Curable resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic device

Abstract

Provided are: a curable resin composition which can be cured at a low temperature and which has excellent pot life; an adhesive; a sealing material; a cured product; a semiconductor device; and an electronic device. This curable resin composition comprises (A) a cation-curable resin, (B) an acid generator including an iodonium salt, and (C) a peroxy dicarbonate-type organic peroxide represented by formula (1). The peroxycarbonate-type organic peroxide represented by formula (1) includes an alkyl group represented by R1 and an alkyl group represented by R2, the alkyl groups each having at least 10 carbon atoms.

Description

Curable resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic device

[0001] The present invention relates to a curable resin composition, an adhesive, an encapsulant, a cured product, a semiconductor device, and an electronic device.

[0002] Curable resin compositions containing cationically polymerizable compounds are used as adhesives in the field of electronic components because the cured products thereof have excellent properties such as adhesiveness, electrical insulation, chemical resistance, and mechanical strength.

[0003] For example, Patent Document 1 describes that in a thermally cationically polymerizable composition that can be used in the field of adhesives, etc., insufficiently cured components volatilize as outgassing during a heat resistance test, etc., and contaminate the surroundings. Patent Document 1 discloses a thermally cationically polymerizable composition in which the amount of a thermally cationically polymerizable initiator added to the composition is adjusted in order to reduce the amount of outgassing.

[0004] Japanese Patent Application Laid-Open No. 2022-105415

[0005] When the adherends to be bonded are components of precision equipment such as camera modules and sensor modules, adhesives that can be cured at low temperatures are desired. In addition, resin compositions used in adhesives and the like are also desired to have good storage stability and an excellent pot life.

[0006] Therefore, an object of the present invention is to provide a curable resin composition, an adhesive, an encapsulant, a cured product obtained by curing these, and a semiconductor device and an electronic device including the cured product, which can be cured by heating at a low temperature of, for example, at least 100°C or less, preferably 80°C or less, and can also be cured by ultraviolet (UV) irradiation, and which has an excellent pot life.

[0007] The means for solving the above problems are as follows, and the present invention includes the following aspects.

[0008] [1] A curable resin composition comprising: (A) a cationically curable resin; (B) an acid generator containing an iodonium salt; and (C) a peroxydicarbonate-type organic peroxide represented by the following formula (1): (In the formula (1), R １and R ２ are each independently an alkyl group having at least 10 carbon atoms. １ and R ２ [3] The curable resin composition according to claim 1, wherein the iodonium salt contained in component (B) is an iodonium salt compound represented by the following formula (2): (In the formula (2), Ar １ and Ar ２ are each independently a substituted or unsubstituted aryl group; Z － is an anion.) [4] Z in the formula (2) － But BF ４ － , SbF ６ -, AsF ６ － , B(C ６ F ５ ) ４ － , or Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , or [P(R ３ ) ａ F ６－ａ ] － , [C(R ３ SO ２ ) ３ ] － , or [N(R ３ SO ２ ) ２ ] － (In the formula, R ３ are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R ３may be the same or different. ) The curable resin composition according to [3] above. [5] The curable resin composition according to any one of [1] to [4] above, wherein component (A) comprises at least one selected from the group consisting of: (A1) an epoxy resin having an epoxy group equivalent of 100 g / eq to 1000 g / eq and having a ring skeleton in the molecule; and (A2) an oxetane resin. [6] The curable resin composition according to [5] above, wherein component (A1) comprises an epoxy resin having an epoxy group equivalent of 200 g / eq or more. [7] The curable resin composition according to any one of [1] to [6] above, wherein the amount of component (C) is 0.1 to 10 parts by mass when the total amount is 100 parts by mass. [8] An adhesive or sealant comprising the curable resin composition according to any one of [1] to [7] above. [9] A cured product obtained by curing the curable resin composition according to any one of [1] to [7] above, or the adhesive or sealant according to [8] above.

[10] The cured product according to [9] above, wherein the glass transition temperature (Tg) of the cured product is 0°C to 200°C.

[11] A semiconductor device comprising the cured product according to [9] or

[10] above.

[12] An electronic device comprising the cured product according to [9] or

[10] above.

[0009] According to the present invention, it is possible to provide a curable resin composition, an adhesive, an encapsulant, a cured product obtained by curing these, and a semiconductor device and an electronic device including the cured product, which can be cured by heating at a low temperature of 100°C or less, preferably 80°C or less, and have an excellent pot life.

[0010] Hereinafter, the curable resin composition, adhesive, encapsulant, cured product obtained by curing these, and semiconductor device and electronic component including the cured product according to the present disclosure will be described based on embodiments. However, the embodiments shown below are examples for embodying the technical idea of ​​the present invention, and the present invention is not limited to the curable resin composition, adhesive, encapsulant, cured product, semiconductor device, and electronic component described below. In this specification, following the convention in the field of synthetic resins, a name including the term "resin," which usually refers to a polymer (particularly a synthetic polymer), may be used for a component constituting a curable resin composition before curing, even though the component is not a polymer.

[0011] Resin Composition The curable resin composition according to a first embodiment of the present invention is a curable resin composition comprising: (A) a cationically curable resin (hereinafter also referred to as “component (A)”); (B) an acid generator containing an iodonium salt (hereinafter also referred to as “component (B)”); and (C) a peroxydicarbonate-type organic peroxide represented by the following formula (1) (hereinafter also referred to as “component C”). (In the formula (1), R １ and R ２ are each independently an alkyl group having at least 10 carbon atoms.

[0012] A curable resin composition that uses an iodonium salt-based cationic polymerization initiator and an organic peroxide as a thermal radical polymerization initiator to obtain a cured product through a radical redox reaction can be cured at a relatively low temperature, and a cured product with almost the same physical properties can be obtained whether the composition is cured by heat or by irradiation with heat and ultraviolet light.

[0013] However, the reaction temperature of a curable resin composition that cures via a radical redox reaction tends to depend on the stability of the organic peroxide contained in the composition, and the lower the one-hour half-life temperature, the more easily the composition can be cured at a low temperature. On the other hand, the lower the one-hour half-life temperature of the organic peroxide contained in the composition, the more the stability of the composition is impaired, and therefore the storage stability also tends to be impaired.

