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

Abstract

Provided are: a curable resin composition which can be cured through heating at a low temperature and / or ultraviolet ray irradiation and with which corrosion of an adherend is suppressed; an adhesive; a sealing material; a cured product obtained by curing same; and a semiconductor device and electronic device including the cured product. This curable resin composition comprises (A) a cation-curable resin, (B) an acid generator including an iodonium salt, and (C) an ion trapping agent including at least one kind of atom selected from the group consisting of Zr, Mg, and Al.

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 devices because the cured products thereof have excellent properties such as adhesiveness, electrical insulation, chemical resistance, and mechanical strength.

[0003] When the adherend to be bonded is a component of a precision instrument such as a camera module or a sensor module, the adhesive must be curable by at least one of low-temperature heating (for example, 100°C or less, preferably 80°C or less) and / or ultraviolet light irradiation. For example, Patent Document 1 describes a thermal polymerization initiator system that can be cured by low-temperature heating, containing, for example, an iodonium salt compound containing an aryl group for initiating the polymerization reaction of a cationically polymerizable compound, and a radical polymerization initiator that is an organic peroxide. Excess aryl iodide not involved in the polymerization reaction, generated by decomposition of the iodonium salt compound, may react with water vapor in the ambient air to produce a gas that corrodes metals. Patent Document 1 also describes an adhesive composition to which a corrosion inhibitor composed of a metal hydroxide or metal oxide can be added or mixed to prevent corrosion of the adherend.

[0004] JP 2011-116977 A

[0005] However, adding a corrosion inhibitor to the composition may reduce the curing properties of the adhesive. In cases where different materials are often bonded, such as in camera modules and sensor modules, a composition that can be cured by heating at 100°C or less and / or by ultraviolet light irradiation, for example, and thereby bond the different materials, may be required.

[0006] Therefore, an object of the present invention is to provide a curable resin composition, an adhesive, a sealant, a cured product obtained by curing these, and a semiconductor device and an electronic device including the cured product, which can be cured by at least one of heating at 100°C or less and / or ultraviolet irradiation, for example, and which inhibits corrosion of an adherend.

[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 cation-curable resin; (B) an acid generator containing an iodonium salt; and (C) an ion-trapping agent containing at least one atom selected from Zr, Mg, and Al. [2] The curable resin composition according to [1], wherein the component (C) is present in an amount of 0.1 to 15 parts by mass per part by mass of the component (B). [3] The curable resin composition according to [1] or [2], wherein the component (C) is a dual ion-exchange ion-trapping agent. [4] The curable resin composition according to any one of [1] to [3], wherein the average particle size of the primary particles of the component (C) is 30 nm to 3,000 nm. [5] The curable resin composition according to any one of [1] to [4], wherein the 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 any one of [1] to [5], further comprising: (D) an organic peroxide. [7] The curable resin composition according to any one of [1] to [6], wherein the iodonium salt contained in the component (B) is an iodonium salt compound represented by the following formula (1): (In the formula (1), Ar １ and Ar ２ are each independently a substituted or unsubstituted aryl group; Z － is an anion.) [8] Z in the formula (1) － But BF ４ － , SbF ６ -, AsF ６ － , B(C６ F ５ ) ４ － , or Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , or [P(R Ｆ ) ａ F ６－ａ ] － , [C(R Ｆ SO ２ ) ３ ] － , or [N(R Ｆ SO ２ ) ２ ] － (In the formula, R Ｆ 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 Ｆ may be the same or different. ) is the curable resin composition according to [7] above. [9] An adhesive or encapsulant comprising the curable resin composition according to any one of [1] to [8] above.

[10] A cured product obtained by curing the curable resin composition according to any one of [1] to [8] above or the adhesive or encapsulant according to [9] above.

[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, a sealant, a cured product obtained by curing these, and a semiconductor device and an electronic device including the cured product, which can be cured by, for example, at least one of heating at 100°C or less and / or ultraviolet irradiation while suppressing a decrease in curability and suppressing corrosion of an adherend.

[0010] Hereinafter, the curable resin composition, adhesive, encapsulant, cured product obtained by curing these, and semiconductor device and electronic device 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 device 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 A 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) an ion trapping agent containing at least one atom selected from Zr, Mg, and Al (hereinafter also referred to as “component (C)”).

