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

Abstract

The invention provides a curable resin composition which can be cured at low temperature and has excellent pot life, an adhesive, a sealing material, a cured product, a semiconductor device and an electronic device. A curable resin composition containing (A) a cationic curable resin, (B) an acid generator containing an iodonium salt, and (C) a peroxydicarbonate type organic peroxide represented by formula (1). An organic peroxide of the peroxydicarbonate type represented by formula (1) contains an alkyl group having at least 10 carbon atoms represented by R1 and R2.

Description

Technical Field

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

[0002] For a curable resin composition containing a cationically polymerizable compound, the cured product has excellent properties such as adhesiveness, electrical insulation, chemical resistance, and mechanical strength, and is therefore used as an adhesive in the field of electronic components.

[0003] For example, Patent Document 1 discloses that for a thermally cationically polymerizable composition that can be used in the field of adhesives and the like, components that are not sufficiently cured volatilize as outgas during a heat resistance test or the like, contaminating the surroundings. Patent Document 1 discloses a thermally cationically polymerizable composition in which the amount of a thermal cationic initiator added to the composition is adjusted to reduce the amount of outgas. Prior Art Documents Patent Documents

[0004] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022-105415 Summary of the Invention Technical Problem to be Solved by the Invention

[0005] When the adherend to be bonded is a component of a precision device such as a camera module or a sensor module, an adhesive that can be cured at a low temperature is desired. In addition, a resin composition for an adhesive or the like is also desired to have good storage stability and an excellent pot life.

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

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

[0008] [1] A curable resin composition, wherein the curable resin composition contains: (A) A cation-curable resin, (B) An acid generator containing an iodonium salt, and (C) An organic peroxide of a peroxydicarbonate type represented by the following formula (1). [Chemical Formula 1] (In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms) [2] The curable resin composition according to [1] above, wherein in the formula (1), R 1 and R 2 are each independently a linear, branched or cyclic alkyl group having at least 11 carbon atoms, or a combination of all three of them.) [3] The curable resin composition according to claim 1 or 2, wherein the iodonium salt contained in the component (B) is an iodonium salt compound represented by the following formula (2), [Chemical formula 2] Ar 1 -I + -Ar 2 ·Z - (2) (In the formula (2), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion) [4] The curable resin composition according to [3] above, wherein Z in the formula (2) - is BF4 - 、SbF6 - 、AsF6 - 、B(C6F5)4 - 、or Ga(C6F5)4 - 、C(CF3SO2)3 - 、or [P(R 3 ) a F 6-a - 、[C(R 3 SO2)3] - 、or [N(R 3 SO2)2] - (In the formula, R 3 are each independently an alkyl group in which at least a part of hydrogen atoms are substituted by fluorine atoms, and a is an integer of 0 to 5; when a is an integer of 2 or more, a plurality of R 3 present may be the same or different from each other) [5] The curable resin composition according to any one of [1] to [4] above, wherein the component (A) contains a selected from ​(A1) An epoxy resin having an epoxy equivalent weight of 100 g / eq to 1000 g / eq and having a ring skeleton in the molecule, and (A2) An oxetane resin At least one selected from the group consisting of. [6] The curable resin composition according to the above [5], wherein The component (A1) contains an epoxy resin having an epoxy equivalent weight of 200 g / eq or more. [7] The curable resin composition according to any one of the above [1] to [6], wherein When the total amount is set to 100 parts by mass, the amount of the component (C) is 0.1 part by mass to 10 parts by mass. [8] An adhesive or a sealing material, wherein the adhesive or the sealing material contains the curable resin composition according to any one of the above [1] to [7]. [9] A cured product, wherein the cured product is a cured product obtained by curing the curable resin composition according to any one of the above [1] to [7] and the adhesive or the sealing material according to the above [8].

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

[11] A semiconductor device, wherein the semiconductor device contains the cured product according to the above [9] or

[10] .