[0014] The curable resin composition includes component (C), a peroxydicarbonate-type organic peroxide represented by the formula (1) and having alkyl groups with at least 10 carbon atoms at both ends. The carbonate radical generated from component (C) rapidly abstracts hydrogen from other compounds contained in the curable resin composition, generating unstable alkyl radicals such as primary radicals. Because unstable alkyl radicals are prone to radical redox reactions, the reaction of unstable alkyl radicals is thought to be faster than the reaction rate of curing inhibition by oxygen. Therefore, the carbonate radical generated from component (C) is thought to be able to rapidly advance the curing reaction of the cationic curable resin. Furthermore, because the carbonate radical's hydrogen abstraction reaction is faster than that of alkoxy radicals, the instantaneous radical concentration in the curable resin composition system is thought to be higher than that of organic peroxides other than component (C). This reaction transfers electrons from the unstable alkyl radical to an acid generator containing an iodonium salt, reductively decomposing the iodonium salt and generating an acid (cation: H ) without light. ＋ ) is generated. Then, it acts on the cationic curable resin to initiate a polymerization reaction. The peroxydicarbonate-type organic peroxide efficiently generates carbonate radicals, allowing the curing reaction of the cationic curable resin to proceed quickly. The curable resin composition can be cured by heating at a low temperature of 100°C or less, preferably 90°C or less, more preferably 85°C or less, and even more preferably 80°C or less.

[0015] In the curable resin composition, the peroxydicarbonate-type organic peroxide of component (C) represented by formula (1) generates a carbonate radical, which generates an unstable alkyl radical in association with a hydrogen abstraction reaction in the curable resin composition, thereby rapidly promoting the curing reaction of the cationic curable resin. Furthermore, since the peroxydicarbonate-type organic peroxide of component (C) represented by formula (1) has alkyl groups having at least 10 carbon atoms bonded to the two oxygen atoms at both ends of the peroxydicarbonate, the organic peroxide is less likely to decompose at room temperature below heating temperatures, for example, 20°C to 40°C, and at low temperatures below 20°C, and has good storage stability and an excellent pot life, compared to peroxydicarbonate-type organic peroxides having alkyl groups having fewer than 10 carbon atoms.

[0016] Component (A): Cationic Curable Resin The cationic curable resin of component (A) refers to a resin having one or more cationic polymerizable groups in the molecule, and examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of cationic curable resins include epoxy resins, oxetane resins, polystyrene compounds, and vinyl ether compounds. The cationic curable resin of component (A) preferably has a molecular weight of 100 to 800, and may have a molecular weight of 110 to 780, in order to be cured by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less.

[0017] In this specification, functional group equivalents such as epoxy group equivalent and oxetane group equivalent refer to the molecular weight of a compound per functional group, and functional group equivalents such as epoxy group equivalent number and oxetane group equivalent number refer to the number of functional groups (equivalent number) per mass (charged amount) of a compound. The epoxy group equivalent or oxetane group equivalent can be measured in accordance with JIS K7236:2001 (corresponding to ISO3001:1999).

[0018] The cationic curable resin of component (A) preferably contains at least one selected from the group consisting of (A1) an epoxy resin having an epoxy group equivalent of 100 g / eq to 10,000 g / eq and having a ring skeleton in the molecule (hereinafter also referred to as "component (A1)"), and (A2) an oxetane resin (hereinafter also referred to as "component (A2)"). By including in component (A) at least one selected from the group consisting of (A1) an epoxy resin having an epoxy group equivalent of 100 g / eq to 1,000 g / eq and having a ring skeleton in the molecule, and (A2) an oxetane resin, the curing reaction proceeds rapidly, resulting in a curable resin composition that cures upon heating at low temperatures, for example, 100°C or below, preferably 80°C or below. Component (A) may contain either component (A1) alone or both component (A1) and component (A2).

[0019] Examples of epoxy resins include aliphatic epoxy resins and epoxy resins having a ring skeleton in the molecule. The epoxy resin preferably includes (A1) an epoxy resin having an epoxy group equivalent of 100 g / eq to 1000 g / eq and having a ring skeleton in the molecule. Examples of ring skeletons include an alicyclic skeleton, an aromatic ring skeleton, a heteroaromatic ring skeleton, and a heterocyclic skeleton. The epoxy resin of component (A1) preferably includes at least one selected from the group consisting of epoxy resins having an aromatic ring skeleton in the molecule and epoxy resins having an alicyclic skeleton in the molecule.

[0020] When component (A) contains an epoxy resin, component (A1) has an epoxy group equivalent of 100 g / eq to 1000 g / eq, and contains an epoxy resin having a ring skeleton in the molecule, if the epoxy group equivalent is 100 g / eq to 1000 g / eq, a cured product can be obtained by curing by heating at a low temperature of, for example, 100° C. or less, preferably 80° C. or less. When component (A) contains an epoxy resin, the epoxy group equivalent of the epoxy resin of component (A1) may be 800 g / eq or less, 600 g / eq or less, 500 g / eq or less, or 400 g / eq or less, 120 g / eq or more, 130 g / eq or more, 150 g / eq or more, 180 g / eq or more, preferably 200 g / eq or more, and may be 250 g / eq or more.

[0021] Epoxy resins having an aromatic ring skeleton include polyfunctional epoxy resins, specifically bisphenol A type epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A skeleton (AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4010S, manufactured by ADEKA Corporation), and phenol F type epoxy resins (EPI manufactured by DIC Corporation). CRON (registered trademark) 830-S, EXA-830LVP, etc.), bisphenol AD ​​type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin (EPICLON (registered trademark), HP-4032D, HP-720H, etc., manufactured by DIC Corporation), phenol novolac type epoxy resin (EPICLON (registered trademark), N-740, N-770, etc., manufactured by DIC Corporation), cresol volac type epoxy resin (EPICLON (registered trademark), N-660, N-670, N-655-EXP-S, etc., manufactured by DIC Corporation). Specific examples of the polyfunctional epoxy compound contained in the polyfunctional epoxy resin include glycidyl ether of tetra(hydrophenyl)alkane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, etc. Specific examples of compounds contained in monofunctional epoxy resins include p-tert-butylphenyl glycidyl ether (ADEKA GLYCIROL (registered trademark), ED-509E, ED-509S, etc., manufactured by ADEKA CORPORATION).

