2023/007785 JP2023007785W WO2023181831A1 WO 2023181831 A1 WO2023181831 A1 WO 2023181831A1 JP 2023007785 W JP2023007785 W JP 2023007785W WO 2023181831 A1 WO2023181831 A1 WO 2023181831A1
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resin composition
compound
group
epoxy
component
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PCT/JP2023/007785
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English (en)
French (fr)
Japanese (ja)
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恵莉 深澤
一希 岩谷
信幸 阿部
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ナミックス株式会社
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Priority to JP2024509905A priority Critical patent/JPWO2023181831A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a resinous composition, an adhesive or a sealing material containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.
  • Examples of resin compositions that have excellent low-temperature and rapid curing properties, have a low Tg (glass transition point) of the cured product, and whose Tg hardly changes even after a long period of time after curing include (A) epoxy that does not contain a benzene ring.
  • a resin composition containing a resin, (B) a thiol compound having two or more thiol groups in the molecule, and (C) a latent curing agent is disclosed (Patent Document 3).
  • an object of the present invention is to provide a low-temperature curable resin composition and an adhesive that can suppress the occurrence of the bleed phenomenon.
  • the first embodiment of the present invention is the following resin composition.
  • a second embodiment of the present invention is the following adhesive or sealant.
  • the third embodiment of the present invention is the following cured product.
  • a fourth embodiment of the present invention is the following semiconductor device or electronic component.
  • (6) A semiconductor device or electronic component comprising the cured product according to (5) above.
  • (7) The semiconductor device or electronic component according to (6) above, which is an image sensor or a camera module.
  • the first embodiment of the present invention it is possible to obtain a low-temperature curable resin composition that can suppress the occurrence of a bleed phenomenon. Furthermore, according to the second embodiment of the present invention, it is possible to obtain a low-temperature curing adhesive or sealing material that can suppress the occurrence of a bleed phenomenon. Furthermore, according to the third embodiment of the present invention, it is possible to obtain a cured product in which the occurrence of a bleed phenomenon is suppressed. According to the fourth embodiment of the present invention, it is possible to obtain a semiconductor device or an electronic component with excellent reliability and bondability because the cured product includes a cured product in which the occurrence of a bleed phenomenon is suppressed.
  • the resin composition that is the first embodiment of the present invention is (A) epoxy compound, (B) polythiol compound, Contains (C) a cyclic carbodiimide compound and (D) a curing catalyst. According to this embodiment, it is possible to obtain a low-temperature curable resin composition that can suppress the occurrence of a bleed phenomenon.
  • Epoxy compound (A) Epoxy compound (hereinafter also referred to as "component (A)") is not particularly limited as long as it contains a compound containing at least two epoxy groups. It can be used as component (A).
  • 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, compounds having two or more epoxy groups are preferred, compounds having 2 to 6 epoxy groups are more preferred, and compounds having two epoxy groups are even more preferred. From the viewpoint of viscosity adjustment, a compound having two or more epoxy groups and a compound containing one epoxy group may be used in combination. Epoxy compounds are broadly classified into aliphatic epoxy compounds and aromatic epoxy compounds.
  • aliphatic epoxy compounds include: -n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, ⁇ -pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)- Aliphatic monofunctional epoxy compounds such as 1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, neodecanoic acid glycidyl ester; -(Poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol
  • cyclohexane-type diglycidyl ether refers to two glycidyl groups each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as a parent structure. means a compound with a structure.
  • Dicyclopentadiene-type diglycidyl ether refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure. means.
  • the aliphatic epoxy compound preferably has an epoxy equivalent of 90 to 450 g/eq.
  • cyclohexane type diglycidyl ether cyclohexanedimethanol diglycidyl ether is more preferable.
  • An aromatic epoxy compound is an epoxy compound having a structure containing an aromatic ring such as a benzene ring.
  • aromatic epoxy compounds include: -Phenylglycidyl ether, cresylglycidyl ether, p-s-butylphenylglycidyl ether, styrene oxide, p-tert-butylphenylglycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, etc.