[12] An electronic device, wherein the electronic device contains the cured product according to the above [9] or

[10] . Advantageous Effects

[0009] According to the present invention, it is possible to provide a curable resin composition, an adhesive, a sealing material, a cured product obtained by curing them, a semiconductor device containing the cured product, and an electronic device that can be cured by low-temperature heating at 100°C or lower, preferably 80°C or lower, and have an excellent pot life. Detailed Embodiments

[0010] Hereinafter, based on the embodiments, the curable resin composition, binder, sealing material, cured product obtained by curing them, semiconductor device containing the cured product, and electronic component of the present disclosure will be described. 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 following curable resin composition, binder, sealing material, cured product, semiconductor device, and electronic component. In this specification, according to the convention in the field of synthetic resins, for the components constituting the curable resin composition before curing, even if the component is not a polymer, there are cases where the name using the term "resin" which generally means a polymer (especially a synthetic polymer) is used.

[0011] Resin composition The curable resin composition of the first embodiment of the present invention is a curable resin composition containing (A) a cation-curable resin (hereinafter also referred to as "component (A)"), (B) an acid generator containing an iodonium salt (hereinafter also referred to as "component (B)"), and (C) a peroxydicarbonate-type organic peroxide represented by the following formula (1) (hereinafter also referred to as "component (C)"). [Chemical formula 3] (In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms)

[0012] The curable resin composition can be cured at a relatively low temperature, and even when cured by heat or when cured by heat and ultraviolet irradiation, a cured product having almost unchanged physical properties can be obtained. Among them, the curable resin composition uses an iodonium salt-based cationic polymerization initiator and an organic peroxide as a thermal radical polymerization initiator, and obtains a cured product through a radical redox reaction.

[0013] However, the curable resin composition cured by a radical redox reaction tends to have its reaction temperature dependent on the stability of the organic peroxide contained in the composition. The lower the 1-hour half-life temperature, the lower the temperature at which curing can be performed. On the other hand, the lower the 1-hour half-life temperature of the organic peroxide contained in the composition, the more the stability of the composition is impaired, and thus there is a tendency for the storage stability to be impaired.

[0014] The curable resin composition contains the organic peroxide of the peroxydicarbonate type represented by the formula (1) of component (C), wherein the peroxydicarbonate-type organic peroxide has alkyl groups at both ends, and the alkyl groups have at least 10 carbon atoms. The reaction of the carbonate radical generated from component (C) to abstract hydrogen from other compounds contained in the curable resin composition is fast, generating an unstable alkyl radical such as a primary radical. The unstable alkyl radical easily causes a radical redox reaction, and thus it is considered that the reaction of the unstable alkyl radical is faster than the reaction of curing inhibition caused by oxygen. Therefore, it is considered that the carbonate radical generated from component (C) can cause the curing reaction of the cation-curable resin to proceed rapidly. Further, the hydrogen abstraction reaction of the carbonate radical is faster than that of the alkoxy radical, and thus it is considered that the instantaneous radical concentration in the system of the curable resin composition becomes higher than that of organic peroxides other than component (C). By this reaction, electrons move from the unstable alkyl radical to the acid generator containing an iodonium salt, reductively decomposing the iodonium salt to generate an acid (cation: H + ). Thereafter, it acts on the cation-curable resin and the polymerization reaction starts. The peroxydicarbonate-type organic peroxide can efficiently generate carbonate radicals and cause the curing reaction of the cation-curable resin to proceed rapidly. The curable resin composition can be cured by low-temperature heating at 100 °C or lower, preferably 90 °C or lower, more preferably 85 °C or lower, and further preferably 80 °C or lower.

[0015] Regarding the curable resin composition, the peroxydicarbonate-type organic peroxide represented by the formula (1) of component (C) generates carbonate radicals, and unstable alkyl radicals are generated along with the hydrogen abstraction reaction in the curable resin composition, thereby causing the curing reaction of the cation-curable resin to proceed rapidly. In addition, the peroxydicarbonate-type organic peroxide represented by the formula (1) of component (C) has alkyl groups having at least 10 carbon atoms bonded to two oxygens at both ends of the peroxydicarbonate. Therefore, compared with peroxydicarbonate-type organic peroxides having alkyl groups containing less than 10 carbon atoms, the organic peroxide is hardly decomposed whether at room temperature such as 20 °C to 40 °C below the heating temperature or at a low temperature below 20 °C, has good storage stability, and has an excellent pot life.