[0022] The epoxy resin having an alicyclic skeleton may be any epoxy resin having an alicyclic skeleton in one molecule, and may include a cycloalkylene oxide compound in which an epoxy group is formed by two carbon atoms and one oxygen atom forming an alicyclic structure. The epoxy resin having an alicyclic skeleton may also include an epoxy compound having an alicyclic skeleton. Examples of the epoxy compound having an alicyclic skeleton include cyclohexane-based, cyclohexyl methyl ester-based, cyclohexyl methyl ether-based, spiro-based, and tricyclodecane-based epoxy compounds. Specific examples of epoxy resins having an alicyclic skeleton include 3',4'-epoxycyclomethyl 3,4-epoxycyclohexane carboxylate (Celloxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), 1,2-epoxy-4-vinylcyclohexane, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.).

[0023] Examples of aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts. Specific examples of aliphatic epoxy compounds contained in aliphatic epoxy resins include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether (such as Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), and polyethylene glycol diglycidyl ether. Examples of aliphatic cyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether (such as jER YX8000 manufactured by Mitsubishi Chemical Corporation).

[0024] Specific examples of vinyl ether compounds include hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexanedimethanol, triethylene glycol divinyl ether, dodecyl vinyl ether, and cyclohexyl vinyl ether.

[0025] Although the polymerization initiation reaction of the oxetane resin of component (A2) is slower than that of the epoxy resin, it polymerizes rapidly once the initiation species for polymerization reaches a certain concentration or higher, and therefore a cured product can be obtained at a low temperature in a short reaction time. Specific examples of the oxetane resin include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (OXT-101 manufactured by Toagosei Co., Ltd., etc.), 2-ethylhexyloxetane (OXT-212 manufactured by Toagosei Co., Ltd., etc.), xylylene bisoxetane (OXT-121 manufactured by Toagosei Co., Ltd., etc.), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221 manufactured by Toagosei Co., Ltd., etc.), oxetanyl silsesquioxetane (OXT-191 manufactured by Toagosei Co., Ltd., etc.), phenol novolac oxetane (PHOX manufactured by Toagosei Co., Ltd., etc.), and 3-ethyl-3-phenoxymethyloxetane (OXT-211 manufactured by Toagosei Co., Ltd., etc.).

[0026] When component (A) contains the oxetane resin of component (A2), the oxetane group equivalent of the oxetane resin is preferably 100 g / eq to 500 g / eq, and may be 110 g / eq to 300 g / eq. When component (A) contains the oxetane resin of component (A2), if the oxetane group equivalent of component (A2) is 100 g / eq to 500 g / eq, a cured product can be obtained by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less. When component (A) contains the oxetane resin of component (A2), the oxetane group equivalent of the oxetane resin may be 250 g / eq or less.

[0027] Component (B): Acid Generator Containing Iodonium Salt The iodonium salt contained in the acid generator of component (B) is preferably an iodonium compound represented by the following formula (2). (In the formula (2), Ar １ and Ar ２are each independently a substituted or unsubstituted aryl group; Z － is an anion.)

[0028] The aryl group represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. １ and Ar ２ are each independently preferably a phenyl group or a naphthyl group. The aryl group may be unsubstituted or substituted with one or more optional substituents. Examples of the substituent include a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched acyloxy group having 2 to 18 carbon atoms, a halogen atom, a cyano group, a nitro group, and a hydroxyl group.

[0029] The anion may be a monovalent counter anion, and is preferably a non-antimony anion. － The anion represented by BF ４ － , SbF ６ -, AsF ６ － , B(C ６ F ５ ) ４ － , or Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , or [P(R ３ ) ａ F ６－ａ ] － , [C(R ３ SO ２ ) ３ ] － , or [N(R ３ SO ２ ) ２ ] － (In the formula, R ３are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R ３ In formula (2), Z may be the same or different. － It is preferable that the nucleophilicity of the anion represented by the formula (I) is relatively low. When the nucleophilicity of the anion contained in the iodonium salt is low, the rate of the propagation reaction of the cationically curable resin increases, and a cured product can be obtained at a low temperature of 100°C or less in a short time.

[0030] Specific examples of component (B) include diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co., Ltd.), 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF), bis(C １０～１４Examples of iodonium salts include 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (e.g., Bluesil (registered trademark) PI2074 manufactured by ELKEM SILICONES). Commercially available iodonium salts can be used, for example, as cationic initiators or as iodonium salts contained in acid generators.

[0031] Component (C): Peroxydicarbonate-Type Organic Peroxide Component (C), a peroxydicarbonate-type organic peroxide represented by the following formula (1) and having alkyl groups with at least 10 carbon atoms at both ends, is a radical source and generates carbonate radicals. The generated carbonate radicals rapidly abstract hydrogen from other compounds contained in the curable resin composition, generating unstable alkyl radicals such as primary radicals. Unstable alkyl radicals are highly reactive and prone to radical redox reactions, which are thought to be faster than the reaction rate of oxygen-induced curing inhibition. Therefore, it is thought that the curing reaction of cationic curable resins can proceed quickly. Organic peroxides other than peroxydicarbonate-type, such as alkyl peroxyester-type, are likely to generate oxygen radicals. The generated oxygen radicals are likely to generate stable alkyl radicals through self-cleavage or decarboxylation. Stable alkyl radicals have low reactivity, which is thought to accelerate the oxygen-inhibited reaction rather than electron transfer to an acid generator containing an iodonium salt. This effect makes the iodonium salt less susceptible to decomposition. Therefore, the acid (cation: H ＋ ) is less likely to be produced, which is thought to make the polymerization reaction more likely to be inhibited.

[0032] (In the formula (1), R １ and R ２are each independently an alkyl group having at least 10 carbon atoms.