  • aromatic monofunctional epoxy compound - Bisphenol A type epoxy compound; - a branched polyfunctional bisphenol A type epoxy compound such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; - Bisphenol F type epoxy compound; - Novolac type epoxy compound; -Tetrabromobisphenol A type epoxy compound; -Fluorene type epoxy compound; - biphenylaralkyl epoxy compound; - diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; - biphenyl-type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; - Glycidylamine-type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylene diamine; and - Naphthalen
  • aromatic epoxy compound bisphenol F type epoxy compounds, bisphenol A type epoxy compounds and glycidylamine type epoxy compounds are preferable, and among them, those having an epoxy equivalent of 90 to 200 g/eq are more preferable, and those having an epoxy equivalent of 110 to 190 g /eq is more preferred.
  • the content of component (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total mass of the resin composition.
  • the resin composition of the present embodiment includes (B) a polythiol compound (hereinafter also referred to as "component (B)").
  • Component (B) is not particularly limited as long as it has two or more thiol groups.
  • Component (B) preferably has three or more thiol groups.
  • the thiol equivalent of component (B) is preferably 90 to 150 g/eq, more preferably 90 to 140 g/eq, even more preferably 90 to 130 g/eq.
  • Some polythiol compounds have low viscosity due to their structure.
  • the resin composition may be left at room temperature without being immediately subjected to heat curing treatment.
  • the polythiol compound contained in the resin composition of the present embodiment preferably has a viscosity at 25°C of 150 mPa ⁇ s or more, more preferably 200 mPa ⁇ s or more, and 250 mPa ⁇ s or more. It is more preferable that the pressure is 300 mPa ⁇ s or more, and it is particularly preferable that the pressure is 300 mPa ⁇ s or more. There is no particular restriction on the upper limit of the viscosity, and solid ones can also be used. Viscosity refers to a value measured at a measurement temperature of 25° C. using an appropriate viscometer depending on the viscosity range.
  • a polythiol compound (B) having an ester bond in the molecule can be used.
  • polythiol compounds having an ester bond in the molecule include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate).
  • component (B) having an ester bond in the molecule examples include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy) -ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis (3-mercaptopropionate) ) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis (3-mercaptobut
  • a polythiol compound (B) that does not have an ester bond in its molecule can be used.
  • examples of such component (B) include glycoluril compounds represented by the following general formula (1).
  • R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
  • n is an integer from 0 to 10.
  • component (B) may be a compound represented by the following chemical formula (2) or chemical formula (3).
  • a polythiol compound (B) having an ether bond in the molecule can be used.
  • examples of the polythiol compound (B) having an ether bond in the molecule include a polythiol compound represented by general formula (4).
  • R 3 , R 4 , R 5 and R 6 are each independently hydrogen or C n H 2n SH (n is 2 to 6 ); and at least two of R 6 are C n H 2n SH (n is 2 to 6).
  • n of the polythiol compound of component (B) represented by general formula (4) is preferably 2 to 4.
  • this polythiol compound is a mercaptopropyl group in which n is 3 from the viewpoint of the balance between the physical properties of the cured product and the curing speed.
  • Component (B) represented by the general formula (4) has a sufficiently flexible skeleton and is therefore effective when it is desired to lower the elastic modulus of the cured product. By adding component (B) represented by the general formula (4), the elastic modulus of the cured product can be controlled, so the adhesive strength (especially peel strength) after curing can be increased.
  • component (B) that do not have an ester bond in the molecule
  • thiol glycoluril derivative manufactured by Shikoku Kasei Kogyo product name: TS-G (corresponding to chemical formula (2), thiol equivalent: 100 g/eq)
  • product name: Examples include, but are not limited to, C3 TS-G (corresponding to chemical formula (3), thiol equivalent: 114 g/eq).
  • component (B) having an ether bond in the molecule there is a thiol compound manufactured by SC Organic Chemical Co., Ltd. (product name: PEPT (corresponding to general formula (4), thiol equivalent: 124 g/eq)).
  • a thiol compound manufactured by SC Organic Chemical Co., Ltd. product name: PEPT (corresponding to general formula (4), thiol equivalent: 124 g/eq)
  • component (B) having an ether bond in the molecule polyethylene glycol polythiol compound manufactured by Sigma-Aldrich (product name: HS-PEG1500-SH), polyether polythiol compound manufactured by Toray Fine Chemical Co., Ltd. (product name : Polythiol (registered trademark) QE340M), but is not limited thereto.
  • component (B) any one type may be used, or two or more types may be used in combination.
  • a component (B) having an ester bond in the molecule and a component (B) not having an ester bond in the molecule may be used together.
