Resin composition, adhesive agent, sealing material, cured product, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: a resin composition that is capable of at least being photocured or being cured at low temperature (for example, 100°C or less) and that provides a cured product that exhibits excellent adhesive strength and high heat-resistance reliability; an adhesive agent or a sealing material that includes the same; a cured product thereof; and a semiconductor device and an electronic component that include the cured product.　Provided are: a resin composition containing (A) an epoxy compound, (B) an oxetane compound, and (C) an acid-generating agent that is a salt of an anion represented by formula (1) (In the formula, R1, R2, R3, and R4 independently represent an alkyl group having 1-18 carbon atoms or an aryl group having 6-14 carbon atoms, provided, however, that at least one of R1, R2, R3, and R4 represents an aryl group having 6-14 carbon atoms.) and of a counter cation, and also satisfying at least one of the following characteristics (a) and (b); an adhesive agent or a sealing material including the same; a cured product thereof; and a semiconductor device and an electronic component including the cured product. (a) (D) A filler is further included. (b) The content of (A) the epoxy compound is 100-1300 parts by weight with respect to 100 pats by weight of (B) the oxetane compound.

Description

Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components

[0001] The present invention relates to a resin composition, an adhesive or sealing material containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0002] BACKGROUND ART Currently, adhesives, sealants, etc. containing curable resin compositions, particularly epoxy resin compositions, are often used in the assembly and mounting of semiconductor devices and electronic components, such as semiconductor chips, for the purpose of maintaining reliability.

[0003] Development of photocurable and / or low-temperature curable resin compositions has been progressing. For example, Patent Document 1 discloses a cationic curable resin composition that maintains photocurability and low-temperature curability while exhibiting storage stability, the cationic curable resin composition containing a cationic polymerizable compound, a photocationic polymerization initiator, and a thermal cationic polymerization initiator containing an amine salt. Patent Document 2 also discloses a UV / thermal curable adhesive composition that does not use an antimony compound as the thermal cationic polymerization initiator, is low in toxicity, can be cured at a low temperature of 120°C or less, and produces a cured product with excellent heat resistance. The composition contains specific amounts of an oxetane compound, an alicyclic epoxy compound, an aromatic glycidyl ether epoxy compound, a photocationic polymerization initiator, and a thermal cationic polymerization initiator containing a tetrakis(pentafluorophenyl)borate compound.

[0004] Republished Patent Publication No. 2017 / 094584 Japanese Patent Application Laid-Open No. 2021-147584

[0005] From the viewpoint of reliability of semiconductor devices and electronic components, the cured product of the curable resin composition used for assembly or mounting is required to have high adhesive strength to the adherend.

[0006] Furthermore, after a module is bonded to a different member by photocuring and / or thermal curing using a curable resin composition, a post-process such as reflow may be performed, in which the module is placed in a high-temperature environment (e.g., 200° C. or higher). Therefore, the cured product of the curable resin composition used for assembly or mounting is required to have heat resistance capable of withstanding the reflow process.

[0007] It has been found that when a cured product of the cationically curable resin composition disclosed in Patent Document 1 or Patent Document 2 is placed in a high-temperature environment such as a reflow process, the glass transition temperature Tg and elastic modulus of the cured product decrease, resulting in a decrease in interfacial adhesion between the cured product and an adherend, and consequently a decrease in adhesive strength.

[0008] The present invention aims to provide a resin composition that can be cured at least by light or at a low temperature (for example, 100°C or less) and that gives a cured product that has excellent adhesive strength and heat resistance reliability, an adhesive or sealant containing the same, a cured product thereof, and a semiconductor device and electronic component that contain the cured product.

[0009] Specific means for solving the above problems are as follows: The present invention encompasses the following aspects of a curable resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component: [1] (A) an epoxy compound, (B) an oxetane compound, and (C) a compound represented by the following formula (1): (In the formula, R １ , R ２ , R ３ and R ４ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, provided that R １ , R ２ , R ３ and R ４and a counter cation, and the resin composition satisfies at least one of the following characteristics (a) and (b): (a) further comprises a (D) filler; and (b) the content of the (A) epoxy compound is 100 to 1,300 parts by weight per 100 parts by weight of the (B) oxetane compound. [2] The resin composition according to [1] above, which satisfies the characteristic (a). [3] The resin composition according to [1] above, which satisfies the characteristic (b). [4] The resin composition according to [1] above, which satisfies the characteristics (a) and (b). [5] The resin composition according to any one of [1] to [4] above, wherein the (A) epoxy compound includes an epoxy compound having a polyalkylene oxide chain, an aliphatic moiety derived from an alicyclic diol, an aliphatic moiety derived from hydrogenated bisphenol A, or a combination thereof. [6] The resin composition according to any one of [1] to [5] above, wherein the counter cation is an iodonium cation or a sulfonium cation. [7] The resin composition according to any one of [1], [2], [4], [5], and [6] above, which satisfies the characteristic (a) and in which the content of the (D) filler is 5 to 100 parts by weight per 100 parts by weight of the total of the (A) epoxy compound and the (B) oxetane compound. [8] The resin composition according to any one of [1] to [7] above, further comprising (E) a photosensitizer. [9] The resin composition according to any one of [1] to [8] above, further comprising (F) a photoradical initiator.

[10] The resin composition according to any one of [1] to [9] above, further comprising (H) a thermal radical initiator.

[11] The resin composition according to any one of [1] to

[10] above, which is at least thermosetting.

[12] The resin composition according to any one of the above [1] to

[11] , wherein when the temperature is raised from 25°C to 250°C at a heating rate of 10°C / min using a differential scanning calorimeter, the heat release value in the temperature range of 200°C to 250°C is 10 J / g or less.

[13] The resin composition according to any one of the above [1] to

[12] , wherein components (A) to (C) or components (A) to (D) are contained in a single container.

[14] The resin composition according to any one of [1] to

[12] above, wherein components (A) to (C) or components (A) to (D) are separated into two or more containers.

[15] An adhesive or sealant comprising the resin composition according to any one of [1] to

[14] above.

[16] A cured product obtained by curing the resin composition according to any one of [1] to

[14] above, or the adhesive or sealant according to

[15] above.

[17] A semiconductor device or electronic component comprising the cured product according to

[16] above.

[0010] According to aspects of the present invention, there are provided a resin composition that can be at least photocured or cured at a low temperature (for example, 100°C or less) and that gives a cured product with excellent adhesive strength and heat resistance reliability, an adhesive or encapsulant containing the same, a cured product thereof, and a semiconductor device and an electronic component that contain the cured product.

[0011] In this specification, following the convention in the field of synthetic resins, a name including the term "resin," which normally refers to a polymer (particularly a synthetic polymer), may be used for a component constituting a curable resin composition before curing, even when the component is not a polymer, for example, a monomer or prepolymer compound before curing.