[0033] In formula (1), R １ and R ２ are each independently an alkyl group having at least 10 carbon atoms, and more preferably an alkyl group having at least 11 carbon atoms. １ and R ２ are each independently an alkyl group having at least 10 carbon atoms, preferably an alkyl group having at least 11 carbon atoms, the organic peroxide is unlikely to decompose even at room temperature, for example, 20°C to 40°C, which is lower than the heating temperature, or at a low temperature below 20°C, and the curable resin composition has good storage stability and an excellent pot life. １ and R ２ may each independently be an alkyl group having 30 or less carbon atoms. １ and R ２ The peroxydicarbonate-type organic peroxide of component (C) is represented by the formula (1) R １ and R ２ The peroxydicarbonate-type organic peroxide of component (C) is an alkyl group represented by the formula (1) R １ and R ２ More preferably, R are each independently a linear or branched alkyl group having at least 10 carbon atoms. １ and R ２ are each independently a linear or branched alkyl group having at least 10 carbon atoms, the organic peroxide is less likely to decompose, has better storage stability, and has an excellent pot life, even when radicals are generated by heating at a low temperature of 100°C or less, preferably 80°C or less, and even at room temperature of, for example, 20°C to 40°C, which is lower than the heating temperature, or at a low temperature below 20°C.

[0034] The peroxydicarbonate-type organic peroxide of component (C) represented by formula (1) preferably has a one-hour half-life temperature of 50°C to 80°C, or alternatively 55°C to 75°C, and more preferably 55°C to 70°C. When the peroxydicarbonate-type organic peroxide of component (C) has a one-hour half-life temperature of 50°C to 80°C, it can generate radicals by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, and reductively decompose the iodonium salt, thereby accelerating the polymerization reaction of the cationic curable resin. The peroxydicarbonate-type organic peroxide of component (C) represented by formula (1) preferably has a molecular weight of 200 to 1,000, or alternatively 250 to 800, or alternatively 300 to 700.

[0035] Examples of the peroxydicarbonate-type organic peroxide of component (C) include di(4-tert-butylcyclohexyl) peroxydicarbonate (e.g., Peroyl TCP manufactured by NOF Corporation), dicetyl peroxydicarbonate (e.g., Perkadox 24L manufactured by Nouryon), dimyristyl peroxydicarbonate (e.g., Perkadox 26 manufactured by Nouryon), ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry), and distearyl peroxydicarbonate (manufactured by SAGECHEM LIMITED).

[0036] The curable resin composition may contain at least one selected from the group consisting of a (D) photosensitizer, a (E) photoradical generator, and a (F) filler (hereinafter also referred to as "component (D)," "component (E)," and "component (F)," respectively). The curable resin composition may further contain at least one selected from the group consisting of a (G) coupling agent, a (H) ion trapping agent, and a (I) colorant such as a pigment (hereinafter also referred to as "component (G)," "component (H)," and "component (I)," respectively). At least one component selected from the group consisting of a (G) coupling agent, a (H) ion trapping agent, and a (I) colorant may be included as an optional component.

[0037] (D) Photosensitizer The photosensitizer is a component that increases the sensitivity of the iodonium salt to light. Examples of photosensitizers include thioxanthone derivatives, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes, with thioxanthone derivatives being preferred. Specific examples of thioxanthone derivatives include isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and thioxanthone ammonium salt, with 2,4-diethylthioxanthone being preferred.

[0038] (E) Photoradical Generator The photoradical generator, together with the peroxydicarbonate-type organic peroxide of component (C), is a radical source that generates alkyl radicals upon irradiation with light, reductively decomposes the iodonium salt, and converts the iodonium salt into an acid (cation: H ＋ ), which accelerates the polymerization reaction. The curable resin composition of the present invention does not need to contain (E) a photoradical generator because it contains the peroxydicarbonate-type organic peroxide of component (C). When the curable resin composition contains (E) a photoradical generator, it generates alkyl radicals by light, reductively decomposes the iodonium salt, and also generates an acid (cation: H ＋ Examples of the photoradical generator include 1-hydroxycyclohexyl phenyl ketone (e.g., Omnirad (registered trademark) 184 manufactured by IGM Resins), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0039] (F) Filler The filler is a component for improving the fluidity, injectability, coatability, adhesion, etc. of the curable resin composition. When the curable resin composition contains a filler, a cured product with good adhesion to the substrate can be obtained even when cured by heating at a low temperature of 100°C or less, preferably 80°C or less. Examples of the filler include known inorganic fillers and organic fillers. One type of filler may be used, or two or more types may be used in combination.

[0040] Examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide (precipitated silica, fumed silica, etc.), kaolin, talc, glass beads, sericite activated clay, aluminum hydroxide, asbestos powder, copper oxide, copper hydroxide, iron oxide, lead oxide, magnesium oxide, tin oxide, carbon, mica, smectite, carbon black, bentonite, aluminum nitride, and silicon nitride. Fillers may be added as thixotropic agents. When a filler is added as a thixotropic agent, fumed silica is preferred. The fumed silica may be surface-treated. Examples of inorganic surface treatment agents for thixotropic agents include monoalkyltrialkoxysilane, dimethyldichlorosilane, polydimethylsiloxane, and hexamethyldisilazane. Commercially available surface-treated or untreated fumed silica can be used. From the viewpoint of adhesion to the adherend, the inorganic filler is preferably silicon dioxide, glass beads, or talc, and from the viewpoint of improving fluidity, injectability, and coatability, silicon dioxide is more preferred. Examples of silicon dioxide include colloidal silica, hydrophobic silica (e.g., Cabosil (registered trademark) TS720 manufactured by Cabot Japan Co., Ltd.), spherical silica (e.g., high-purity synthetic spherical silica SE5200SEE manufactured by Admatechs Co., Ltd.), and nanosilica. As for silicon dioxide, two or more types having different types or different particle sizes may be used in combination, or one type may be used alone.