[0016] Component (A): Cation-curable resin The cation-curable resin of component (A) refers to a resin having one or more cation-polymerizable groups in the molecule. Examples of the cation-polymerizable group include an epoxy group, an oxetanyl group, a vinyl ether group, etc. Examples of the cation-curable resin include an epoxy resin, an oxetane resin, a polystyrene-based compound, and a vinyl ether compound. In order to cure by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, the cation-curable resin of component (A) preferably has a molecular weight of 100 to 800, and may also be 110 to 780.

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

[0018] The cation-curable resin of component (A) preferably contains at least one selected from the group consisting of (A1) an epoxy resin having an epoxy equivalent of 100 g / eq to 10,000 g / eq and having a ring skeleton in the molecule (hereinafter also referred to as "component (A1)"), and (A2) an oxetane resin (hereinafter also referred to as "component (A2)"). By including at least one selected from the group consisting of the epoxy resin having an epoxy equivalent of 100 g / eq to 1,000 g / eq and having a ring skeleton in the molecule of component (A1) and the oxetane resin of (A2) in component (A), the curable resin composition undergoes a curing reaction rapidly, and a curable resin composition that can be cured by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, can be obtained. Component (A) may contain component (A1) alone, or may contain both component (A1) and component (A2).

[0019] 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 contains (A1) an epoxy resin having an epoxy equivalent of 100 g / eq to 1,000 g / eq and 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 of component (A1) preferably contains 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.

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

[0021] Regarding epoxy resins having an aromatic ring skeleton, as polyfunctional epoxy resins, specific examples include bisphenol A type epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc. manufactured by DIC Corporation), special epoxy resins formed by adding polyalkylene oxide structures to epoxy resins and bisphenol A skeletons (AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4010S manufactured by ADEKA Corporation), bisphenol F type epoxy resins (EPICRON (registered trademark) 830-S, EXA-830LVP, etc. manufactured by DIC Corporation), bisphenol AD type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins (EPICRON (registered trademark), HP-4032D, HP-720H, etc. manufactured by DIC Corporation), phenol novolac type epoxy resins (EPICLON (registered trademark) N-740, N-770, etc. manufactured by DIC Corporation), cresol novolac type epoxy resins (EPICRON (registered trademark), N-660, N-670, N-655-EXP-S, etc. manufactured by DIC Corporation), etc. As polyfunctional epoxy compounds contained in polyfunctional epoxy resins, specifically, glycidyl ethers of tetra(hydroxyphenyl)alkane, glycidyl ethers of tetrahydroxybenzophenone, epoxy polyvinylphenol, etc. can be cited. Regarding monofunctional epoxy resins, as compounds contained in monofunctional epoxy resins, specifically, p-tert-butylphenyl glycidyl ether (ADEKA GLYCERYL (registered trademark), ED-509E, ED-509S, etc. manufactured by ADEKA Corporation) can be cited.

[0022] As an epoxy resin having an alicyclic skeleton, it suffices that it has an alicyclic skeleton in one molecule, and it is a cycloalkylene oxide compound having an epoxy group formed by two carbon atoms and one oxygen atom that form an alicyclic structure. The epoxy resin having an alicyclic skeleton may be a compound containing an epoxy compound having an alicyclic skeleton. As the epoxy compound having an alicyclic skeleton, cyclohexane-based, cyclohexylmethyl ester-based, cyclohexylmethyl ether-based, spiro-based, and tricyclodecane-based epoxy compounds can be cited. As the epoxy resin having an alicyclic skeleton, specifically, 3',4'-epoxycyclomethyl 3,4-epoxycyclohexanecarboxylate (such as Celoxide (registered trademark) 2021P manufactured by Daicel Corporation), (3,3',4,4'-diepoxy)bicyclohexane (such as Celoxide (registered trademark) 8010 manufactured by Daicel Corporation), 1,2-epoxy-4-vinylcyclohexane, and an adduct of 1,2-epoxy-4-(2-oxiranyl)cyclohexane with 2,2-bis(hydroxymethyl)-1-butanol (such as EHPE3150 manufactured by Daicel Corporation) can be cited.

[0023] As an aliphatic epoxy resin, polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts can be cited. As the aliphatic epoxy compounds contained in the aliphatic epoxy resin, specifically, 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, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether (such as Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), and polyethylene glycol diglycidyl ether can be cited. In addition, as an aliphatic cyclic epoxy resin, for example, hydrogenated bisphenol A diglycidyl ether (such as jERYX8000 manufactured by Mitsubishi Chemical Corporation) can be cited.