[0012] [Resin Composition] The resin composition according to one embodiment of the present invention comprises: (A) an epoxy compound; (B) an oxetane compound; and (C) a compound represented by the following formula (1): (In the formula, R １ , R ２ , R ３ and R ４ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, provided that R １ , R ２ , R ３ and R ４and a counter cation, and at least one of the following characteristics (a) and (b) is satisfied: (a) further comprises a (D) filler; (b) the content of the (A) epoxy compound is 100 to 1,300 parts by weight per 100 parts by weight of the (B) oxetane compound. According to this aspect, there is provided a resin composition that can be at least photocured or cured at a low temperature (for example, 100°C or lower) and that gives a cured product that is excellent in adhesive strength and heat resistance reliability.

[0013] (A) Epoxy Compound The resin composition of this embodiment contains (A) an epoxy compound (hereinafter also referred to as "component (A)"). In this specification, an epoxy compound refers to a compound having at least one epoxy group in the molecule, and examples thereof include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In this embodiment, (A) the epoxy compound contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds, depending on the type of skeleton.

[0014] Examples of epoxy compounds having an aromatic ring skeleton include polyfunctional epoxy resins, such as bisphenol A epoxy resins (for example, EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), polyalkylene oxide-modified bisphenol A epoxy resins, for example, polypropylene oxide-modified bisphenol A epoxy resins (for example, AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4005, EP-4010S, manufactured by ADEKA Corporation), polyethylene oxide-modified bisphenol A epoxy resins (for example, Rikaresin BEO-60E manufactured by New Japan Chemical Co., Ltd.), bisphenol F epoxy resins (for example, EPICLON (registered trademark) 830-S, EXA-830LVP, EXA-835LV, manufactured by DIC Corporation), Examples of epoxy resins include, but are not limited to, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins (for example, EPICLON (registered trademark) HP-4032D, HP-720H, etc., manufactured by DIC Corporation), phenol novolac type epoxy resins (for example, EPICLON (registered trademark) N-740, N-770, etc., manufactured by DIC Corporation), cresol novolac type epoxy resins (for example, EPICLON (registered trademark) N-660, N-670, N-655-EXP-S, etc., manufactured by DIC Corporation), polyfunctional epoxy compounds such as glycidyl ethers of tetra(hydrophenyl)alkanes and glycidyl ethers of tetrahydroxybenzophenone, and epoxidized polyvinylphenols. Examples of monofunctional epoxy compounds having a polyaromatic ring skeleton include, but are not limited to, p-tert-butylphenyl glycidyl ether (e.g., ADEKA GLYCIROL (registered trademark) ED-509E, ED-509S, etc., manufactured by ADEKA Corporation) and 2-phenylphenol glycidyl ether (e.g., OPP-G, etc., manufactured by SANKO CO., LTD.).

[0015] The epoxy equivalent of the epoxy compound having an aromatic ring skeleton is preferably 90 to 1000 g / eq, more preferably 120 to 800 g / eq, and even more preferably 150 to 500 g / eq.

[0016] Aliphatic epoxy compounds are epoxy compounds that do not have either an aromatic ring skeleton or an alicyclic epoxy group, and examples thereof include glycidyl ethers of aliphatic alcohols (including chain alcohols and alicyclic alcohols) or polyalkylene oxide adducts thereof, and hydrogenated bisphenol-type epoxy resins obtained by hydrogenating bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins. Examples of aliphatic epoxy compounds 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 (e.g., Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether (e.g., jER manufactured by Mitsubishi Chemical Corporation), and the like. YX7400N, etc.), lauryl alcohol polyethylene glycol glycidyl ether (e.g., Denacol EX-171, etc., manufactured by Nagase ChemteX Corporation), diglycidyl ether of alicyclic diol (e.g., ADEKA RESIN EP-4088S and EP-4088L, manufactured by ADEKA Corporation), diglycidyl ether of polyalkylene oxide adduct of alicyclic diol, and hydrogenated bisphenol A diglycidyl ether (e.g., jER YX8000, etc., manufactured by Mitsubishi Chemical Corporation), but are not limited to these.

[0017] The epoxy equivalent of the aliphatic epoxy compound is preferably 90 to 1000 g / eq, more preferably 120 to 800 g / eq, and even more preferably 150 to 500 g / eq.

[0018] One type of alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in its molecule, i.e., a cycloalkene oxide structure. The cycloalkene oxide structure is a structure in which an alicyclic ring and an epoxy ring share a portion of the ring structure, such as a cyclohexene oxide structure or a cyclopentene oxide structure, obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. From the viewpoint of ensuring heat resistance, alicyclic epoxy compounds preferably have 2 to 6 alicyclic epoxy groups, and even more preferably have 2 alicyclic epoxy groups. The number of carbon atoms in the alicyclic ring is not particularly limited. The alicyclic ring of the cycloalkene oxide structure is, for example, preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 6-membered ring. In this specification, alicyclic epoxy compounds may have epoxy groups other than alicyclic epoxy groups. Furthermore, compounds having an aromatic ring are also considered alicyclic epoxy compounds as long as they have an alicyclic epoxy group.

[0019] Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celloxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3, 4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxy

[0033] Examples of epoxy cyclohexane include, but are not limited to, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexyl-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, and the like.

[0020] In this specification, the term "alicyclic epoxy compound" includes not only compounds having the above-mentioned cycloalkene oxide structure, but also compounds containing an epoxy group other than an alicyclic epoxy group and an aliphatic ring, and compounds having an epoxy group in which oxygen atoms are bonded to two carbon atoms in an aliphatic chain. Examples of such alicyclic epoxy compounds include, but are not limited to, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150 manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., EPOLEAD PB manufactured by Daicel Corporation), and compounds in which some or all of the double bonds of a styrene-butadiene copolymer have been epoxidized (e.g., EPOFRIEND manufactured by Daicel Corporation).

[0021] The epoxy equivalent of the alicyclic epoxy compound is preferably 90 to 1000 g / eq, more preferably 100 to 800 g / eq, further preferably 100 to 500 g / eq, and particularly preferably 110 to 300 g / eq.

[0022] The epoxy compounds may be used alone or in combination of two or more.

[0023] The content of the epoxy compound (A) in the resin composition is preferably 1 to 90 parts by weight, and more preferably 5 to 80 parts by weight, per 100 parts by weight of the total amount of the resin composition.