[0041] Examples of organic fillers include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester microparticles, polyurethane microparticles, and rubber microparticles (acrylic rubber particles, isoprene rubber particles). The organic filler may have a core-shell structure. The polysiloxane resin particles may be silicone particles. From the viewpoint of adhesion, the organic filler is preferably rubber microparticles, and rubber microparticles having a core-shell structure are particularly preferred. When the filler is an organic filler, the weight-average molecular weight of the organic filler is not particularly limited, but is preferably 50,000 to 4,000,000, and particularly preferably 300,000 to 3,000,000. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0042] The average particle size of the filler is not particularly limited, but is preferably 0.01 μm or more and less than 10 μm, and particularly preferably 0.012 μm or more and 5 μm or less, in order to improve fluidity, injectability, coatability, adhesion, etc. The average particle size of the filler can be measured using a laser diffraction particle size distribution analyzer, a dynamic light scattering nanotrack particle size distribution analyzer, etc. The average particle size may be the 50% cumulative particle size in a volume-based particle size distribution, or may be the 50% cumulative particle size in a number-based particle size distribution.

[0043] (G) Coupling Agent 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 is a functional group that chemically bonds with an organic material. By including a coupling agent in the curable resin composition, the adhesion of the curable resin composition can be improved when bonding different materials, such as in a camera module or a sensor module.

[0044] Examples of the coupling agent include, but are not limited to, a silane coupling agent, an aluminum coupling agent, a titanium coupling agent, etc. One type of coupling agent may be used, or two or more types may be used in combination.

[0045] Examples of functional groups contained in the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. Examples of the silane coupling agent include silane compounds having an epoxy group and an alkoxy group, and which may have an alkyl group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; silane compounds having an alkenyl group and an alkoxy group, and which may have an alkyl group, such as vinyltrimethoxysilane and p-styryltrimethoxysilane; silane compounds having a (meth)acrylic group and an alkoxy group, and which may have an alkyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amino silane compounds having a primary or secondary amino group and an alkoxy group, and optionally an alkyl group, such as N-(1,3-dimethyl-butylidene)propylamine, N-(2-(ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; and silane compounds having one or more groups selected from the group consisting of a mercapto group, an isocyanato group, a ureido group, and a halogen atom, and one or more alkoxy groups, and optionally an alkyl group, such as 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane.

[0046] (H) Ion trapping agent The ion trapping agent captures free iodonium ions and improves the reliability of the cured product in various ways. There are no particular restrictions on the ion trapping agent, and it can be selected from those commonly used as materials for sealing materials and the like. Specific examples include hydrotalcites, and hydrated oxides of elements such as magnesium, aluminum, titanium, zirconium, and bismuth. Commercially available products include IXEPLAS-A1 and IXEPLAS-A2 manufactured by Toagosei Co., Ltd. One type of ion trapping agent may be used, or two or more types may be used in combination.

[0047] (I) Colorant A colorant can be used for the purpose of coloring the curable resin composition. Examples of colorants that can be used include pigments, dyes, and pigments. Known colorants such as red, blue, green, yellow, black, and white can be used as the colorant. Examples of pigments that can be used include black colorants such as carbon black, graphite, iron oxide, titanium black, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, and bismuth sulfide. Commercially available pigments include Titanium Black 13M, 13M-C, and 13M-T manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.

[0048] Examples of optional components include (G) coupling agent, (H) ion trapping agent, and (I) colorant, as well as additives, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, and solvents.

[0049] In order to obtain a cured product by heating at a low temperature of, for example, 100° C. or less, preferably 80° C. or less, the amount of component (A) in the curable resin composition is preferably 90% by mass or more, or may be 91% by mass or more, or may be 92% by mass or more, relative to 100% by mass of the total amount of components (A), (B), and (C). The total amount of components (B) and (C) is preferably 10% by mass or less, or may be 9% by mass or less, or may be 8% by mass or less, or is preferably 1% by mass or more, or may be 2% by mass or more, or may be 3% by mass or more, relative to the total amount of components (A), (B), and (C).

[0050] In order to obtain a cured product by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, relative to 100% by mass of the total amount of the curable resin composition, the total amount of component (A), component (B), and component (C) is preferably 50 to 100% by mass, more preferably 55 to 95% by mass, and even more preferably 60 to 90% by mass.

[0051] When the curable resin composition contains, as the cationic curable resin of component (A) in the composition, at least one selected from the group consisting of an epoxy resin having a ring skeleton in the molecule of component (A1) and an oxetane resin of component (A2), the total amount of component (A1) and component (A2) is preferably 20 to 100 mass%, more preferably 30 to 90 mass%, and even more preferably 30 to 70 mass%, when the total amount of component (A) is taken as 100 mass%. In order to obtain a cured product having a low elastic modulus, component (A) may be entirely at least one component selected from the group consisting of component (A1) and component (A2) (the total amount of component (A1) and component (A2) is 100 mass%) when the total amount of component (A) is taken as 100 mass%. When the total amount of component (A1) and component (A2) in component (A) is less than 100 mass%, the remainder excluding component (A1) and component (A2) may be at least one selected from the group consisting of epoxy resins not having a ring skeleton in the molecule (e.g., aliphatic epoxy resins), polystyrene-based compounds, and vinyl ether compounds.

[0052] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains component (A1), an epoxy resin having an aromatic ring skeleton, in order to obtain a cured product by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, the amount of the epoxy resin having an aromatic ring skeleton in component (A) is preferably 20 to 100% by mass, more preferably 15 to 95% by mass, and even more preferably 20 to 95% by mass, when the total amount of component (A) is taken as 100% by mass.

[0053] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains component (A1), an epoxy resin having an aromatic ring skeleton, in order to cure by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, the ratio 1 of the number of epoxy group equivalents in component (A1) to the number of functional group equivalents in component (A) (functional group equivalent ratio 1 = [number of epoxy group equivalents in component (A1) having an aromatic ring skeleton] / [number of functional group equivalents in component (A)]) is preferably 0.001 to 1.0, more preferably 0.01 to 0.8, and even more preferably 0.1 to 0.6. The number of functional group equivalents in component (A) refers to the total number of functional group equivalents contained in component (A); when component (A) contains, for example, both an epoxy resin and an oxetane resin, it refers to the total number of epoxy group equivalents and oxetane group equivalents.

[0054] When component (A) in the curable resin composition contains an epoxy resin, in order to obtain a cured product by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, the amount of the epoxy resin having an alicyclic skeleton in component (A) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and even more preferably 1 to 30% by mass, when the total amount of component (A) is taken as 100% by mass.