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

[0025] Although the polymerization initiation reaction of the oxetane resin of component (A2) is slower than that of epoxy resin, it will polymerize at high speed if the polymerization initiation species reach a certain concentration or more. Therefore, a cured product can be obtained by a reaction at a low temperature for a short time. Specifically, examples of the oxetane resin include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (such as OXT-101 manufactured by Toagosei Co., Ltd.), 2-ethylhexyl oxetane (such as OXT-212 manufactured by Toagosei Co., Ltd.), xylylene bisoxetane (such as OXT-121 manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane (such as OXT-221 manufactured by Toagosei Co., Ltd.), oxetanyl sesquioxetane (such as OXT-191 manufactured by Toagosei Co., Ltd.), phenol novolac oxetane (such as PHOX manufactured by Toagosei Co., Ltd.), and 3-ethyl-3-phenoxymethyloxetane (such as OXT-211 manufactured by Toagosei Co., Ltd.).

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

[0027] Component (B): An acid generator containing an iodonium salt The iodonium salt contained in the acid generator of component (B) is preferably an iodonium compound represented by the following formula (2). [Chemical formula 4] Ar 1 -I + -Ar 2 ·Z - (2) (In the formula (2), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion)

[0028] Aryl group means an aromatic hydrocarbon group having 6 to 18 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthryl group, etc. Ar in formula (2) 1and Ar 2 Each is independent, and preferably phenyl or naphthyl is preferred. The aryl group may be unsubstituted or substituted with one or more arbitrary 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, a hydroxyl group, and the like.

[0029] The anion only needs to be a monovalent counter anion, and a non-antimony-based anion is preferred. In formula (2), Z - The shown anion is preferably BF4 - , SbF6 - , AsF6 - , B(C6F5)4 - , or Ga(C6F5)4 - , C(CF3SO2)3 - , or [P(R 3 ) a F 6-a - , [C(R 3 SO2)3] - , or [N(R 3 SO2)2] - (In the formula, R 3 are each independently an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and a is an integer of 0 to 5; when a is an integer of 2 or more, multiple R 3 may be the same as or different from each other). In formula (2), it is preferred that the anion shown by Z - has a relatively low nucleophilicity. If the anion contained in the iodonium salt has a low nucleophilicity, the growth reaction rate of the cation-curable resin becomes faster, and a cured product can be obtained at a low temperature of 100 °C or lower and in a short time.

[0030] Regarding component (B), specific examples include diphenyliodonium hexafluoroarsenate, bis(4-chlorophenyl)iodonium hexafluoroarsenate, bis(4-bromophenyl)iodonium hexafluoroarsenate, phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium tris(pentafluoroethyl)trifluorophosphate (for example, IK-1 manufactured by San Apro Ltd.), 4-methylphenyl-4-(1-methylethyl)phenyl iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(2-methylpropyl)phenyl iodonium hexafluorophosphate (for example, IRGACURE (registered trademark) 250 manufactured by BASF Corporation), bis(C 10～14 ​-alkylphenyl) iodonium hexafluorophosphate (for example, WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4-methylphenyl-4-(1-methylethyl)phenyl iodonium hexafluoroantimonate (for example, WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), other IK-1FG (manufactured by Sanya Pro Co., Ltd.), 4-isopropyl-4'-methyldiphenyl iodonium tetrakis(pentafluorophenyl)borate (for example, Bluesil (registered trademark) PI2074 manufactured by ELKEM SILICONES Co., Ltd.). Such iodonium salts can be used commercially, for example, as a cationic initiator or as an iodonium salt contained in an acid generator.