[0024] The epoxy compound preferably contains an epoxy compound having a flexible skeleton. This reduces the change in the glass transition temperature Tg and elastic modulus of the cured product even when the cured product of the resin composition is placed in a high-temperature environment. In one embodiment, the epoxy compound preferably contains an epoxy compound having a polyalkylene oxide chain, an aliphatic moiety derived from an alicyclic diol, an aliphatic moiety derived from hydrogenated bisphenol A, or a combination thereof, and more preferably contains an epoxy compound having a polyalkylene oxide chain. In one embodiment, the polyalkylene oxide chain is a polyethylene oxide chain, a polypropylene oxide chain, a polybutylene oxide chain, a polytrimethylene oxide chain, a polytetramethylene oxide chain, or a combination thereof. Examples of epoxy compounds having such a polyalkylene oxide chain, an aliphatic portion derived from an alicyclic diol, an aliphatic portion derived from hydrogenated bisphenol A, or a combination thereof include polyalkylene oxide-modified bisphenol A-type epoxy resins, such as polypropylene oxide-modified bisphenol A-type epoxy resins (e.g., AER9000 manufactured by Asahi Kasei Corporation, and EP-4000S, EP-4003S, EP-4005, and EP-4010S manufactured by ADEKA Corporation), polyethylene oxide-modified bisphenol A-type epoxy resins (e.g., Rikaresin BEO-60E manufactured by New Japan Chemical Co., Ltd.), polybutylene glycol diglycidyl ether (e.g., jER manufactured by Mitsubishi Chemical Corporation), and the like. YX7400N, etc.), lauryl alcohol polyethylene glycol glycidyl ether (e.g., Denacol EX-171, etc., manufactured by Nagase ChemteX Corporation), diglycidyl ether of alicyclic diol (e.g., ADEKA RESIN EP-4088S and EP-4088L, manufactured by ADEKA Corporation), diglycidyl ether of polyalkylene oxide adduct of alicyclic diol, hydrogenated bisphenol A diglycidyl ether (e.g., jER YX8000, etc., manufactured by Mitsubishi Chemical Corporation), and the like, but are not limited to these.In one embodiment, the amount of the epoxy compound having a polyalkylene oxide chain, an aliphatic moiety derived from an alicyclic diol, an aliphatic moiety derived from hydrogenated bisphenol A, or a combination thereof, relative to 100 parts by weight of the total epoxy compounds, is preferably 20 to 100 parts by weight, more preferably 30 to 100 parts by weight, and even more preferably 40 to 100 parts by weight. In one embodiment, the amount of the epoxy compound having a polyalkylene oxide chain, relative to 100 parts by weight of the total epoxy compounds, is preferably 10 to 100 parts by weight, and more preferably 15 to 100 parts by weight.

[0025] (B) Oxetane Compound The resin composition of this embodiment contains (B) an oxetane compound (hereinafter also referred to as "component (B)"). The oxetane compound is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in the molecule. Although the polymerization initiation reaction of an oxetane compound is slower than that of an epoxy compound, it polymerizes rapidly once the polymerization initiation species reaches a certain concentration or higher, thereby contributing to the curing reaction of the resin composition at low temperatures and in a short time. Furthermore, by including the above-mentioned (A) epoxy compound and oxetane compound in combination in the resin composition, the adhesive strength of the cured product is improved. In one embodiment, the oxetane compound preferably has 1 to 6 oxetane rings in the molecule, and more preferably has 1 to 2 oxetane rings in the molecule.

[0026] Examples of oxetane compounds include, but are not limited to, bis[1-ethyl(3-oxetanyl)]methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane)), xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and the like. Other examples of the oxetane compound include oxetanyl silsesquioxetane (such as OXT-191 manufactured by Toagosei Co., Ltd.), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (such as OXT-221 manufactured by Toagosei Co., Ltd.), and phenol novolac oxetane (such as PHOX manufactured by Toagosei Co., Ltd.). Any one of the oxetane compounds may be used alone, or two or more of them may be used in combination.

[0027] The oxetane equivalent of the oxetane compound is preferably 90 to 500 g / eq, and more preferably 100 to 300 g / eq.

[0028] The content of the oxetane compound (B) in the resin composition is preferably 1 to 60 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the total amount of the resin composition.

[0029] (C) Acid Generator The resin composition of this embodiment contains (C) an acid generator represented by the following formula (1): (In the formula, R １ , R ２ , R ３ and R ４ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, provided that R １ , R ２ , R ３ and R４ wherein at least one of the groups represents an aryl group having 6 to 14 carbon atoms.) The resin composition includes an acid generator (hereinafter also referred to as "(C) acid generator," "(C) gallate-based acid generator," or "component (C)") that is a salt formed from an anion represented by formula (1) and a counter cation. The acid generator generates an acid as an active species in response to light or heat, thereby promoting polymerization of the cationically polymerizable compound. By including an acid generator that is a salt formed from an anion represented by formula (1) (hereinafter also referred to as "gallate anion") and a counter cation, the resin composition can be cured at least by light or at low temperatures (for example, 100°C or less) and can give a cured product with excellent heat resistance reliability.

[0030] A typical acid generator is BF as the anion moiety. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － The strength of the acid generated by the acid generator depends on the anion moiety. The stronger the acid generated by the acid generator, the higher the polymerization activity of cationic polymerization. The strength of the acid generated depends on the anion moiety. ４ － <PF ６ － <AsF ６ － <SbF ６ － AsF generates strong acid ６ － and SbF ６ － The use of acid generators having As and Sb is limited due to the toxicity of As and Sb. Therefore, acid generators having B (C ６ F ５ ) ４ －Acid generators having a tetrakis(pentafluorophenyl)borate anion (hereinafter also referred to as "borate anion") as the anion are sometimes used. However, because such borate anions have a very stable structure, it has been found that when a cured product of a resin composition cured using an acid generator having such an anion moiety is placed in a high-temperature environment such as a reflow process, the anion moiety remaining in the cured product remains as a super strong acid without thermal decomposition, and this acid induces cleavage of molecular crosslinks in the cured product. As the cured product decomposes, the glass transition temperature Tg and elastic modulus of the cured product decrease, resulting in a decrease in interfacial adhesion between the cured product and the adherend, resulting in a decrease in adhesive strength. While the gallate anion in the acid generator (C) of this embodiment generates a strong acid, it has lower thermal stability than the borate anion and is decomposed at high temperatures. Although the decomposition product may generate a weak acid, it does not induce decomposition of the cured product, thereby suppressing a decrease in the Tg and elastic modulus of the cured product. As a result, a cured product of a resin composition with excellent heat resistance reliability can be obtained.

[0031] In formula (1), R １ , R ２ , R ３ and R ４ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R １ , R ２ , R ３ and R ４ At least one of R represents an aryl group having 6 to 14 carbon atoms. １ , R ２ , R ３ and R ４ is any combination of the following: (i) R １ , R ２ , R ３ and R ４ (ii) R is a combination of one aryl group and the remaining three alkyl groups. １ , R ２ , R ３ and R ４ (iii) R is a combination of two aryl groups and the remaining two alkyl groups. １ , R ２ , R ３and R ４ (iv) R is a combination of three aryl groups and the remaining one alkyl group. １ , R ２ , R ３ and R ４ Among the above combinations, the anion of (iii) or (iv) is preferred, and the anion of (iv) is more preferred.

[0032] R in formula (1) １ , R ２ , R ３ and R ４ The alkyl group having 1 to 18 carbon atoms represented by may be any of a linear, branched, or cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a t-pentyl group, a sec-pentyl group, an n-hexyl group, an isohexyl group, an n-heptyl group, a sec-heptyl group, an n-octyl group, an n-nonyl group, a sec-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a cyclopentyl group, and a cyclohexyl group. １ , R ２ , R ３ and R ４ The alkyl group having 1 to 18 carbon atoms represented by may have a substituent. The term "substituted alkyl group" used herein means an alkyl group in which a hydrogen atom in the alkyl group structure is substituted with a substituent, and the position and number of the substituent are not particularly limited. When the substituent has a carbon atom, R １ , R ２ , R ３ and R ４ The number of carbon atoms in the alkyl group represented by does not include the number of carbon atoms in the substituent. Specifically, for example, an ethyl group having a phenyl group as a substituent is an alkyl group having two carbon atoms.