[0055] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains component (A1), an epoxy resin having an alicyclic skeleton, in order to cure by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, the ratio 2 of the number of epoxy group equivalents of component (A1) to the number of functional group equivalents in component (A) (functional group equivalent ratio 2 = [number of epoxy group equivalents of component (A1) having an alicyclic skeleton] / [number of functional group equivalents of component (A)]) is preferably 0.001 to 0.8, more preferably 0.01 to 0.6, and even more preferably 0.1 to 0.5.

[0056] When component (A) in the curable resin composition contains an epoxy resin and the epoxy resin is an aliphatic epoxy resin, the aliphatic epoxy resin in component (A) may be 0 to 70 mass % or 0 to 60 mass % when the total amount of component (A) is taken as 100 mass %.

[0057] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains an aliphatic epoxy resin, in order to cure by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, the ratio 3 of the epoxy group equivalent number of the aliphatic epoxy resin to the functional group equivalent number of component (A) (functional group equivalent ratio 3 = [epoxy group equivalent number of aliphatic epoxy resin component (A1)] / [functional group equivalent number of component (A)]) is preferably 0.01 to 0.8, more preferably 0.05 to 0.6, and even more preferably 0.1 to 0.5.

[0058] In component (A) in the curable resin composition, the oxetane resin of component (A2) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass, when the total amount of component (A) is taken as 100% by mass. When component (A) contains the oxetane resin of component (A2), in order to accelerate the curing rate and efficiently obtain a cured product by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, the content of the oxetane resin of (A2) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and more preferably 3 to 20% by mass, when the total amount of component (A) is taken as 100% by mass.

[0059] When component (A) in the curable resin composition contains the oxetane resin of component (A2), in order to cure by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less, the ratio 4 of the number of oxetane group equivalents of the oxetane resin of component (A2) to the number of functional group equivalents of component (A) (functional group equivalent ratio 4 = [number of oxetane group equivalents of component (A2)] / [number of functional group equivalents of component (A)]) is preferably 0.001 to 0.8, more preferably 0.01 to 0.6, and even more preferably 0.01 to 0.5.

[0060] The blending ratio of component (A1) to component (A2) in component (A) in the curable resin (component (A1):component (A2)) is preferably 100:0 to 60:40 by mass, more preferably 99:1 to 70:30, and even more preferably 98:2 to 80:20. When the blending ratio of component (A1) to component (A2) in component (A) is 100:0 to 60:40, a cured product can be obtained by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less.

[0061] In order to cure the curable resin by heating at a low temperature, for example, 100°C or less, preferably 80°C or less, the amount of component (B) in the curable resin is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1.0 to 5 parts by mass, relative to 100 parts by mass of component (A).

[0062] In order to cure the curable resin by heating at a low temperature, for example, 100°C or less, preferably 80°C or less, the amount of component (C) in the curable resin is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1.0 to 5 parts by mass, per 100 parts by mass of component (A).

[0063] The blending ratio of component (B) and component (C) in the curable resin (component (B):component (C)) is preferably approximately equal, and may be a mass ratio of 25:75 to 75:25, 30:70 to 70:30, 40:60 to 60:40, or 50:50.

[0064] The amount of the photosensitizer of component (D) in the curable resin composition may be 0 to 3.0 mass%, 0.05 to 3.0 mass%, 0.05 to 2.0 mass%, or 0.1 to 1.0 mass%, relative to 100 mass% of the total amount of the curable resin composition.

[0065] The amount of the photoradical generator of component (E) in the curable resin composition may be 0 to 3.0 mass%, 0.05 to 3.0 mass%, 0.05 to 2.0 mass%, or 0.1 to 1.0 mass%, relative to 100 mass% of the total amount of the curable resin composition.

[0066] The amount of the filler of component (F) in the curable resin composition may be 0 to 50% by mass, 1 to 45% by mass, or 3 to 40% by mass, relative to 100% by mass of the total amount of the curable resin composition. For example, in order to obtain a cured product by heating at a low temperature of 100° C. or less, preferably 80° C. or less, the amount of the filler of component (F) in the curable resin composition is preferably 1 to 45% by mass, and more preferably 3 to 40% by mass, relative to 100% by mass of the total amount of the curable resin composition.

[0067] The amount of the optional components in the curable resin composition is 10% by mass or less, and may be 0 to 10% by mass, 0.1 to 5% by mass, or 0.3 to 3% by mass, relative to 100% by mass of the total amount of the curable resin composition. As described above, the optional components may include at least one selected from the group consisting of (G) a coupling agent, (H) an ion trapping agent, and (I) a colorant.

[0068] Method for Producing Curable Resin Composition The curable resin composition can be produced by mixing components (A), (B), and (C). The curable resin composition can also be produced by further mixing components (D), (E), (F), (G), (H), (I), and other optional components as needed. The curable resin composition may be produced by mixing the components together with additives as needed. The components can be introduced simultaneously or separately into an appropriate mixer, and stirred and mixed while melting by heating if necessary to obtain a curable resin composition. The method for producing the curable resin composition is not particularly limited. The curable resin composition can be produced by mixing the raw materials for each component using a mixer such as a Raikai mixer, Henschel mixer, roll mill, three-roll mill, ball mill, planetary mixer, or bead mill equipped with a stirrer and a heater. The curable resin composition may also be produced using an appropriate combination of two or more devices.

[0069] The curable resin composition is preferably liquid or paste-like at room temperature, for example, 20°C to 30°C. The viscosity of the curable resin composition is preferably 100 Pa s or less, and may be 80 Pa s or less, or preferably 1 Pa s or more, measured using a Brookfield rotational viscometer (HBDV-I or RVDV-I type, spindle: SC4-14 spindle, rotation speed: 50 rpm, measurement temperature: 25°C) immediately after preparation of the resin composition (for example, within 30 minutes), and after leaving the curable resin composition at room temperature, for example, 20°C to 30°C, for a predetermined time. The viscosity is preferably 100 Pa s or less, and may be 80 Pa s or less, or preferably 1 Pa s or more. The viscosity of the curable resin composition at 20°C to 30°C measured by the above-mentioned method may be 3 Pa s to 10 Pa s.

[0070] Adhesive or sealant The curable resin composition can be used as an adhesive or sealant for fixing, joining, or protecting components constituting an electronic device, a camera module, or a sensor module, and can also be used as an adhesive or sealant containing a curable resin composition.