[0012] The curable resin composition is heated to decompose the iodonium salt to form protonic acid H ＋ X － This protonic acid coordinates to the functional group of the cationic curable resin, and the functional group to which the protonic acid is coordinated is attacked by the functional group of another cationic curable resin to generate a cation that becomes an active species, and a polymerization reaction proceeds. In the case of an iodonium salt compound containing an iodonium substituted with an aryl group, the aryl iodide produced by decomposition of the iodonium salt upon heating reacts with water vapor in the air to generate a corrosive gas (hydrogen iodide). Therefore, the corrosive gas (hydrogen iodide) is captured by an ion trapping agent containing at least one atom selected from the group consisting of Zr, Mg, and Al, thereby suppressing the release of a gas that corrodes metals. Since the release of a corrosive gas generated by the reaction of water vapor with the aryl iodide produced from the iodonium salt after heating is suppressed, corrosion of the adherend can be suppressed when the curable resin composition is cured.

[0013] 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. Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Examples of the cationic curable resin include an epoxy resin, an oxetane resin, a polystyrene compound, and a vinyl ether compound. 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 obtain a cured product that cures upon heating at a low temperature of 100°C or less, preferably 80°C or less, and / or upon ultraviolet irradiation.

[0014] 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 1000 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 an epoxy resin having the ring skeleton of component (A1) in the molecule and an oxetane resin (A2), the curable resin composition can obtain a cured product by heating, for example, at 100°C or less, preferably 80°C or less. Component (A) may contain component (A1) alone or both component (A1) and component (A2). Functional group equivalents, such as the epoxy group equivalent number and the oxetane group equivalent number described below, refer to the number of functional groups (equivalents) per compound mass (charge amount).

[0015] Examples of the epoxy resin include an aliphatic epoxy resin and an epoxy resin having a ring skeleton in the molecule. The epoxy resin preferably includes an epoxy resin having a ring skeleton in the molecule. Examples of the ring skeleton include an alicyclic skeleton, an aromatic ring skeleton, a heteroaromatic ring skeleton, and a heterocyclic skeleton. The epoxy resin having a ring skeleton in the molecule preferably includes at least one selected from the group consisting of an epoxy resin having an aromatic ring skeleton in the molecule and an epoxy resin having an alicyclic skeleton in the molecule, and more preferably includes an epoxy resin having an aromatic ring skeleton.

[0016] Epoxy resins having an aromatic ring skeleton include polyfunctional epoxy resins, specifically bisphenol A epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins containing compounds 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 epoxy resins (EP-4000S, EP-4003S, EP-4010S, manufactured by DIC Corporation). Examples of the polyfunctional epoxy resin include EPICRON (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).

[0017] 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.), 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.).

[0018] 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).

[0019] 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.

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

[0021] 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.).

[0022] 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 curing, for example, by heating at a low temperature of 100°C or less, preferably 80°C or less, and / or by ultraviolet irradiation. 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.

[0023] 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 (1). (In the formula (1), Ar １ and Ar ２ are each independently a substituted or unsubstituted aryl group; Z － is an anion.)

[0024] 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.

[0025] 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 － , or B(C６ F ５ ) ４ － , or Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , or [P(R Ｆ ) ａ F ６－ａ ] － , [C(R Ｆ SO ２ ) ３ ] － , or [N(R Ｆ SO ２ ) ２ ] － (In the formula, R Ｆ 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 Ｆ may be the same or different. In formula (1), it is preferable that the anion represented by Z- has relatively low nucleophilicity. When the anion contained in the iodonium salt has low nucleophilicity, the rate of the propagation reaction of the cationic curable resin increases, and a cured product can be obtained in a short time by heating at a low temperature of 100°C or less and / or irradiating with ultraviolet light.

[0026] 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 １０～１４ Examples 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.

[0027] Component (C): Ion-trapping agent The ion-trapping agent of component (C) is preferably a layered compound containing at least one atom selected from the group consisting of Zr, Mg, and Al. ２＋ or Mg ２＋ A part of ３＋Because of the structure in which Zr is replaced by Sb, the interlayer space is positively charged, can interact with anions, and has the property of trapping ions between the layers. Therefore, the ion trapping agent of component (C), which is a layered compound containing at least one atom selected from the group consisting of Zr, Mg, and Al, is preferred because it can trap iodide ions with a large ionic radius. On the other hand, ion trapping agents that are not layered compounds and contain Bi or Sb are thought to be unable to trap iodide ions with a large ionic radius. When the ion trapping agent of component (C) is a layered compound containing at least one atom selected from the group consisting of Zr, Mg, and Al, it is preferable that the interlayer distance be approximately 4 Å to 13 Å.