[0033] R in formula (1) １ , R ２ , R ３ and R４ The substituents that the alkyl group having 1 to 18 carbon atoms represented by the formula (I) may have are not particularly limited (excluding alkyl groups). Examples of such substituents include an alkoxy group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ２ group), a cyano group, an isocyano group, etc.

[0034] R in formula (1) １ , R ２ , R ３ and R ４ The alkoxy group that may be substituted on the alkyl group having 1 to 18 carbon atoms represented by is a substituent in which an oxygen atom and an alkyl group are bonded. Examples of the alkyl group that this alkoxy group has include, for example, R １ , R ２ , R ３ and R ４ The alkyl groups represented by R in formula (1) are the same as those described in the section on the alkyl group having 1 to 18 carbon atoms. １ , R ２ , R ３ and R ４ The aromatic group that may be substituted on the alkyl group having 1 to 18 carbon atoms represented by is not particularly limited as long as it is a residue in which one hydrogen atom has been removed from the aromatic ring of an aromatic compound. Examples of such aromatic groups include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a tolyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a phenanthenyl group, and a mestyl group. １ , R ２ , R ３ and R ４The heterocyclic group which may be substituted by the alkyl group having 1 to 18 carbon atoms represented by the formula (I) is not particularly limited as long as it is a residue in which one hydrogen atom has been removed from the heterocyclic ring of a heterocyclic compound. Examples of such heterocyclic groups include a furanyl group, a thienyl group, a thienothienyl group, a pyrrolyl group, an imidazolyl group, an N-methylimidazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a quinolyl group, an indolyl group, a benzopyrazyl group, a benzopyrimidyl group, a benzothienyl group, a naphthothienyl group, a benzofuranyl group, a benzothiazolyl group, a pyridinothiazolyl group, a benzimidazolyl group, a pyridinoimidazolyl group, an N-methylbenzimidazolyl group, a pyridino-N-methylimidazolyl group, a benzoxazolyl group, a pyridinooxazolyl group, a benzothiadiazolyl group, a pyridinothiadiazolyl group, a benzoxadiazolyl group, a pyridinooxadiazolyl group, a carbazolyl group, a phenoxazinyl group, and a phenothiazinyl group. １ , R ２ , R ３ and R ４ Examples of the halogen atom that may be substituted on the alkyl group having 1 to 18 carbon atoms represented by the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １ , R ２ , R ３ and R ４ The alkyl-substituted amino group that may be substituted by the alkyl group having 1 to 18 carbon atoms represented by may be either a mono-alkyl-substituted amino group or a di-alkyl-substituted amino group. Examples of the alkyl group in these alkyl-substituted amino groups include R １ , R ２ , R ３ and R ４ The alkyl groups represented by R in formula (1) are the same as those described in the section on the alkyl group having 1 to 18 carbon atoms. １ , R ２ , R ３ and R ４The aryl-substituted amino group which may be substituted on the alkyl group having 1 to 18 carbon atoms represented by the formula (1) may be either a monoaryl-substituted amino group or a diaryl-substituted amino group. The aryl group in these aryl-substituted amino groups is R １ , R ２ , R ３ and R ４ Examples of the aromatic groups include the same aromatic groups that may be substituted on the alkyl group having 1 to 18 carbon atoms represented by the formula (I).

[0035] R in formula (1) １ , R ２ , R ３ and R ４ Specific examples of the aryl group having 6 to 14 carbon atoms represented by R in formula (1) include １ , R ２ , R ３ and R ４ Examples of the aromatic groups include the same as the aromatic groups which may be substituted on the alkyl group having 1 to 18 carbon atoms represented by the formula (I).

[0036] R in formula (1) １ , R ２ , R ３ and R ４ The aryl group having 6 to 14 carbon atoms represented by may have a substituent. The term "substituted aryl group" used herein means an aryl group in which a hydrogen atom in the structure of the aryl group is substituted with a substituent, and the position and number of the substituent are not particularly limited. When the substituent has a carbon atom, R １ , R ２ , R ３ and R ４ The number of carbon atoms in the aryl group represented by does not include the number of carbon atoms in the substituent. Specifically, for example, a phenyl group having an ethyl group as a substituent is an aryl group having 6 carbon atoms.

[0037] R in formula (1) １ , R ２ , R ３ and R ４There is no particular limitation on the substituent that the aryl group having 6 to 14 carbon atoms represented by the formula (I) may have. Examples of such a substituent include an alkyl group, an alkoxy group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ２ group), a cyano group, an isocyano group, etc.

[0038] R in formula (1) １ , R ２ , R ３ and R ４ Examples of the alkyl group that may be substituted on the aryl group having 6 to 14 carbon atoms represented by R １ , R ２ , R ３ and R ４ The alkyl groups represented by R in formula (1) are the same as those described in the section on the alkyl group having 1 to 18 carbon atoms. １ , R ２ , R ３ and R ４ Specific examples of the alkoxy group, aromatic group, heterocyclic group, halogen atom, alkyl-substituted amino group and aryl-substituted amino group that may be substituted by the aryl group having 6 to 14 carbon atoms represented by R in formula (1) include: １ , R ２ , R ３ and R ４ Examples of the alkoxy group, aromatic group, heterocyclic group, halogen atom, alkyl-substituted amino group and aryl-substituted amino group that may be substituted by the alkyl group having 1 to 18 carbon atoms represented by the formula (I) include the same as the alkoxy group, aromatic group, heterocyclic group, halogen atom, alkyl-substituted amino group and aryl-substituted amino group that may be substituted by the alkyl group having 1 to 18 carbon atoms represented by the formula (I).

[0039] R in formula (1) １ , R ２ , R ３ and R ４ As the alkyl group, a phenyl group having a perfluoroalkyl group as a substituent or a phenyl group having a fluorine atom as a substituent is preferred, and a pentafluorophenyl group or a bis(trifluoromethyl)phenyl group is more preferred.

[0040] Specific examples of the gallate anion of formula (1) include, but are not limited to, the following:

[0041] The counter cation that forms a salt with the gallate anion represented by (1) is not particularly limited as long as it is a monovalent cation, and examples thereof include an iodonium cation, a sulfonium cation, an ammonium cation, and a phosphonium cation. In one embodiment, the counter cation is preferably an iodonium cation or a sulfonium cation, and more preferably an iodonium cation.

[0042] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium. Acid generators whose counter cation is an iodonium cation can function as photoacid generators and thermal acid generators.

[0043] Examples of sulfonium cations include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]di Phenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio) )phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthrenium, 5-tolylthiaanthrenium, 5-(4-ethoxyphenyl)thiaanthrenium and 5-(2,4,triarylsulfonium such as diphenylphenacylsulfonium, diphenyl-4-nitrophenacylsulfonium, diphenylbenzylsulfonium and diphenylmethylsulfonium; monoarylsulfonium such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium and 9-anthracenylmethylphenacylsulfonium; Examples of suitable acid generators include trialkylsulfonium compounds such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium. Acid generators whose counter cation is a triarylsulfonium cation can function as photoacid generators. Acid generators whose counter cation is a diarylsulfonium cation, monoarylsulfonium cation, or trialkylsulfonium cation can function as thermal acid generators.