[0071] Method for Supplying Curable Resin Composition The curable resin composition can be supplied using a jet dispenser, an air dispenser, etc. Alternatively, the curable resin composition can be supplied by a known coating method (dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, etc.) or a known printing method (lithographic printing, carton printing, metal printing, offset printing, screen printing, gravure printing, flexographic printing, inkjet printing, etc.).

[0072] Curing Conditions for Curable Resin Composition The resin composition is thermosetting and can be cured by heating at a temperature of 100° C. or less, preferably 80° C. or less, more preferably 75° C. or less, even more preferably 70° C. or more, preferably 45° C. or more, and more preferably 55° C. or more. The heating time for curing the curable resin composition is preferably 15 minutes to 4 hours, more preferably 30 minutes to 2 hours, and even more preferably 30 minutes to 60 minutes.

[0073] Cured Product A cured product can be obtained by curing a curable resin composition, or an adhesive or sealant containing the curable resin composition. The curable resin composition can be cured, for example, at a temperature of at least 100°C or less, preferably at 80°C, for 60 minutes. The glass transition temperature (Tg) of the cured product, measured using a dynamic viscoelasticity measuring device (e.g., a DMA7100 manufactured by Hitachi High-Tech Science Corporation), is preferably 0°C to 200°C, more preferably 1°C to 150°C, even more preferably 2°C to 130°C, and even more preferably 3°C to 120°C. If the Tg of the resulting cured product is 200°C or less, the resulting cured product can be cured at low temperatures. The glass transition temperature is measured using a tensile method in the range of -20°C to 250°C, at a frequency of 10 Hz, a heating rate of 3°C / min, and a strain amplitude of 5 μm. The storage modulus (E') and loss modulus (E'') of the cured product are measured, and the peak temperature of the dielectric loss tangent (tan δ) calculated from E'' / E' is used as Tg.

[0074] Semiconductor Devices, Electronic Devices When the curable resin composition, or an adhesive or encapsulant containing the curable resin composition, is used to fix, bond, or protect electronic components, an electronic device containing a cured product obtained by curing the curable resin composition, or the adhesive or encapsulant containing the curable resin composition is obtained. The electronic device may be a semiconductor device containing a semiconductor element. Examples of electronic devices include mobile phones, smartphones, laptops, tablet terminals, and camera modules. The curable resin composition, or the adhesive or encapsulant containing the curable resin composition is used to fix, bond, or protect electronic components, and an electronic device can be provided using an adhesive that can be cured by heating at a low temperature of 100°C or less, preferably 80°C or less.

[0075] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0076] The components used in the curable resin compositions of the Examples and Comparative Examples are shown below.

[0077] Component (A): Cationic curable resin Component (A1): Epoxy resin having a ring structure in the molecule (A1-1): AER9000 (manufactured by Asahi Kasei Corporation), a special epoxy resin containing a compound in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A skeleton, with a molecular weight of 760 and an epoxy group equivalent of 380 g / eq. (A1-2): EPICLON (registered trademark) EXA-850CRP (manufactured by DIC Corporation), a bisphenol A-type epoxy resin with a molecular weight of 344 and an epoxy group equivalent of 172 g / eq. (A1-3): jER YX8000 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A diglycidyl ether with a molecular weight of 410 and an epoxy group equivalent of 205 g / eq. (A1-4): CELLOXIDE (registered trademark) 2021P (manufactured by Daicel Corporation), 3',4'-epoxycyclomethyl 3,4-epoxycyclohexanecarboxylate, molecular weight 260, epoxy group equivalent 130 g / eq. (A1-5): ADEKA GLYCILOR (registered trademark) ED-509S (manufactured by ADEKA Corporation), p-tert-butylphenyl glycidyl ether, molecular weight 206, epoxy group equivalent 206 / eq.

[0078] Component (A): Cationic curable resin Component (A2): Oxetane resin (A2-1): OXT-221 (manufactured by Toagosei Co., Ltd.), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, molecular weight 214, oxetane group equivalent 107 g / eq. (A2-2): OXT-101 (manufactured by Toagosei Co., Ltd.), 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), molecular weight 116, oxetane group equivalent 116 g / eq.

[0079] Component (B): Acid generator containing an iodonium salt (B-1): Bluesil (registered trademark) PI2074 (manufactured by Elkem Silicones), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (B-2): IK-1FG (manufactured by San-Apro Co., Ltd.)

[0080] Component (C): Peroxydicarbonate-type organic peroxide represented by the formula (1) (C-1): Perkadox 24L (manufactured by Nouryon), dicetyl peroxydicarbonate, 1-hour half-life temperature of 65°C, molecular weight of 570.9, R in formula (1) １ and R ２ are hexadecane groups (-(CH ２ ) １５ -CH ３ ), and is solid (powder) at room temperature (approximately 20°C to 25°C). (C-2): Perkadox 26 (manufactured by Nouryon) dimyristyl peroxydicarbonate, molecular weight 514.8, R in formula (1) １ and R ２ are tetradecane groups (-(CH ２ ) １３ -CH ３ ). (C-3): Perloyl TCP (manufactured by NOF Corporation), bis(4-tert-butylcyclohexyl) peroxydicarbonate, one-hour half-life temperature of 58°C, molecular weight of 398.5, solid (powder) at room temperature (approximately 20°C to 25°C). (C-4): Ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry), molecular weight 486.72, solid (powder) at room temperature (approximately 20°C to 25°C). (C-5): Distearyl peroxydicarbonate (manufactured by SAGECHEM LIMITED), molecular weight 626.99, solid (powder) at room temperature (approximately 20°C to 25°C).

[0081] Component (C'): In the formula (1), R １ and R ２ are each an alkyl group having less than 10 carbon atoms. (C'-1): Luperox 225 (manufactured by Arkema Yoshitomi Co., Ltd.), di(secondary butyl) peroxydicarbonate, one-hour half-life temperature of 69°C, molecular weight of 234.2, liquid at room temperature (approximately 20°C to 25°C).