  • the ratio of the number of thiol group equivalents of component (B) to the number of epoxy group equivalents of component (A) is preferably 0.3 to 1.4, more preferably 0.6 to 1.35, and 0.8 to 1.3. It is more preferable that If the ratio of the polythiol compound in the resin composition is too high, bleeding may easily occur. On the other hand, if the ratio of the epoxy compound is too high, it may be difficult to obtain curability at low temperatures.
  • functional group equivalents such as thiol equivalents and epoxy equivalents represent the molecular weight of a compound per functional group
  • functional group equivalents such as thiol group equivalents and epoxy group equivalents refer to the number of functional group equivalents such as the number of thiol group equivalents and the number of epoxy group equivalents. Represents the number of functional groups (number of equivalents) per mass (amount charged).
  • the epoxy equivalent of component (A) is the number obtained by dividing the molecular weight of component (A) by the number of epoxy groups in one molecule.
  • the actual epoxy equivalent can be determined by the method described in JIS K7236.
  • the number of equivalents of epoxy groups in component (A) is the number of epoxy groups (number of equivalents) per mass (charged amount) of component (A), and the mass (g) of the epoxy compound of component (A) is the number of epoxy groups per mass (charged amount) of component (A). It is the quotient divided by the epoxy equivalent of the compound (if more than one epoxy compound is included, the sum of such quotients for each epoxy compound).
  • the thiol equivalent of component (B) is the number obtained by dividing the molecular weight of component (B) by the number of thiol groups in one molecule.
  • the actual thiol equivalent can be determined, for example, by determining the thiol value by potentiometric measurement. This method is widely known and is disclosed, for example, in paragraph 0079 of JP-A-2012-153794.
  • the number of thiol group equivalents of component (B) is the number of thiol groups (number of equivalents) per mass (charged amount) of component (B), and the mass (g) of the polythiol compound (B) is It is the quotient divided by the thiol equivalent (or the sum of such quotients for each polythiol compound if more than one polythiol compound is included).
  • the resin composition of the present embodiment includes (C) a cyclic carbodiimide compound (hereinafter also referred to as "component (C)").
  • a cyclic carbodiimide compound has a cyclic structure.
  • One cyclic structure has only one carbodiimide group.
  • the number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, even more preferably 10 to 20.
  • the cyclic carbodiimide compound may have a plurality of cyclic structures.
  • the cyclic carbodiimide compound used in this embodiment is preferably a cyclic carbodiimide compound represented by the following general formula (5).
  • Ar 1 to Ar 4 are each independently an aromatic group.
  • the aromatic group may be substituted with an alkyl group or an aryl group having 1 to 6 carbon atoms.
  • Examples of the aromatic group include aromatic groups such as a phenylene group and a naphthalenediyl group.
  • Ar 1 to Ar 4 are phenylene groups because film forming properties are improved.
  • X is a divalent or tetravalent group. When X is divalent, q is 0, and when X is quadrivalent, q is 1. X is any of the following formulas (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), (5-vii) It is preferable.
  • n is an integer from 1 to 6.
  • Examples of the group (5-i) include a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentane group, and a 1,6-hexane group.
  • m and n are each independently an integer of 0 to 4.
  • R 1 and R 2 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms methyl group, ethyl group, n-propyl group, sec-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group , n-pentyl group, sec-pentyl group, iso-pentyl group, n-hexyl group, sec-hexyl group, iso-hexyl group, and the like.
  • X is the above-mentioned (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), ( 5-vii) is preferred.
  • Y and Z are each independently an alkyl group having 1 to 6 carbon atoms or a substituent other than a phenyl group. Conventionally known substituents can be applied as substituents other than alkyl groups having 1 to 6 carbon atoms or phenyl groups, such as alkyl groups having 7 or more carbon atoms, aryl groups other than phenyl groups, alkoxy groups, hydroxy groups, aldehydes.
  • acyl group carboxyl group, ester group, nitro group, amino group, sulfo group, sulfonyloxy group, halogeno group, silyl group, vinyl group, fluoroalkyl group, cyano group, isonitrile group, amide group, imide group, thiol
  • examples include groups.
  • the content of the cyclic carbodiimide compound (C) in the resin composition is 0.1 to 50% by mass based on 100% by mass of the total amount of the epoxy compound (A) and the polythiol compound (B) in the resin composition. It is preferably 0.5% to 45% by mass, and even more preferably 1% to 40% by mass.