[0028] Component (C) is preferably a double ion exchange type ion trapping agent. When component (C) is a double ion exchange type ion trapping agent, it is thought that it can efficiently proceed with the polymerization reaction because it not only traps iodide ions but also has the potential to trap weak acids that can inhibit cationic polymerization. As a result, it is possible to suppress a decrease in the curability of the cationically curable resin.

[0029] When the ion trapping agent of component (C) is a layered compound containing at least one atom selected from Zr, Mg, and Al, a commercially available product can be used. Examples of the ion trapping agent of component (C) include Zr, Mg, and Al-based inorganic ion trapping agents (e.g., IXEPLAS (registered trademark)-A1 and IXEPLAS (registered trademark)-A2 manufactured by Toagosei Co., Ltd.), hydrotalcite (e.g., manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and Mg, Al-based inorganic anion trapping agents (e.g., IXE-700F manufactured by Toagosei Co., Ltd.) (e.g., SWMNA-010-1 and SWMNA-050-1 manufactured by Toda Kogyo Co., Ltd.).

[0030] The hydrotalcite that can be used is represented by the following formula (2): Mg ｐ Al ｑ (OH) ｕ (CO ３ ) ｒ ・nH ２O (2) (In formula (2), p, q, r, and s are positive numbers and satisfy the equation 2p + 3q - r - 2s = 0. Also, n represents the number of hydrations and is 0 or a positive number.)

[0031] Hydrotalcite is, for example, Mg ４．５ Al ２ (OH) １３ CO ３ ・3.5H ２ O, Mg ５ Al １．５ (OH) １２．５ CO ３ ・3.5H ２ O, Mg ６ Al ２ (OH) １６ CO ３ ・4H ２ O, Mg ４．２ Al ２ (OH) １２．４ CO ３ ・3.5H ２ O, Mg ４．３ Al ２ (OH) １２．６ CO ３ ・3.5H ２ O, Mg ４．２ Al ２ (OH) １２．４ CO ３ ・2.5H ２ O, Mg ４．２ Al ２ (OH) １２．４ CO ３ ・H ２ O, Mg ４ Al ２ (OH) １２ CO ３ ・3.5H ２ Examples include O.

[0032] The ion trapping agent of component (C) preferably has an average primary particle size of 30 nm to 3,000 nm, more preferably 50 nm to 2,500 nm, even more preferably 100 nm to 2,000 nm, still more preferably 150 nm to 1,500 nm, and even more preferably 200 nm to 1,000 nm. The average primary particle size of the ion trapping agent of component (C) refers to the arithmetic mean value of 50 random primary particles measured by SEM image analysis observed with a scanning electron microscope (SEM). When a commercially available product is used as the ion trapping agent of component (C), the average primary particle size may be the catalog value.

[0033] (D): Organic Peroxide The curable resin composition preferably further contains (D) an organic peroxide (hereinafter also referred to as "component (D)"). The organic peroxide of component (D) is preferably a peroxydicarbonate-type organic peroxide. Among organic peroxides, the peroxydicarbonate-type organic peroxide of component (D) generates a carbonate radical. The generated carbonate radical quickly abstracts hydrogen from other compounds contained in the curable resin composition, and unstable alkyl radicals such as primary alkyl radicals are generated from the carbonate radical. Unstable alkyl radicals are highly reactive and prone to radical redox reactions, which are thought to be faster than the reaction rate of curing inhibition by oxygen. Therefore, the peroxydicarbonate-type organic peroxide of component (D) is thought to be able to rapidly proceed with the curing reaction of the cationic curable resin. By including a peroxydicarbonate-type organic peroxide as the organic peroxide of component (D), the curable resin composition can be cured by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less.

[0034] When the curable resin composition contains an organic peroxide as component (D), even when a resin having a large functional group equivalent is used as the cationically curable resin, the curing reaction of the cationically curable resin can be rapidly progressed, and a cured product can be obtained by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less.