[0031] Ingredient (C): Organic peroxide of peroxydicarbonate type The peroxydicarbonate type organic peroxide represented by the following formula (1) of component (C) is a radical source and generates carbonate radicals, wherein the peroxydicarbonate type organic peroxide has alkyl groups at both ends, and the alkyl groups have at least 10 carbon atoms. The generated carbonate radicals quickly extract hydrogen from other compounds contained in the curable resin composition, generating unstable alkyl radicals such as primary radicals. Unstable alkyl radicals are highly reactive and easily cause radical redox reactions, so they are considered to be faster than the reaction rate of curing hindrance caused by oxygen. Therefore, it is believed that the curing reaction of the cationic curable resin can be carried out quickly. Organic peroxides other than the peroxydicarbonate type (such as alkyl peroxyester type organic peroxides) easily generate oxygen radicals. The generated oxygen radicals easily generate stable alkyl radicals by self-cleavage or decarbonation reaction. It is believed that the reactivity of stable alkyl radicals is low, and the reaction of oxygen hindrance will become faster than that of the electron transfer to the acid generator containing iodonium salt. This effect causes the iodonium salt to become difficult to decompose. Therefore, it is believed that the acid (cation: H + ) becomes difficult to generate, so the polymerization reaction becomes easily inhibited.

[0032] [Chemistry 5] (In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms)

[0033] In formula (1), R 1 and R 2 Each independently is an alkyl group having at least 10 carbon atoms, more preferably an alkyl group having at least 11 carbon atoms. 1 and R 2Each is independently an alkyl group having at least 10 carbon atoms, preferably each is independently an alkyl group having at least 11 carbon atoms. Then, whether at room temperature such as 20°C to 40°C below the heating temperature or at a low temperature below 20°C, the organic peroxide is difficult to decompose, the storage stability of the curable resin composition is good, and it has an excellent pot life. In formula (1), R 1 and R 2 can each independently be an alkyl group having 30 or fewer carbon atoms. In formula (1), R 1 and R 2 can be the same or different. Regarding the organic peroxide of the peroxydicarbonate type as component (C), R 1 and R 2 in formula (1) can each independently be a linear, branched or cyclic alkyl group, or a combination of the three. Regarding the organic peroxide of the peroxydicarbonate type as component (C), R 1 and R 2 are more preferably each independently a linear or branched alkyl group having at least 10 carbon atoms. In formula (1), if R 1 and R 2 each independently are a linear or branched alkyl group having at least 10 carbon atoms, then even when generating free radicals by heating at a low temperature of 100°C or lower, preferably 80°C or lower, whether at room temperature such as 20°C to 40°C below the heating temperature or at a low temperature below 20°C, the organic peroxide is even more difficult to decompose, the storage stability is better, and it has an excellent pot life.

[0034] The organic peroxide of the peroxydicarbonate type represented by the formula (1) of component (C) preferably has a 1-hour half-life temperature of 50°C to 80°C, can be 55°C to 75°C, and is preferably 55°C to 70°C. If the 1-hour half-life temperature of the organic peroxide of the peroxydicarbonate type of component (C) is 50°C to 80°C, then free radicals can be generated by heating at a low temperature of 100°C or lower, preferably 80°C or lower, to reductively decompose the iodonium salt, thereby promoting the polymerization reaction of the cationic curable resin. The organic peroxide of the peroxydicarbonate type represented by the formula (1) of component (C) preferably has a molecular weight of 200 to 1000, can be 250 to 800, and can be 300 to 700 or less.

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

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

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

[0038] (E) Photo radical generator The photo radical generator, together with the organic peroxide of the peroxydicarbonate type of the component (C), is a radical source, generates an alkyl radical by irradiation with light, reductively decomposes the iodonium salt, and generates an acid (cation: H +), thereby promoting the polymerization reaction. Since the curable resin composition of the present invention contains a peroxydicarbonate type organic peroxide as component (C), it may not contain (E) a photo radical generator. When the curable resin composition contains (E) a photo radical generator, alkyl radicals are generated by light, the iodonium salt is reductively decomposed, and an acid (cation: H + ) is also generated by light, thereby further promoting the polymerization reaction. Examples of the photo radical generator include 1-hydroxycyclohexyl phenyl ketone (such as Omnirad (registered trademark) 184 manufactured by IGM Resins), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propanone, 2-hydroxy-2-methyl-1-phenylpropanone, and the like.

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

[0040] Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, aluminum oxide, zinc oxide, silicon dioxide (precipitated silica, fumed silica (pyrogenic 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. The filler may also be added as a thixotropy imparting agent. When the filler is added as a thixotropy imparting agent, fumed silica is preferred. The fumed silica may be surface-treated. Examples of the surface treating agent for the inorganic thixotropy imparting agent include monoalkyltrialkoxysilane, dimethyldichlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. Commercially available products of surface-treated or untreated fumed silica may be used. From the viewpoint of the adhesion to the adherend, the inorganic filler is preferably silica, glass beads, and talc, and more preferably silica from the viewpoints of improving fluidity, injectability, and coatability. Examples of the silica 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.), nano silica, etc. Two or more types of silica having different types or different particle diameters may be used in combination, or one type may be used alone.