  • the present inventors believed that controlling the thiol group of a polythiol compound is important in order to suppress the bleeding phenomenon, and focused on the carbodiimide group that is thought to react with the thiol group. After further investigation, we found that the occurrence of the bleed phenomenon can be further suppressed by appropriately selecting a cyclic carbodiimide compound from among carbodiimide compounds. Since the cyclic carbodiimide compound has a cyclic structure having a carbodiimide group, steric hindrance around the carbodiimide group is reduced, the reaction with the thiol group of the polythiol compound proceeds more quickly, and unused substances are left in the cured product of the resin composition.
  • acyclic polycarbodiimide compounds that do not contain carbodiimide groups in their cyclic structure have multiple carbodiimide groups in their molecules that can react with thiol groups, but because they are chain-like, the degree of freedom in the molecular chain is limited. It is thought that this is largely due to the fact that the carbodiimide group receives steric hindrance from the molecular chain, which lowers its reactivity with the thiol group of the polythiol compound.
  • the method for producing the cyclic carbodiimide compound is not particularly limited, and the cyclic carbodiimide compound can be produced by a conventionally known method (for example, the method described in International Publication No. 2010/071211, JP 2011-256139, etc.). can.
  • a method of producing an amine form via an isocyanate form For example, a method of producing an amine form via an isocyanate form, a method of producing an amine form via an isothiocyanate form, a method of manufacturing from an amine form via a triphenylphosphine form, a method of producing a urea form from an amine form via a triphenylphosphine form, A method of manufacturing from an amine form via a thiourea form, a method of manufacturing from a carboxylic acid form via an isocyanate form, and a method of manufacturing by deriving a lactam form.
  • a commercially available cyclic carbodiimide compound may be used.
  • the resin composition of the present embodiment includes (D) a curing catalyst (hereinafter also referred to as "component (D)").
  • component (D) the resin composition of this embodiment can be cured in a short time even under low temperature conditions.
  • the curing catalyst used in this embodiment is not particularly limited as long as it is a basic curing catalyst for the epoxy compound (A), and any known catalyst can be used.
  • Component (D) is preferably a latent curing catalyst.
  • a latent curing catalyst is a compound that is inactive at room temperature but activated by heating to function as a curing catalyst.
  • an imidazole compound that is solid at room temperature a reaction product of an amine compound and an epoxy compound.
  • Examples include solid-dispersed amine adduct-based latent curing catalysts such as amine-epoxy adducts (amine-epoxy adducts); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adducts), and the like.
  • component (D) from the viewpoint of pot life and curability, a solid dispersion type amine adduct type latent curing catalyst is preferable.
  • Epoxy compounds used as one of the raw materials for producing solid-dispersed amine adduct-based latent curing catalysts include, for example, polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or glycerin.
  • the amine compound used as another raw material for producing the solid-dispersed amine adduct-based latent curing catalyst has one or more active hydrogens in its molecule that can undergo an addition reaction with an epoxy group, and has a primary amino group, a secondary Any material having at least one functional group selected from amino groups and tertiary amino groups in its molecule may be used. Examples of such amine compounds are shown below, but the invention is not limited thereto.
  • aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane, 2 - Aromatic amine compounds such as methylaniline; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine; etc., but are not limited to these.
  • compounds having a tertiary amino group in the molecule are raw materials that provide latent curing catalysts with excellent curing accelerating ability, and examples of such compounds include, for example, dimethylaminopropylamine. , diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, and 2-methylimidazole, 2-ethylimidazole, 2-ethyl- Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol
  • Isocyanate compounds that can be used as another production raw material in the solid-dispersed amine adduct latent curing catalyst include, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; Methylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.
  • monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate
  • Polyfunctional isocyanate compounds Furthermore, terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds, etc. can also be used.
  • terminal isocyanate group-containing compounds include addition compounds having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and terminal isocyanate groups obtained by the reaction of toluylene diisocyanate and pentaerythritol. Examples include, but are not limited to, addition compounds having the following.
  • urea compounds include urea, thiourea, etc., but are not limited thereto.
  • the solid dispersed latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned (a) two components of an amine compound and an epoxy compound, (b) three components of these two components and an active hydrogen compound, or (c) ) It is a combination of two or three components of an amine compound, an isocyanate compound and/or a urea compound. These can be prepared by taking each component, mixing them, reacting at a temperature between room temperature and 200°C, cooling to solidify, and then pulverizing, or reacting in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and removing the solvent. , can be easily produced by pulverizing the solid content.