[0035] When the organic peroxide of component (D) is a peroxydicarbonate-type organic peroxide, it has a structure represented by -O-C(=O)-O-O-C(=O)-O-. Component (D) is a radical source, and when component (D) is a peroxydicarbonate-type organic peroxide, it is likely to generate carbonate radicals without a decarboxylation reaction. The organic peroxide of component (D) preferably has a one-hour half-life temperature of 50°C to 80°C, or alternatively 55°C to 75°C, and preferably 55°C to 70°C. When the organic peroxide of component (D) has a one-hour half-life temperature of 50°C to 80°C, it generates radicals upon heating at a low temperature of 100°C or less, reductively decomposes the iodonium salt, and even when a thin-film cured product having a thickness of, for example, 100 μm or less is obtained, curing inhibition by oxygen can be suppressed and the polymerization reaction of the cationic curable resin can be promoted. The organic peroxide of component (D) preferably has a molecular weight of 180 to 1000, but may also have a molecular weight of 200 to 800, or may have a molecular weight of 220 to 700. When the organic peroxide of component (D) has a molecular weight of 180 to 1000, the polymerization reaction can be promoted by heating at a low temperature, for example, of 100°C or less, preferably 80°C or less.

[0036] When component (D) is a peroxydicarbonate-type organic peroxide, examples thereof include di(secondary butyl)peroxydicarbonate (e.g., Luperox 225 manufactured by Arkema Yoshitomi Co., Ltd.), dicetyl peroxydicarbonate (e.g., Perkadox 24L manufactured by Nouryon), and di(4-tert-butylcyclohexyl)peroxydicarbonate (e.g., Peroyl TCP manufactured by NOF Corporation). Examples of component (D) include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (e.g., Perocta O manufactured by NOF Corporation).

[0037] The curable resin composition may contain at least one selected from the group consisting of (E) a photosensitizer, (F) a photoradical generator, and (G) a filler (hereinafter also referred to as "component (E)," "component (F)," and "component (G)," respectively). The curable resin composition may further contain at least one selected from the group consisting of (H) a coupling agent and (I) a colorant such as a pigment (hereinafter also referred to as "component (H)" and "component (I)," respectively). At least one component selected from the group consisting of (H) the coupling agent and (I) the colorant may be included as an optional component.

[0038] (E) 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.

[0039] (F) Photoradical generator The photoradical generator, together with the organic peroxide of component (D), is a radical source, and generates alkyl radicals upon irradiation with light, reductively decomposes the iodonium salt, and converts the iodonium salt into an acid (cation: H ＋ ) and promotes the polymerization reaction. When the curable resin composition of the present invention contains a peroxydicarbonate-type organic peroxide as the organic peroxide of component (D), it does not need to contain the photoradical generator (F). When the curable resin composition contains the photoradical generator (F), it generates an alkyl radical 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.

[0040] (G) 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 can be obtained by curing into a thin film having a thickness of, for example, 100 μm or less, preferably 50 μm 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.

[0041] 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, 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. Two or more types of silicon dioxide having different types or different particle sizes may be used in combination, or one type may be used alone.

[0042] 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. 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.

[0043] 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.

[0044] (H) 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.

[0045] 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.

[0046] 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.

[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 (H) coupling agent or (I) colorant, as well as additives, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, and the like.

[0049] The content of component (A) in the curable resin composition is preferably 40 to 95% by mass, more preferably 45 to 90% by mass, and even more preferably 50 to 85% by mass, relative to 100% by mass of the total amount of the curable resin composition. When the content of component (A) in the curable resin composition is 40 to 90% by mass, relative to 100% by mass of the total amount of the curable resin composition, a cured product can be obtained by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, and / or by ultraviolet irradiation.

[0050] When the curable resin composition contains, as component (A), at least one selected from the group consisting of component (A1) an epoxy resin having a ring skeleton in the molecule with an epoxy group equivalent of 100 g / eq to 1000 g / eq and component (A2) an oxetane resin, 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 with 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.

[0051] When component (A) in the curable resin composition contains an epoxy resin of component (A1) having in its molecule a ring skeleton with an epoxy group equivalent of 100 g / eq to 1000 g / eq, in order to obtain a cured product cured by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, and / or ultraviolet irradiation, the ratio 1 of the number of epoxy group equivalents in the epoxy resin of component (A1) to the number of functional group equivalents contained in component (A) (functional group equivalent ratio 1 = [number of epoxy group equivalents in component (A1) having in its molecule a ring skeleton with an epoxy group equivalent of 100 g / eq to 1000 g / eq / number of functional group equivalents in component (A)]) is preferably 0.01 to 1.0, more preferably 0.2 to 0.9, and even more preferably 0.4 to 0.8.

[0052] In the curable resin composition, the oxetane resin of component (A2) is preferably 0 to 40 mass%, more preferably 0 to 30 mass%, and even more preferably 0 to 20 mass%, of component (A) in component (A) taken as 100 mass% of the total amount of component (A). When component (A2) contains the oxetane resin, it is possible to obtain a cured product by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, and / or by ultraviolet irradiation.