[0082] (D) Photosensitizer (D-1): DETX, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

[0083] (E) Photoradical Generator (E-1): Omnirad (registered trademark) 184 (manufactured by IGM Resins), 1-hydroxycyclohexyl phenyl ketone

[0084] (F) Fillers (F-1): SE5200SEE (manufactured by Admatechs Co., Ltd.), high-purity synthetic spherical silica, 50% cumulative average particle size of 1.5 μm (catalog value) in volume-based particle size distribution determined by laser diffraction scattering. (F-2): Cabosil (registered trademark) TS720 (manufactured by Cabot Japan Co., Ltd.), hydrophobic silica, 50% cumulative average particle size of 0.012 μm (catalog value) in number-based particle size distribution determined by laser diffraction scattering.

[0085] (G) Coupling Agent (G-1): Silane coupling agent, S530 (manufactured by JNC Corporation), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0086] (H) Ion trapping agent (H-1): IXEPLAS-A1 (manufactured by Toagosei Co., Ltd.), a zirconium-magnesium based ion trapping agent, with an average particle size of 0.5 μm (catalog value).

[0087] (I) Colorant (I-1): Titanium Black 13M (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0088] Examples 1 to 11, Comparative Example 1 Curable resin compositions were prepared by mixing the respective amounts of each component using a three-roll mill according to the blending ratios shown in Tables 1 and 2. In Tables 1 and 2, the numbers indicating the blending ratio of each component contained in the curable resin composition represent mass % relative to 100 mass % of the total amount of the curable resin composition, unless otherwise specified. In the tables, each component is represented mainly by the symbol of the product name or trade name. In addition, in the tables, the symbol "-" indicates that the corresponding component is not contained in the curable resin composition.

[0089] Examples 12 and 13 Resin compositions of Examples 12 and 13 were produced in the same manner as in Example 1, except that the component (C-1) used in Example 1 was replaced with components (C-4) and (C-5), respectively. The properties of the resin compositions of Examples 12 and 13 and the cured products obtained by curing the resin compositions were measured in the same manner as in Example 1. It is expected that the resin compositions of Examples 12 and 13 can also be cured by heating at a low temperature of 80°C or less, and have a long pot life.

[0090] In the examples and comparative examples, the properties of the curable resin compositions and the cured products were measured as follows. The results are shown in Tables 1 and 2.

[0091] Viscosity of Curable Resin Composition Using a Brookfield rotational viscometer (HBDV-I type or RVDV-I type, spindle: SC4-14 spindle, rotation speed: 50 rpm, measurement temperature: 25°C), the viscosity of the curable resin composition was measured at 25°C within 1 hour after preparation as the initial viscosity. The viscosity of the curable resin composition after standing at 25°C for 10 hours was taken as the 10-hour (10 hr) viscosity. The viscosity of the curable resin composition after standing at 25°C for 24 hours was taken as the 24-hour (24 hr) viscosity.

[0092] Pot Life Using a Brookfield rotational viscometer (HBDV-I or RVDV-I, spindle: SC4-14 spindle, rotation speed: 50 rpm, measurement temperature: 25°C), the viscosity of the curable resin composition was measured at 25°C within 1 hour after preparation. Next, a portion of the curable resin composition stored in a sealed container in an environment of 25°C and 50% humidity was removed from the sealed container after 10 and 24 hours, and the viscosity of the curable resin composition was measured. When the viscosity increase ratio (viscosity after 10 hours ÷ initial viscosity) from the initial viscosity measurement to 10 hours later was 1.0 times or less, it was judged as excellent (Excellent, "E"); when it was more than 1.0 times but not more than 2.0 times, it was judged as good (Good, "G"); and when it was more than that, it was judged as not good (Bad, "B"). Furthermore, if the viscosity increase ratio (viscosity after 24 hours divided by the initial viscosity) was 1.0 or less after 24 hours, it was judged as excellent (E), if it was more than 1.0 but not more than 5.0, it was judged as good (G), and if it was more than that, it was judged as not good (Bad (B)). In the table, ">5.0" indicates that the viscosity increase ratio after 24 hours exceeded 5.0.

[0093] Preparation of Cured Products Each of the curable resin compositions of Examples 1 to 11 and Comparative Example 1 was heated at 80° C. for 60 minutes using an air dryer to obtain a cured product.

[0094] Curability at 80°C First, a Teflon (registered trademark) sheet was attached to the surface of a 3 mm thick glass plate, and spacers (heat-resistant tape laminated thereon) were placed in two locations so that the film thickness upon curing would be 400±150 μm. Next, the curable resin composition was applied between the spacers, and the plate was sandwiched between two glass plates with Teflon (registered trademark) sheets attached to the surface to prevent air bubbles from being trapped. The plate was then heated in a blower dryer at 80°C for 60 minutes to cure. If the curable resin composition was solid and had no tackiness, it was rated as excellent (Excellent, "E"); if it was solid and had tackiness, it was rated as good (Good, "G"); and if it was liquid and not cured, it was rated as not good (Bad, "B"). By sandwiching the plate between glass plates, the curability could be judged without considering the influence of oxygen inhibition.

[0095]

[0096]

[0097] As shown in Tables 1 and 2, the cured products of the curable resin compositions of Examples 1 to 11 had good curability and could be cured by heating at low temperatures, for example, 100°C or less, preferably 80°C or less. Furthermore, the viscosity increase ratio was 1.0 after 10 hours, demonstrating excellent pot life. After 24 hours, Example 10 had cured with a viscosity increase ratio exceeding 2.0. Furthermore, the Tg values ​​obtained in the examples were all within the range of 0°C to 200°C. Furthermore, the Tg values ​​obtained in the examples, except for Examples 4, 7, and 8, were all within the range of 0°C to 150°C.

[0098] Comparative Example 1 could be cured at 80°C, but an increase in viscosity was observed after 10 hours, impairing the pot life effect.

[0099] The curable resin composition according to the present invention can be suitably used as an adhesive or sealant for fixing, joining, or protecting components constituting an electronic device. The resin composition according to an embodiment of the present invention, an adhesive or sealant containing the resin composition, a cured product obtained by curing the die attach agent, and an electronic device containing the cured product can be used in, for example, mobile phones, smartphones, laptop computers, tablet terminals, camera modules, sensor modules, etc.

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