  • a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc.
  • latent curing catalysts include "Amicure PN-23” (product name of Ajinomoto Fine Techno Co., Inc.) and “Amicure PN-40" for amine-epoxy adduct systems (amine adduct systems).
  • Ajinomoto Fine-Techno Co., Inc. product name "Ajinomoto Fine-Techno Co., Inc. product name”
  • Amicure PN-50 (Ajinomoto Fine-Techno Co., Ltd. product name)
  • “Hardener X-3661S” ACR Co., Ltd. product name
  • Harddener X-3670S A.C.R. Co., Ltd. product name
  • Novacure HX-3742 Asahi Kasei Co., Ltd.
  • Component (D) is preferably contained in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total mass of the resin composition.
  • component (D) is provided in the form of a dispersion in an epoxy compound.
  • component (D) in such a form, it should be noted that the amount of epoxy compound in which it is dispersed is also included in the amount of component (A) in the resin composition of the present embodiment. .
  • the resin composition of this embodiment can further contain (E) filler (hereinafter also referred to as "component (E)").
  • component (E) By containing the filler in the resin composition, the coefficient of linear expansion of the cured product obtained by curing the resin composition can be lowered, and the thermal cycle resistance is improved. Moreover, if the filler has a low elastic modulus, the stress generated in the cured product can be alleviated, improving long-term reliability.
  • Fillers are broadly classified into inorganic fillers and organic fillers.
  • the inorganic filler is not particularly limited as long as it is made of granules made of an inorganic material and has the effect of lowering the coefficient of linear expansion when added.
  • Inorganic materials 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, and oxide. Titanium, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. can be used. Any one type of inorganic filler may be used, or two or more types may be used in combination. As the inorganic filler, it is preferable to use silica filler because the filling amount can be increased.
  • Silica is preferably amorphous silica.
  • the surface of the inorganic filler is preferably treated with a coupling agent such as a silane coupling agent.
  • a coupling agent such as a silane coupling agent.
  • organic fillers include, but are not limited to, polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, styrene fillers, and the like.
  • PTFE polytetrafluoroethylene
  • silicone fillers silicone fillers
  • acrylic fillers acrylic fillers
  • styrene fillers and the like.
  • the organic filler may be surface-treated.
  • the shape of the filler is not particularly limited, and may be spherical, flaky, acicular, amorphous, or the like.
  • the resin composition of this embodiment preferably does not substantially contain fillers having an average particle size of 10 ⁇ m or more.
  • the average particle size refers to the volume-based median diameter (d 50 ) measured by laser diffraction according to 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 0.1 ⁇ m or more.
  • the average particle size of the filler (E) is preferably 0.1 ⁇ m or more and less than 6.0 ⁇ m, more preferably 0.1 ⁇ m or more and less than 5.0 ⁇ m, and even more preferably 0.1 ⁇ m or more and less than 5.0 ⁇ m. It is 1 ⁇ m or more and less than 4.0 ⁇ m, particularly preferably 0.1 ⁇ m or more and less than 2.0 ⁇ m, and most preferably 0.1 ⁇ m or more and less than 1.0 ⁇ m.
  • the filler content in the resin composition of the present embodiment is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and 20 to 40% by mass based on the total mass of the resin composition. % is more preferable.
  • the resin composition of the present embodiment may contain optional components other than the above-mentioned components (A) to (D) or component (E), such as those described below.
  • the resin composition of the present embodiment may contain (F) a thixotropic agent (hereinafter also referred to as "component (F)”) to the extent that the effects of the present invention are not impaired.
  • component (F) a thixotropic agent
  • examples of the thixotropic agent include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, bentonite, acetylene black, and Ketjen black. preferable.
  • the thixotropic agent is more preferably nanosilica with an average particle size of 10 to 750 nm, from the viewpoint of preventing the resin composition from being bitten during bonding and moisture-resistant adhesion. Nanosilica is more preferred.
  • hydrophobic fumed silica manufactured by CABOT product name: CAB-O-SIL (registered trademark) TS720, average particle size: 12 nm
  • hydrophobic fumed silica manufactured by Nippon Aerosil product name: R805, average particle size :20 nm
  • amorphous silica manufactured by Nippon Shokubai product name: Seahoster KE-P10, average particle size 100 nm
  • the thixotropic agent may be used alone or in combination of two or more.