[0053] When component (A) in the curable resin composition contains the oxetane resin of component (A2), 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, and / or by ultraviolet irradiation, the ratio 2 of the number of oxetane group equivalents in the oxetane resin of component (A2) to the number of functional group equivalents contained in component (A) (functional group equivalent ratio 2 = [number of oxetane group equivalents in component (A2) / number of functional group equivalents in component (A)] is preferably 0.01 to 0.8, more preferably 0.1 to 0.6, and even more preferably 0.1 to 0.4.

[0054] The blending ratio of component (A1) to component (A2) in component (A) in the curable resin composition (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 curing, for example, by heating at a low temperature of 100°C or less, preferably 80°C or less, and / or by ultraviolet irradiation.

[0055] In order to cure the curable resin composition by heating at a low temperature of, for example, 100°C or less, preferably 80°C or less, and / or by ultraviolet irradiation, the amount of component (B) in the curable resin composition 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).

[0056] The amount of component (C) in the curable resin composition is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.25 to 5 parts by mass, per part by mass of component (B). When the amount of component (C) in the curable resin composition is 0.1 to 15 parts by mass per part by mass of component (B), excess iodonium cations generated by decomposition of the iodonium salt can be captured, thereby suppressing the generation of gases that corrode the adherend. The content of component (C) is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and may even be 0.5 to 10% by mass, based on 100% by mass of the total amount of the curable resin composition.

[0057] The amount of component (D) in the thermosetting resin composition is preferably 0 to 10.0 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A).

[0058] When the thermosetting resin composition contains component (D), the blending ratio of component (B) and component (D) (component (B):component (D)) 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.

[0059] The amount of the photosensitizer 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.

[0060] The amount of the photoradical generator of component (F) 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.

[0061] The amount of the filler of component (G) in the curable resin composition may be 0 to 50 mass%, 1 to 45 mass%, or 3 to 40 mass%, relative to 100 mass% of the total amount of the curable resin composition.

[0062] 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 (H) a coupling agent and (I) a colorant.

[0063] 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.

[0064] 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 measured 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 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 is preferably 200 Pa s or less, may be 190 Pa s or less, and is 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.

[0065] 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.

[0066] 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.).

[0067] 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. The resin composition is also ultraviolet-curable, preferably at a wavelength of 300 to 500 nm and with an integrated light dose of 500 to 5000 mJ / cm. ２ It can be cured at .

[0068] Cured Products A cured product is obtained by curing the curable resin composition, or an adhesive or sealant containing the curable resin composition. The cured product obtained by curing the curable resin composition at 80°C for 60 minutes preferably has a glass transition temperature (Tg) of 0°C to 150°C, more preferably 1°C to 120°C, even more preferably 2°C to 90°C, and even more preferably 3°C to 70°C, as measured using a dynamic viscoelasticity measuring device (e.g., DMA7100 manufactured by Hitachi High-Tech Science Corporation). The lower the Tg of the cured product, the fewer the number of functional group equivalents in the resin composition, and the lower the crosslink density. Therefore, cured products with low Tg are more likely to react with aryl iodides in the resin composition and water vapor, generating corrosive gases. In curable resin compositions, adhesives, or sealants containing the curable resin composition, the ion trapping agent traps the generated corrosive gases, and it is believed that the lower the Tg, the more pronounced the corrosive gas trapping effect of component (C). The glass transition temperature can be measured using the method described in the Examples below.

[0069] 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 can be cured by heating at a low temperature of 100°C or less, preferably 80°C or less, thereby providing a highly reliable electronic device in which corrosion of the adherend is suppressed.

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0071] The components used in the curable resin compositions of the Examples and Comparative Examples are shown below.

[0072] 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): ADEKA GLYCIROL (registered trademark) ED-509S (manufactured by ADEKA Corporation), p-tert-butylphenyl glycidyl ether, with a molecular weight of 206 and an epoxy group equivalent of 206 / eq. (A1-4): jER YX8000 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A diglycidyl ether, molecular weight 410, epoxy group equivalent weight 205 g / eq. (A1-5): CELLOXIDE (registered trademark) 2021P (manufactured by Daicel Corporation), 3',4'-epoxycyclomethyl 3,4-epoxycyclohexane carboxylate, molecular weight 260, epoxy group equivalent weight 130 g / eq.

[0073] 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.

[0074] 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.)