[0044] Examples of ammonium cations include pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; and morpholiniums such as N,N'-dimethylmorpholinium. pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazolium such as N,N'-dimethylimidazolium; quinolium such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.

[0045] Examples of the phosphonium cation include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0046] In this embodiment, the content of the acid generator (C) in the resin composition is preferably 0.1 to 10 parts by weight, and more preferably 0.3 to 8 parts by weight, per 100 parts by weight of the total amount of the resin composition. The content of the acid generator (C) in the resin composition is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 15 parts by weight, and even more preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the epoxy compound (A) and the oxetane compound (B).

[0047] The resin composition of this embodiment satisfies at least one of the following characteristics (a) and (b): (a) further contains a filler (D), and (b) the content of the epoxy compound (A) is 100 to 1,300 parts by weight per 100 parts by weight of the oxetane compound (B). This provides a resin composition that gives a cured product with excellent adhesive strength.

[0048] (D) Filler The resin composition of this embodiment contains a filler (hereinafter also referred to as "component (D)"), which can improve the fluidity, injectability, coatability, adhesion, etc. of the resin composition, thereby providing a cured product with excellent adhesive strength. Fillers are broadly classified into inorganic fillers and organic fillers.

[0049] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it allows for a high loading. Amorphous silica is preferred as the silica. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0050] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, filler having a urethane skeleton, filler having a butadiene skeleton, styrene filler, etc. The organic filler may be surface-treated.

[0051] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0052] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d ５０ ) By setting the average particle size of the filler to the upper limit or less, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, which can prevent wear on the jet dispenser nozzle and scattering of the resin composition ejected from the jet dispenser nozzle outside the desired area. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.01 μm or more. In some embodiments of this aspect, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 6.0 μm.

[0053] The filler may be used alone or in combination of two or more.

[0054] When the resin composition of this embodiment contains a (D) filler, the content of the (D) filler in the resin composition is preferably 15 to 50 parts by weight, more preferably 20 to 50 parts by weight, and even more preferably 30 to 50 parts by weight, per 100 parts by weight of the total amount of the resin composition.

[0055] In the resin composition of this embodiment, the content of the (A) epoxy compound is 100 to 1,300 parts by weight relative to 100 parts by weight of the (B) oxetane compound, so that even in an embodiment that does not contain the (D) filler, the adhesion of the resin composition can be improved and a cured product with excellent adhesive strength can be obtained. From the viewpoint of more easily achieving the above-mentioned effect, the content of the (A) epoxy compound is preferably 200 to 1,300 parts by weight, more preferably 300 to 1,250 parts by weight relative to 100 parts by weight of the (B) oxetane compound.

[0056] In one embodiment, the resin composition of this aspect satisfies the characteristic (a). In one embodiment, the resin composition of this aspect satisfies the characteristic (b). In one embodiment, the resin composition of this aspect satisfies the characteristics (a) and (b).

[0057] In one embodiment, the resin composition of this aspect satisfies the characteristic (a), and the content of the (D) filler is 5 to 100 parts by weight, preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight, relative to 100 parts by weight of the total of the (A) epoxy compound and the (B) oxetane compound.

[0058] The resin composition of this embodiment may, if desired, contain optional components other than the above components (A) to (C) or (A) to (D), such as those described below, as necessary.

[0059] (E) Photosensitizer The resin composition of this embodiment may contain (E) a photosensitizer (hereinafter also referred to as "component (E)"), if desired, to the extent that the effects of the present invention are not impaired. The photosensitizer absorbs light energy and transmits it to the acid generator, thereby increasing the sensitivity of the acid generator 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.

[0060] 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.

[0061] Other examples of photosensitizers include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluorenamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9'-spirobi[9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, 2- Examples of suitable hydroxy-2-methyl-1-phenylpropan-1-one include, but are not limited to, hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, nitro compounds, and dyes.

[0062] The photosensitizer may be used alone or in combination of two or more. When the resin composition contains a photosensitizer, the content of the photosensitizer is preferably 0.1 to 20 parts by weight, and more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the acid generator.

[0063] (F) Photoradical Initiator The resin composition of this embodiment may contain (F) a photoradical initiator (hereinafter also referred to as "component (F)"), if desired, within a range that does not impair the effects of the present invention. The photoradical initiator absorbs light to generate radicals as active species, which can reductively decompose the acid generator and promote the generation of acid from the acid generator. Examples of photoradical initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0064] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369 manufactured by IGM Resins BV), etc., but are not limited to these. These may be used alone or in combination of two or more.

[0065] Examples of the acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.). These compounds may be used alone or in combination of two or more.

[0066] Examples of the oxime ester compound include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation).

[0067] Examples of compounds having a photosensitive moiety and a peroxide structure or commercially available products thereof include 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation), but are not limited to these.

[0068] In addition to the above-mentioned photoradical initiators, examples of the photoradical initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyl dimethyl ketone. Examples of the benzoyl benzoates include, but are not limited to, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzil, camphorquinone, etc. These may be used alone or in combination of two or more.

[0069] The photoradical initiators may be used alone or in combination of two or more.

[0070] When the resin composition contains a photoradical initiator, the content of the photoradical initiator is preferably 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, per 100 parts by weight of the acid generator.

[0071] (G) Coupling Agent The resin composition of this embodiment may contain (G) a coupling agent (hereinafter also referred to as "component (G)"), if desired, to the extent that the effects of the present invention are not impaired. The coupling agent has two or more different functional groups in the 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 resin composition, the adhesive strength of the resin composition to an adherend such as a substrate is improved.

[0072] Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, etc., depending on the type of functional group that chemically bonds with the inorganic material.

[0073] Examples of coupling agents include, but are not limited to, various coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto coupling agents depending on the type of functional group that chemically bonds with the organic material. Among these, epoxy coupling agents containing an epoxy group are preferred from the viewpoint of moisture resistance reliability.

[0074] The coupling agents may be used alone or in combination of two or more.

[0075] When a coupling agent is added, the amount of the coupling agent added is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of the resin composition, from the viewpoint of improving adhesive strength.

[0076] (H) Thermal Radical Initiator The resin composition of this embodiment may contain (H) a thermal radical initiator (hereinafter also referred to as "component (H)"), if desired, within a range that does not impair the effects of the present invention. The thermal radical initiator generates an active radical by cleavage at a predetermined temperature, which can reductively decompose the acid generator and promote the generation of an acid from the acid generator. Examples of thermal radical initiators include organic peroxides, inorganic peroxides, and azo compounds. In one embodiment, the thermal radical initiator is preferably an organic peroxide.

[0077] Examples of organic peroxides include at least one selected from ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, and peroxycarbonates. Specific examples of the organic peroxides include 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1,3,3-tetrabutylperoxydecanoate, t-butyl peroxybenzoate, dicumyl peroxide, tert-butyl-α-cumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, and the like. peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,2-di(4,4-di-(butylperoxy)cyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, 1,1-di(t-butylperoxy)cyclohexane, cyclohexanone peroxide, 1,1-di(t-hexylperoxy)cyclohexane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, t-amylperoxyneodecanoate, bis(1-methyl-1-phenylethyl)peroxide, and the like, but are not limited to these. These can be used alone or in combination of two or more. Examples of commercially available organic peroxides include Perocta (registered trademark) O manufactured by NOF Corporation and Perkadox 24L manufactured by Kayaku Nouryon Co., Ltd.