  • the amount added is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total mass of the resin composition. More preferably, it is 0.1 to 20% by mass.
  • the resin composition of the present embodiment may contain (G) a stabilizer (hereinafter also referred to as "component (G)") to the extent that the effects of the present invention are not impaired. But that's fine.
  • the stabilizer can improve the storage stability and lengthen the pot life of the resin composition of this embodiment.
  • Various known stabilizers can be used, but at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is used because of its high effectiveness in improving storage stability. One is preferred.
  • liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, Tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, tricyclohexylborate, trioctylborate, trinonylborate, tridecylborate, tridodecylborate, trihexadecylborate, triotadecylborate, tris( 2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl ) Borane, tribenzylborate, triphenylborate,
  • a liquid boric acid ester compound is preferable because it is liquid at room temperature (25° C.) and can keep the viscosity of the compound low.
  • aluminum chelate for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used.
  • organic acid for example, barbituric acid can be used. Any one type of stabilizer may be used, or two or more types may be used in combination.
  • the amount added is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total mass of the resin composition. More preferably, it is 0.1 to 20% by mass.
  • the resin composition of the present embodiment may contain (H) a coupling agent (hereinafter also referred to as "component (H)”) to the extent that the effects of the present invention are not impaired. But that's fine.
  • a coupling agent has two or more different functional groups in its molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other one that chemically bonds with an organic material. It is a functional group.
  • the resin composition contains a coupling agent, the adhesive strength of the resin composition to a substrate or the like is improved.
  • Examples of the coupling agent include, but are not limited to, a silane coupling agent, an aluminum coupling agent, a titanium coupling agent, etc., depending on the type of functional group that chemically bonds with the inorganic material.
  • coupling agents include various coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto, depending on the type of functional group that chemically bonds with the organic material. Not limited to these. Among these, epoxy coupling agents containing epoxy groups are preferred from the viewpoint of moisture resistance reliability.
  • epoxy-based silane coupling agents include 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (product name: KBE-403, Shin-Etsu Chemical Co., Ltd.) 3-glycidoxypropylmethyldimethoxysilane (product name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (product name: KBM402, manufactured by Shin-Etsu Chemical Co., Ltd.) , 8-glycidoxyoctyltrimethoxysilane (product name: KBM-4803, Shin-Etsu Chemical Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: Sila Ace S530, JNC Corporation), etc. These include, but are not limited
  • methacrylic silane coupling agents include 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (product name: KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.) ), 3-methacryloxypropylmethyldiethoxysilane (product name: KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (product name: KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Not limited.
  • acrylic silane coupling agent examples include, but are not limited to, 3-acryloxypropyltrimethoxysilane (product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • mercapto-based silane coupling agents include 3-mercaptopropyltrimethoxysilane (product name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (product name KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.). These include, but are not limited to:
  • Any one type of coupling agent may be used, or two or more types may be used in combination.
  • the amount of the coupling agent added is preferably 0.01% by mass to 50% by mass, and 0.1% by mass based on the total mass of the resin composition, from the viewpoint of improving adhesive strength. More preferably, the amount is from % by mass to 30% by mass.
  • the resin composition of this embodiment may contain other additives, such as carbon black, titanium black, ion trapping agents, and leveling agents, to the extent that it does not impair the spirit of this embodiment. , an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a coloring agent, a solvent, etc. may be further contained.
  • additives such as carbon black, titanium black, ion trapping agents, and leveling agents, to the extent that it does not impair the spirit of this embodiment.
  • an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a coloring agent, a solvent, etc. may be further contained.
  • the types and amounts of each additive are as usual.
  • Photo- and thermosetting resin compositions are known that can be temporarily fixed by light irradiation and can be permanently cured by heating, and in that case, the epoxy resin composition is photocurable. It may contain a radically polymerizable compound or a photoradical polymerization initiator as a component.
  • Such photo- and thermosetting resin compositions have a problem in that they tend to bleed, for example, from areas where UV light does not reach sufficiently and remain uncured, such as in the shadows of parts, or during only thermosetting. . From the viewpoint of suppressing bleeding, it is desirable that the resin composition of the present embodiment does not substantially contain a radically polymerizable compound and/or a photoradical polymerization initiator.
  • the amount of the compound is preferably 5% by mass or less, more preferably 4% by mass or less, It is more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less.