[0075] Component (C): An ion trapping agent which is a layered compound and contains at least one atom selected from the group consisting of Zr, Mg, and Al. (C-1): IXEPLAS (registered trademark)-A1 (manufactured by Toagosei Co., Ltd.), components: Zr, Mg, Al-based, average particle size of primary particles (primary particle diameter): 500 nm (catalog value). (C-2): IXEPLAS (registered trademark)-A2 (manufactured by Toagosei Co., Ltd.), components: Zr, Mg, Al-based, average particle size of primary particles (primary particle diameter): 200 nm (catalog value). (C-3): Hydrotalcite (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), average particle size of primary particles: 20 μm. (C-4): IXE (registered trademark)-700F (manufactured by Toagosei Co., Ltd.), components: Mg, Al-based, anion exchange-based, average particle size of primary particles (median diameter): 1.5 μm (1500 nm) (catalog value). (C-5): SWMNA-010-1 (manufactured by Toda Kogyo Co., Ltd.), components: Mg, Al-based, anion exchange system, average particle size of primary particles (primary particle diameter): 300 nm (C-6): SWMNA-050-1 (manufactured by Toda Kogyo Co., Ltd.), components: Mg, Al-based, anion exchange system, average particle size of primary particles (primary particle diameter): 60 nm (C-7): IXEPLAS (registered trademark)-B1 (manufactured by Toagosei Co., Ltd.), components: Zr, Bi-based, average particle size of primary particles (primary particle diameter): 200 nm (catalog value)

[0076] Component (C'): an ion trapping agent that does not contain at least one atom selected from the group consisting of Zr, Mg, and Al and is not a layered compound. (C'-8): IXE (registered trademark)-500 (manufactured by Toagosei Co., Ltd.), component: Bi-based, anion exchange-based, average particle size (median diameter) of primary particles: 1.5 μm (1500 nm) (catalog value).

[0077] Component (D): Organic Peroxide (D-1): Perkadox 24L (manufactured by Nouryon), dicetyl peroxydicarbonate, 1-hour half-life temperature: 65°C, molecular weight: 570.9, SADT: 40°C. (D-2): Peroyl TCP (manufactured by NOF Corporation), di(4-tert-butylcyclohexyl) peroxydicarbonate, 1-hour half-life temperature: 58°C, molecular weight: 398.5, SADT: 45°C. (D-3): Perocta O (manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-hour half-life temperature: 84°C, molecular weight: 272.4, SADT: 40°C.

[0078] (E) Photosensitizer (E-1): DETX, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

[0079] (F) Photoradical Generator (F-1): Omnirad (registered trademark) 184 (manufactured by IGM Resins), 1-hydroxycyclohexyl phenyl ketone

[0080] (G) Filler (G-1): SE5200SEE (manufactured by Admatechs Co., Ltd.), high-purity synthetic spherical silica. (G-2): Cabosil (registered trademark) TS720 (manufactured by Cabot Japan Co., Ltd.), hydrophobic silica.

[0081] (H) Coupling Agent (H-1): Silane coupling agent, S530 (manufactured by JNC Corporation), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0082] (I) Colorant (I-1): Titanium Black 13M (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0083] Examples 1 to 18 and Comparative Examples 1 to 4 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 to 3. In Tables 1 to 3, the numbers indicating the blending ratio of each component contained in the curable resin composition represent parts by mass 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 there is no corresponding item.

[0084] In the examples and comparative examples, the properties of the curable resin compositions and the cured products were measured as follows, and the results are shown in Tables 1 to 3.

[0085] Average particle size of primary particles of ion trapping agent The ion trapping agent refers to the arithmetic average value of 50 randomly selected primary particles measured by observing the particles with a scanning electron microscope (SEM) and analyzing the resulting SEM image. When a commercially available product is used as the ion trapping agent of component (C), the average particle size of the primary particles may be the value listed in the catalog.

[0086] Preparation of Cured Products Each of the curable resin compositions of Examples 1 to 7, 11 to 16, and 18 and Comparative Examples 1 to 4 was irradiated with a UV LED irradiation device AC475 manufactured by Excelitas Technologies, Inc. at an accumulated light dose of 2000 mJ / cm ２ After irradiation (measured using a Ushio Inc. UIT-250 (connected to a UVD-365 photodetector)), the composition was heated at 80°C for 60 minutes using a blower dryer to obtain a cured product. Each of the curable resin compositions of Examples 8 to 10 and 17 was heated at 80°C for 60 minutes using a blower dryer to obtain a cured product. The following measurements were carried out on each cured product. The results are shown in Tables 1 to 3.