[0078] Examples of azo compounds include, but are not limited to, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane. These compounds may be used alone or in combination of two or more.

[0079] The thermal radical initiators may be used alone or in combination of two or more.

[0080] When the resin composition contains a thermal radical initiator, the content of the thermal radical initiator is preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight, per 100 parts by weight of the acid generator.

[0081] (I) Pigment The resin composition of this embodiment may contain a pigment (I) (hereinafter also referred to as "component (I)") to the extent that the effects of the present invention are not impaired. Depending on the application of the cured product of the resin composition, light-blocking properties may be required. In such cases, the resin composition of this embodiment may contain a pigment. Examples of pigments include inorganic pigments 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, as well as organic pigments such as azo, cyanine, phthalocyanine, and quinacridone pigments. Examples of commercially available pigments include Titanium Black 13M, 13M-C, and 13MT manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. The amount of pigment added can be determined appropriately depending on the application of the cured product of the resin composition.

[0082] Other Additives If desired, the resin composition of this embodiment may further contain other additives, such as a conductive filler, a stabilizer, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a plasticizer, a solvent, etc. The type and amount of each additive are as per usual, provided that the purpose of the embodiment is not impaired.

[0083] From the viewpoint of preventing a reduction in curing strength and adhesion and preventing outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, ionic liquids, etc. (excluding the liquid components (A) to (C)). For example, the content of liquid components relative to the total weight of the resin composition is preferably 3 wt % or less, and more preferably 1 wt % or less. Examples of the solvent include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, butyrolactone, propylene carbonate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0084] The method for producing the resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (C) or components (A) to (D), and other optional components as needed, into an appropriate mixer, and stirring and mixing while melting by heating if necessary to form a homogeneous composition. The mixer is not particularly limited, but examples of the mixer that can be used include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirrer and a heater. These devices may also be used in appropriate combinations.

[0085] The resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition divided into two or more containers, depending on the application. When a two-component (or multi-component) resin composition is used, the components (A) to (C) or (A) to (D), and other optional components as needed, can be selected in the same way as for a one-component resin composition. Furthermore, when a two-component (or multi-component) resin composition is used, the components (A) to (C) or (A) to (D), and other optional components as needed, can be divided into two or multiple components in any way without particular limitation, but it is preferable to separate component (C) from component (E) and / or component (F) and / or component (H) as separate liquids. When the mixture is separated into two or more liquids by any separation method, each liquid may contain one or more components selected from the components (A) to (C) or the components (A) to (D) and other optional components as required, the components (A) to (C) or the components (A) to (D) may be contained in one liquid, or there may be a liquid consisting only of the components (A) to (C) or the components (A) to (D) and / or other optional components as required. For example, when separating into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (C), liquid B: component (B), liquid A: component (A), liquid B: component (B), component (C), and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), liquid A: component (A) and component (D), liquid B: component (B) and component (C). Alternatively, the liquid A may be component (B), the liquid B may be component (A), component (C), and component (D), the liquid A may be component (A), component (B), and component (D), the liquid B may be component (A), component (C), and component (D), the liquid A may be component (A), component (E), and component (H), the liquid B may be component (B), component (C), and component (D), the liquid A may be component (A), component (F), and component (H), the liquid B may be component (B), component (C), and component (D).When components (A) to (C) or components (A) to (D) are contained in Liquid A and the other components are contained in Liquid B, Liquid A alone, or Liquid A and Liquid B together, can be considered to be the resin composition of this embodiment. On the other hand, when components (A) to (C) or components (A) to (D) are each contained in a separate liquid, the respective liquids together can be considered to be the resin composition of this embodiment. An example of a case where components (A) to (C) or components (A) to (D) are each contained in a separate liquid is a resin composition in which components (A) to (C) or components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C) or components (A) to (D).

[0086] The resin composition thus obtained may be photocurable, thermosetting, or photo- and thermosetting, depending on the type of acid generator contained in the resin composition. When the resin composition is photocurable, the photocuring of the resin composition is carried out, for example, by irradiating the resin composition with UV light. When the resin composition is thermosetting, it is preferably cured within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour at a temperature of 100°C. In one embodiment, for example, the resin composition of this aspect is thermally cured at a temperature of 70 to 100°C for 30 to 120 minutes. When the resin composition is photo- and thermosetting, it can be further cured with heat, for example, after curing with light (UV) or during light irradiation.

[0087] The resin composition of this embodiment inhibits decomposition of the cured product, even when the cured product is placed in a high-temperature environment (e.g., 200°C or higher) such as a reflow process, and inhibits a decrease in the Tg and elastic modulus of the cured product. Decomposition of the cured product in a high-temperature environment can be confirmed by DSC measurement. When the resin composition of this embodiment is heated from 25°C to 250°C at a heating rate of 10°C / min using a differential scanning calorimeter, it is preferable that the heat generation amount in the temperature range from 200°C to 250°C is 10 J / g or less.

[0088] In the resin composition of this embodiment, the Tg of the cured product obtained by photocuring and / or heat curing under conditions of a temperature of 100° C. or less is preferably 10 to 150° C., more preferably 20 to 120° C., and even more preferably 25 to 90° C. This results in smaller changes in the glass transition temperature Tg and elastic modulus of the cured product, even when the cured product of the resin composition is placed in a high-temperature environment.

[0089] In the resin composition of this embodiment, the elastic modulus of the cured product obtained by photocuring and / or heat curing under conditions of a temperature of 100° C. or less is preferably 0.01 to 5 GPa, more preferably 0.1 to 4 GPa, and even more preferably 0.2 to 3.8 GPa. This results in smaller changes in the glass transition temperature Tg and elastic modulus of the cured product, even when the cured product of the resin composition is placed in a high-temperature environment.

[0090] The resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining or protecting semiconductor devices or electronic components or components constituting them, or as a raw material thereof.

[0091] The method for applying the resin composition is not particularly limited, and for example, the resin composition can be applied to a desired portion of a component such as a substrate by a known printing method, dispensing method, or coating method. Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, and flexographic printing. Dispensing methods include, but are not limited to, methods using a jet dispenser or an air dispenser. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.

[0092] [Adhesive or Sealant] Another embodiment of the present invention is an adhesive or sealant that includes the resin composition of the above-described embodiment. This adhesive or sealant enables good fixation, bonding, or protection of general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, polyphthalamide, polybutylene terephthalate, etc.), glass, ceramics, and metals (e.g., copper, nickel, SUS, etc.), and organic substrates (e.g., FR4, etc.), and can be used to fix, bond, or protect components that make up a semiconductor device or electronic component. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules and time-of-flight sensor modules, other semiconductor modules, and integrated circuits.