  • the radically polymerizable compound is a compound such as an allyl compound that does not react with the polythiol compound depending on the base, the amount is preferably 3% by mass or less, more preferably 2% by mass or less, and 1% by mass or less. It is more preferable that
  • the method for producing the resin composition of this embodiment is not particularly limited.
  • the resin composition of this embodiment can be obtained by introducing the components into a mixer simultaneously or separately and stirring and mixing them while melting them by heating if necessary to obtain a uniform composition.
  • This mixer is not particularly limited, but a Laikai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. equipped with a stirring device and a heating device can be used. Further, these devices may be used in combination as appropriate.
  • the resin composition thus obtained is thermosetting, and preferably cures within 5 hours, more preferably within 1 hour, at a temperature of 80°C. It is also possible to cure at a high temperature and in an extremely short time, such as several seconds at a temperature of 150°C.
  • the curable composition of this embodiment is used to manufacture an image sensor module or a camera module that includes parts that deteriorate under high temperature conditions, the composition is thermally cured at a temperature of 50 to 90°C for 30 to 120 minutes. It is preferable to heat cure at a temperature of 120 to 200°C for 1 to 300 seconds.
  • the resin composition of the present embodiment can be used, for example, as an adhesive or sealant for fixing, bonding, or protecting components constituting a semiconductor device or electronic component, or as a raw material thereof.
  • the adhesive or sealant according to the second embodiment of the present invention contains the resin composition according to the first embodiment described above.
  • This adhesive or encapsulant 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.). It can be used to fix, bond, or protect components constituting a semiconductor device or electronic component. Examples of the semiconductor device or electronic component include, but are not limited to, an HDD, a semiconductor element, a semiconductor module, an integrated circuit, and the like.
  • the adhesive or sealant of this embodiment can be used for fixing, adhering, or protecting components constituting an image sensor or a camera module.
  • the adhesive or sealing material of the present embodiment can provide a cured product in which the occurrence of bleeding phenomenon is suppressed when curing at a low temperature of about 50°C to 90°C that does not have a thermal effect on components.
  • it is suitable for use in manufacturing semiconductor modules that include miniaturized electronic components. This improves the reliability and bondability of the resulting semiconductor module.
  • the cured product of the third embodiment of the present invention is a cured product of the resin composition of the first embodiment or the adhesive or sealant of the second embodiment. This cured product is one in which the occurrence of a bleed phenomenon is suppressed.
  • the semiconductor device or electronic component according to the fourth embodiment of the present invention includes the cured product according to the third embodiment described above, and therefore has high reliability and bondability.
  • semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, and the like. Examples of the semiconductor device or electronic component include an HDD, a semiconductor element, a semiconductor module, an integrated circuit, and more specifically, an image sensor or a camera module.
  • Examples 1 to 7, Comparative Examples 1 to 2 A resin composition was prepared by mixing predetermined 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 mass (unit: g).
  • the components used in the examples and comparative examples are as follows.
  • E) Filler (ingredient (E))
  • E1 Silica filler (product name: SE5200SEE, average particle size 2 ⁇ m, manufactured by Admatex Co., Ltd.)
  • E2 Silica filler (product name: SE2200SEE, average particle size 0.6 ⁇ m, manufactured by Admatex Co., Ltd.)
  • F1 Hydrophobic fumed silica (product name: R805, manufactured by Nippon Aerosil Co., Ltd., average particle size: 20 nm)
  • the present invention is a low-temperature curable resin composition that can suppress the occurrence of a bleed phenomenon, and is very useful as an adhesive or sealant used for fixing or bonding electronic components.

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JP2022026245A (ja) * 2020-07-30 2022-02-10 パナソニックＩｐマネジメント株式会社 熱硬化性組成物、硬化物、機器、及び機器の製造方法
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WO2016039486A1 (ja) * 2014-09-11 2016-03-17 帝人株式会社 熱硬化性樹脂組成物
CN104774584A (zh) * 2014-12-29 2015-07-15 北京海斯迪克新材料有限公司 一种用于led背光模组lens粘接的单组份环氧胶粘剂
JP2017125150A (ja) * 2016-01-15 2017-07-20 住友ベークライト株式会社 樹脂組成物
WO2019138919A1 (ja) * 2018-01-15 2019-07-18 日立化成株式会社 液状封止樹脂組成物、電子部品装置及び電子部品装置の製造方法
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