[0087] The glass transition temperature (Tg) of the cured product was measured in accordance with Japanese Industrial Standard JIS C6481. Specifically, a silicone-based release agent was first applied to a 3 mm-thick glass plate. Spacers (heat-resistant tape laminated on top) were placed in two locations on the glass plate so that the cured film thickness would be 400±150 μm. Next, the curable resin composition was applied between the spacers, and the glass plate was sandwiched between other glass plates coated with a silicone-based release agent on their surfaces, taking care not to trap air bubbles. Each of the curable resin compositions of Examples 1 to 7, 11 to 16, and 18 and Comparative Examples 1 to 4 was subjected to a UV curing treatment by UV irradiation using an Excelitas Technologies UV LED irradiation device AC475 with an integrated light dose of 2000 mJ / cm2 (measured with a Ushio Inc. UIT-250 (with a UVD-365 receiver connected)). Each curable resin composition was cured to obtain a cured product. Furthermore, each of the curable resin compositions of Examples 8 to 10 and 17 was heated using an air blower to cure the curable resin composition, thereby obtaining a cured product. Finally, these cured products were peeled from the glass plate coated with the silicone-based release agent and then cut into predetermined dimensions (10 mm long, 40 mm wide) using a cutter to obtain test pieces. The cut edges were smoothed with sandpaper. The initial Tg of each of these cured products was measured using a dynamic thermomechanical analyzer (DMA) (manufactured by Seiko Instruments Inc.) in the range of -20°C to 200°C, at a frequency of 10 Hz, a heating rate of 3°C / min, and a strain amplitude of 5 μm using a tensile method. The storage modulus (E') and loss modulus (E") of the cured product were measured, and the Tg was determined as the peak temperature of the dielectric dissipation factor (tan δ) calculated from E" / E'.

[0088] Discoloration (Discoloration Evaluation): Heating A resin composition was applied by stencil printing to a size of 6 mmφ (diameter: 6 mm) and a thickness of 600 μm on a copper-plated glass epoxy substrate (NEMA or ANSI standard FR4 substrate) with a width of 3 cm, a height of 3 cm, and a thickness of 1 mm. The resin composition was then thermally cured in a fan dryer at 80°C for 60 minutes. The resulting test specimen was left in a constant temperature and humidity chamber at a temperature of 85°C and a humidity of 85% for 500 hours. The test specimen was removed from the constant temperature and humidity chamber, and the copper surrounding the cured resin composition was visually inspected for discoloration. If discoloration was observed, the length (unit: mm) from the cured product to the discolored area was measured. The discoloration measured using this test specimen was defined as discoloration after heating. The discoloration after heating is preferably 1 mm or less, more preferably 0.5 mm or less, and even more preferably 0.1 mm or less.

[0089] Discoloration (discoloration evaluation): ultraviolet (UV: 365 nm) irradiation A resin composition was applied by stencil printing to a size of 6 mmφ (diameter: 6 mm) and a thickness of 600 μm on a copper-plated glass epoxy substrate (NEMA or ANSI standard FR4 substrate) having a width of 3 cm, a height of 3 cm, and a thickness of 1 mm. Thereafter, a UV LED irradiation device AC475 manufactured by Excelitas Technologies was used to irradiate the resin composition from the perpendicular direction to the surface to which the resin composition was applied, with an integrated light dose of 2000 mJ / cm. ２ The resin composition was cured at a temperature of 85°C and a humidity of 85% (measured using a UIT-250 manufactured by Ushio Inc., connected to a UVD-365 photodetector). The obtained test piece was left in a constant temperature and humidity chamber for 500 hours under conditions of a temperature of 85°C and a humidity of 85%. The test piece was removed from the constant temperature and humidity chamber, and visually inspected to see if the copper around the cured resin composition had discolored. If discoloration was observed, the length (unit: mm) from the cured product to the discolored area was measured. The discoloration determined using this test piece was defined as the discoloration after ultraviolet irradiation. The discoloration after ultraviolet irradiation is preferably 1 mm or less, more preferably 0.5 mm or less, and even more preferably 0.1 mm or less.