[0093] The adhesive or sealant of this embodiment can be a one-component adhesive or sealant contained in a single container, or a two-component (or multi-component) adhesive or sealant divided into two or more containers, depending on its intended use. When a two-component (or multi-component) adhesive or sealant is used, the components (A) to (C) or (A) to (D), and other optional components as needed, can be selected in the same manner as for a one-component adhesive or sealant. Furthermore, when a two-component (or multi-component) adhesive or sealant is used, the components (A) to (C) or (A) to (D), and other optional components as needed, can be divided into two or multiple components in any manner without particular limitation, but it is preferable to separate component (C) from component (E) and / or component (F) and / or component (H) as separate liquids. When the mixture is separated into two or more liquids by any separation method, each liquid may contain one or more components selected from the components (A) to (C) or the components (A) to (D) and other optional components as required, the components (A) to (C) or the components (A) to (D) may be contained in one liquid, or there may be a liquid consisting only of the components (A) to (C) or the components (A) to (D) and / or other optional components as required. For example, when separating into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (C), liquid B: component (B), liquid A: component (A), liquid B: component (B), component (C), and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), liquid A: component (A) and component (D), liquid B: component (B) and component (C). Alternatively, the liquid A may be component (B), the liquid B may be component (A), component (C), and component (D), the liquid A may be component (A), component (B), and component (D), the liquid B may be component (A), component (C), and component (D), the liquid A may be component (A), component (E), and component (H), the liquid B may be component (B), component (C), and component (D), the liquid A may be component (A), component (F), and component (H), the liquid B may be component (B), component (C), and component (D).When components (A) to (C) or components (A) to (D) are contained in Liquid A and the other components are contained in Liquid B, Liquid A alone, or Liquid A and Liquid B together, can be considered to be the adhesive or sealant of this embodiment. On the other hand, when components (A) to (C) or components (A) to (D) are each contained in a separate liquid, the respective liquids together can be considered to be the adhesive or sealant of this embodiment. An example of a case where components (A) to (C) or components (A) to (D) are each contained in a separate liquid is an adhesive or sealant in which components (A) to (C) or components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C) or components (A) to (D).

[0094] [Cured product of resin composition, adhesive, or encapsulant] Another aspect of the present invention is a cured product obtained by curing the resin composition, adhesive, or encapsulant of the above-described aspect. This cured product has excellent adhesive strength to an adherend and heat resistance reliability.

[0095] [Semiconductor Device, Electronic Component] Another aspect of the present invention is a semiconductor device or electronic component that includes the cured product of the above-described aspect. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules and time-of-flight (TOF) sensor modules, other semiconductor modules, and integrated circuits.

[0096] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and percentages are by weight unless otherwise specified.

[0097] [Production of Resin Composition] Resin compositions of the Examples and Comparative Examples were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by weight (unit: g). The components used in the Examples and Comparative Examples are as follows.

[0098] (A) Epoxy Compounds (A-1): Hydrogenated bisphenol A diglycidyl ether (product name: jER YX8000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 205 g / eq) (A-2): Bisphenol A epoxy resin (product name: EXA-850CRP, manufactured by DIC Corporation, epoxy equivalent: 170 g / eq) (A-3): Polypropylene oxide-modified bisphenol A epoxy resin (product name: AER9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380 g / eq) (A-4): 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (product name: CELLOXIDE (registered trademark) 2021P, manufactured by Daicel Corporation, alicyclic epoxy, epoxy equivalent: 130 g / eq) (A-5): p-tert-butylphenyl glycidyl ether (product name: ADEKA GLYCIROL (registered trademark) ED-509S, manufactured by ADEKA Corporation, monofunctional epoxy, epoxy equivalent: 205 g / eq)

[0099] (B) Oxetane Compound (B-1): 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (product name: OXT-221, manufactured by Toagosei Co., Ltd., oxetane equivalent: 107 g / eq)

[0100] (C) Acid generators (gallate-based acid generators) which are salts of a gallate anion of formula (1) and a counter cation (C-1): Acid generators represented by the following formula: This acid generator was synthesized by the method described in JP 2022-080366 A. This acid generator can function as both a photoacid generator and a thermal acid generator. (C-2): Photoacid generator represented by the following formula: This photoacid generator was synthesized by the method described in WO 2018 / 020974. (C-3): A thermal acid generator represented by the following formula: This thermal acid generator was synthesized by the method described in WO2018 / 020974. (C') Acid generator other than component (C) (borate-based acid generator) (C'-1): 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (product name: BLUESIL (registered trademark) PI 2074, manufactured by ELKEM SILICONES)

[0101] (D) Filler (D-1): Hydrophobic fumed silica (product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT Corporation, average particle size: 12 nm) (D-2): Surface-treated silica filler (product name: SE5200SEE, average particle size 2 μm, manufactured by Admatechs Co., Ltd.)

[0102] (E) Photosensitizer (E-1): 2,4-diethylthioxanthone (DETX) (F) Photoradical initiator (F-1): 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.) (G) Coupling agent (G-1): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) (H) Thermal radical initiator (H-1): dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd.) (H-2): 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (product name: Perocta (registered trademark) O, manufactured by NOF Corporation) (I) Pigment (I-1): Titanium black (product name: 13M, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0103] [Measurement of calorific value of resin composition] The resin compositions of the examples and comparative examples were subjected to DSC measurement using a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation) by heating from 25°C to 250°C at a heating rate of 10°C / min. From the obtained DSC curve, the calorific value (J / g) in the temperature range of 200°C to 250°C was determined. In this specification, the calorific value in the temperature range of 200°C to 250°C determined under the above conditions is preferably 10 J / g or less.

[0104] [Measurement of adhesive strength (shear strength) and heat resistance of cured product] (1) On an organic substrate (FR4), the resin compositions of the Examples and Comparative Examples were applied by stencil printing to a size of φ2 mm and a thickness of 100 μm, and a 3.2 mm × 1.6 mm × 0.45 mm thick alumina chip was laminated on the applied resin composition. The resin composition was photocured under a light load and then thermally cured to prepare a test piece. The photocuring conditions were as follows: ultraviolet light with a wavelength of 365 nm and an irradiation intensity of 500 mW / cm, using a single-wavelength UV LED light source (OmniCure (registered trademark) AC475, manufactured by Excelitas Technologies) at a position 4 cm above the light source from the top surface of the test piece. ２ The cumulative light intensity is 2000 mJ / cm ２(Measured using a UV integrating actinometer UIT-250 and a UVD-S365 receiver (manufactured by Ushio Inc.)). The thermal curing conditions were 80°C and 60 minutes in a blower dryer. (2) The alumina chip on the FR4 plate of the test piece obtained in (1) above was poked from the side with a bond tester (manufactured by Dage, Series 4000) at 23°C, and the stress (N) at which the alumina chip peeled off was measured. This measurement was performed on seven test pieces, and the average value of the obtained stresses was calculated. This average value is shown in Table 1 as the initial shear strength (unit: N / chip) of the cured product. In this specification, the initial shear strength is preferably 120 N / chip or more. (3) The test piece obtained in (1) above was placed in a reflow furnace and preheated at 160°C for 60 seconds. Then, it was held at 240°C for 60 seconds. The alumina chip on the FR4 plate of this reflowed test piece was poked from the side with a bond tester (Dage, Series 4000) at 23°C, and the stress (N) at which the alumina chip peeled off was measured. This measurement was performed on 10 test pieces, and the average value of the obtained stress was calculated. This average value is shown in Table 1 as the post-reflow shear strength (unit: N / chip) of the cured product. (4) The post-reflow shear strength retention was calculated based on the following formula. The results are shown in Table 1. In this specification, the post-reflow shear strength retention is preferably 50% or more. Shear strength retention after reflow (%) = ([post-reflow shear strength obtained in (3) above] / [initial shear strength obtained in (2) above]) × 100 (5) For the resin compositions of Examples 1 and 7, the initial shear strength, post-reflow shear strength, and post-reflow shear strength retention were determined in the same manner as in (1) to (4) above, except that the substrate was changed from an organic substrate (FR4) to an inorganic substrate (SUS304). The results are shown in Table 2.