[0090] Discoloration (discoloration evaluation): Heating and ultraviolet (UV: 365 nm) irradiation A resin composition was applied by stencil printing to a size of 6 mmφ (diameter: 6 mm) and a thickness of 600 μm on a copper-plated glass epoxy substrate (NEMA or ANSI standard FR4 substrate) having a width of 3 cm, a height of 3 cm, and a thickness of 1 mm. Then, a UV LED irradiation device AC475 manufactured by Excelitas Technologies was used to apply an integrated light dose of 2000 mJ / cm from the perpendicular direction to the surface on which the resin composition was applied. ２ The resin composition was cured at 200°C (measured using a UIT-250 manufactured by Ushio Inc. (connected to a UVD-365 photodetector)). The composition was then thermally cured in a fan dryer at 80°C for 60 minutes. The resulting test piece was left in a constant temperature and humidity chamber at a temperature of 85°C and a humidity of 85% for 500 hours. The test piece was removed from the constant temperature and humidity chamber, and visually inspected for discoloration of the copper surrounding the cured resin composition. If discoloration was observed, the length (unit: mm) from the cured product to the discolored area was measured. The discoloration determined using this test piece was defined as the discoloration after heating and ultraviolet irradiation. The discoloration after heating and ultraviolet irradiation is preferably 1 mm or less, more preferably 0.5 mm or less, and even more preferably 0.1 mm or less.

[0091] Discoloration (discoloration evaluation): Evaluation When no discoloration was observed by heating, by ultraviolet (UV) irradiation, or by both heating and ultraviolet (UV) irradiation, the product was evaluated as "G (Good)." When discoloration was 1 mm or less in any of the evaluations, the product was evaluated as "A (Average)." When discoloration of more than 1 mm was observed by either heating or ultraviolet (UV) irradiation, the product was evaluated as "B (Bad)." When component (E) or component (F) was not contained and the product did not cure by ultraviolet irradiation, the product was evaluated as "-."

[0092]

[0093]

[0094]

[0095] As shown in Tables 1 to 3, the cured products of the curable resin compositions of Examples 1 to 17 did not discolor and corrosion of the adherend was suppressed even when heated at a low temperature of 80°C or when irradiated with ultraviolet light having a peak wavelength of 365 nm. The cured product of the curable resin composition of Example 18 showed discoloration of 1 mm or less even when heated at a low temperature of 80°C or when irradiated with ultraviolet light having a peak wavelength of 365 nm.

[0096] As shown in Table 3, the cured products of the curable resin compositions of Comparative Examples 1 to 4, which did not contain the ion trapping agent of component (C) or contained the ion trapping agent of component (C') that did not contain at least one atom selected from the group consisting of Zr, Mg, and Al, showed discoloration when heated at a low temperature of 80°C or irradiated with ultraviolet light having a peak wavelength of 365 nm, and corrosion of the adherend was not suppressed.

[0097] 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.

Claims

1. (A) Cationic curable resin, (B) Acid generator containing an iodonium salt, A curable resin composition comprising (C) an ion trapping agent containing at least one atom selected from the group consisting of Zr, Mg, and Al.

2. The curable resin composition according to claim 1, wherein component (C) is 0.1 to 15 parts by mass per 1 part by mass of component (B).

3. The curable resin composition according to claim 1 or 2, wherein the component (C) is a double ion exchange type ion trap agent.

4. The curable resin composition according to claim 1 or 2, wherein the average particle size of the primary particles of component (C) is 30 nm to 3000 nm.

5. The aforementioned component (A) is (A1) An epoxy resin having an epoxy group equivalent of 100 g / eq to 1000 g / eq and having a ring skeleton in its molecule, and (A2) The curable resin composition according to claim 1 or 2, comprising at least one selected from the group consisting of oxetane resins.

6. (D) A curable resin composition according to claim 1 or 2, further comprising an organic peroxide.

7. The curable resin composition according to claim 1 or 2, wherein the iodonium salt contained in component (B) is an iodonium salt compound represented by the following formula (1). 【Chemistry 1】 (In the above formula (1), Ar １ and Ar ２ Each of these is independently a substituted or unsubstituted aryl group, and Z － (This is an anion.)

8. Z in the above formula (1) － is 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 Ｆ ) ａ F ６－ａ － 、[C(R Ｆ SO ２ ) ３ － 、or [N(R Ｆ SO ２ ) ２ － (In the formula, R Ｆ is each independently an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R Ｆ may be the same as or different from each other.), The curable resin composition according to claim 7.​​​

9. An adhesive or sealant comprising the curable resin composition according to claim 1 or 2.

10. A cured product obtained by curing the curable resin composition according to claim 1 or 2, or the adhesive or sealant according to claim 9.

11. A semiconductor device comprising the cured product described in claim 10.

12. An electronic device comprising the cured product described in claim 10.

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