[0105] [Measurement of Tg and Elastic Modulus of Cured Product] The resin compositions of Example 1 and Comparative Example 1 were applied to a glass substrate to a thickness of 250±100 μm, and the resin compositions were photocured and then thermally cured to prepare test specimens. The photocuring conditions were as follows: ultraviolet light with a wavelength of 365 nm and an irradiation intensity of 500 mW / cm was applied using a single-wavelength UV LED light source (OmniCure (registered trademark) AC475, manufactured by Excelitas Technologies) at a position 4 cm above the light source from the top surface of the test specimen. ２ The cumulative light intensity is 2000 mJ / cm ２ The cured product was subjected to dynamic mechanical analysis (DMA) to determine the initial Tg [°C] and modulus of elasticity [GPa] at 25°C of the cured product. The cured product was then subjected to reflow under the same conditions as above, and the Tg [°C] and modulus of elasticity [GPa] of the cured product after reflow were determined. The modulus of elasticity was measured at 25°C using a dynamic mechanical analysis (DMA) device manufactured by TA Instruments in accordance with Japanese Industrial Standard JIS C6481. The Tg was measured using a dynamic mechanical analysis (DMA) device manufactured by TA Instruments in accordance with Japanese Industrial Standard JIS C6481. The results are shown in Table 3. The Tg and elastic modulus of the cured products were similarly measured for the resin compositions of Examples 2 to 10. The initial Tg of the cured products of the resin compositions of Examples 2 to 10 was in the range of 25° C. or higher and lower than 90° C., and the Tg of the cured products after reflow was in the range of 25° C. or higher and lower than 90° C. The elastic modulus of the cured products of the resin compositions of Examples 2 to 10 showed the same results as in Example 1.

[0106]

[0107]

[0108]

[0109] The cured products of the resin compositions of Examples 1 to 10, which satisfy the configuration of the present invention, exhibited high initial adhesive strength (shear strength) and suppressed a decrease in adhesive strength (shear strength) even after reflow. Similar results were observed for both organic substrates (FR4) and inorganic substrates (SUS304) as adherends. On the other hand, the cured product of the resin composition of Comparative Example 1, which contained a borate-based acid generator (C') instead of a gallate-based acid generator (C), exhibited a significant decrease in adhesive strength (shear strength) after reflow. Furthermore, the cured product of the resin composition of Comparative Example 2, which did not contain an oxetane compound (B), exhibited low initial adhesive strength (shear strength). The cured product of the resin composition of Example 1, which satisfied the configuration of the present invention, did not show significant changes in Tg and modulus of elasticity before and after reflow. On the other hand, the cured product of the resin composition of Comparative Example 1, which contained a borate-based acid generator (C') instead of a gallate-based acid generator (C), exhibited a significant decrease in Tg and modulus of elasticity after reflow. The cured product of the resin composition of Comparative Example 1, which contained a borate-based acid generator (C') instead of a gallate-based acid generator (C), exhibited a large heat release in the temperature range of 200°C to 250°C as measured by DSC. This suggests that decomposition of the cured product occurred in a high-temperature environment, resulting in a decrease in the Tg and elastic modulus of the cured product and a significant decrease in adhesive strength. On the other hand, the cured products of the resin compositions of Examples 1 to 10 exhibited no or only a small heat release in the temperature range of 200°C to 250°C as measured by DSC. This suggests that decomposition in a high-temperature environment was suppressed, and a decrease in adhesive strength was suppressed. Although not shown in Tables 1 to 3, a similar evaluation was also performed on a two-component resin composition in Example 1, in which component A was component (A), component (D), component (E), component (G), component (H), and component (I), and component B was component (B) and component (C). The results were similar to those of the one-component resin composition.

[0110] The resin composition of the present invention is very useful, for example, as an adhesive or sealant for fixing, joining or protecting semiconductor devices or electronic components or components constituting them, or as a raw material thereof.

[0111] The disclosure of Japanese Patent Application No. 2024-048022 (filing date: March 25, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. (A) an epoxy compound, (B) an oxetane compound, and (C) a compound represented by the following formula (1): (In the formula, R １ , R ２ , R ３ and R ４ each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, provided that R １ , R ２ , R ３ and R ４ and a counter cation, and the resin composition satisfies at least one of the following characteristics (a) and (b): (a) further comprises a (D) filler; and (b) the content of the (A) epoxy compound is 100 to 1,300 parts by weight per 100 parts by weight of the (B) oxetane compound.

2. The resin composition according to claim 1, which satisfies the characteristic (a).

3. The resin composition according to claim 1, which satisfies the characteristic (b).

4. The resin composition according to claim 1, which satisfies the above characteristics (a) and (b).

5. The resin composition according to any one of claims 1 to 4, wherein the epoxy compound (A) comprises an epoxy compound having a polyalkylene oxide chain, an aliphatic moiety derived from an alicyclic diol, an aliphatic moiety derived from hydrogenated bisphenol A, or a combination thereof.

6. The resin composition according to any one of claims 1 to 5, wherein the counter cation is an iodonium cation or a sulfonium cation.

7. The resin composition according to any one of claims 1, 2, 4, 5, and 6, which satisfies characteristic (a) and in which the content of the (D) filler is 5 to 100 parts by weight per 100 parts by weight of the total of the (A) epoxy compound and the (B) oxetane compound.

8. The resin composition according to any one of claims 1 to 7, further comprising (E) a photosensitizer.

9. The resin composition according to any one of claims 1 to 8, further comprising (F) a photoradical initiator.

10. The resin composition according to any one of claims 1 to 9, further comprising (H) a thermal radical initiator.

11. The resin composition according to any one of claims 1 to 10, which is at least thermosetting.

12. The resin composition according to any one of claims 1 to 11, which, when heated from 25°C to 250°C at a heating rate of 10°C / min using a differential scanning calorimeter, generates a heat value of 10 J / g or less in the temperature range from 200°C to 250°C.

13. The resin composition according to any one of claims 1 to 12, wherein components (A) to (C) or components (A) to (D) are contained in a single container.

14. The resin composition according to any one of claims 1 to 12, wherein components (A) to (C) or components (A) to (D) are separated into two or more containers.

15. An adhesive or sealant comprising the resin composition according to any one of claims 1 to 14.

16. A cured product obtained by curing the resin composition according to any one of claims 1 to 14, or the adhesive or sealant according to claim 15.

17. A semiconductor device or electronic component comprising the cured product according to claim 16.

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