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

[0042] The average particle diameter of the filler is not particularly limited. In order to improve fluidity, injectability, coatability, adhesion, etc., it 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. The average particle diameter of the filler can be measured by a laser diffraction particle size distribution measuring device, a dynamic light scattering type NANOTRAC particle size distribution meter, etc. The average particle diameter may be the 50% cumulative particle diameter in the volume-based particle size distribution, or the 50% cumulative particle diameter in the number-based particle size distribution.

[0043] (G) Coupling agent The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds to an inorganic material, and the other is a functional group that chemically bonds to an organic material. The curable resin composition contains a coupling agent, so that the adhesion of the curable resin composition can be improved when bonding dissimilar materials such as in a camera module, a sensor module, etc.

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

[0045] Examples of the functional group possessed by the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacrylic group, an acrylic group, an amino group, an isocyanurate group, a urea group, a mercapto group, a thioether group, and an isocyanate group. Examples of the silane coupling agent include silane compounds having an epoxy group and an alkoxy group and optionally 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 optionally an alkyl group, such as vinyltrimethoxysilane and p-phenylvinyltrimethoxysilane; silane compounds having a (meth)acrylic group and an alkoxy group and optionally an alkyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Silane compounds having a primary or secondary amino group and an alkoxy group and optionally an alkyl group, such as aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; Silane compounds having one or more groups selected from the group consisting of a mercapto group, an isocyanate group, a urea group and a halogen atom and one or more alkoxy groups and optionally an alkyl group, such as thiol, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane.

[0046] (H) Ion Traps The ion trapping agent captures free iodonium ions and improves the various reliability of the cured product. The ion trapping agent is not particularly limited and can be selected from substances generally used as materials such as sealing materials. Specifically, hydrous oxides of elements such as hydrotalcites, magnesium, aluminum, titanium, zirconium, and bismuth can be cited. As commercially available products, IXEPLAS-A1, IXEPLAS-A2 manufactured by Toa Synthetic Co., Ltd. (Toa Synthetic Co., Ltd.) can be cited. One ion trapping agent can be used, or two or more can be used in combination.

[0047] (I) Colorant A colorant may be used for the purpose of coloring the curable resin composition. As the colorant, for example, pigments, dyes, coloring matters, etc. may be used. Known colorants such as red, blue (cyan), green, yellow, black, white, etc. may be used as the colorant. As the pigment, for example, as a black colorant, carbon black-based, graphite-based, iron oxide-based, titanium black, anthraquinone-based, cobalt oxide-based, copper oxide-based, manganese-based, antimony oxide-based, nickel oxide-based, perylene-based, aniline-based, molybdenum sulfide, bismuth sulfide, etc. may be cited. As commercially available products, for example, as the pigment, titanium black 13M, 13M-C, 13M-T, etc. manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd. may be cited.

[0048] In addition to (G) coupling agent, (H) ion scavenger, or (I) colorant, other optional components may include additives, leveling agents, antioxidants, defoaming agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, etc.

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

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

[0051] The cation-curable resin as the component (A) in the curable resin composition, when containing at least one selected from the group consisting of the epoxy resin having a ring skeleton in the molecule of the component (A1) and the oxetane resin of the component (A2), when the total amount of the component (A) is set to 100% by mass, the total amount of the component (A1) and the component (A2) is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass. In order to obtain a cured product having a low elastic modulus, when the total amount of the component (A) is set to 100% by mass, the component (A) may be at least one component selected entirely from the group consisting of the component (A1) and the component (A2), or may be (the total amount of the component (A1) and the component (A2) is 100% by mass). In the component (A), when the total amount of the component (A1) and the component (A2) is less than 100% by mass, the remaining part excluding the component (A1) and the component (A2) may be at least one selected from the group consisting of an epoxy resin having no ring skeleton in the molecule (such as an aliphatic epoxy resin, etc.), a polystyrene-based compound, and a vinyl ether compound).

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

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

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

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

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

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

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

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

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

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

[0062] In order to cure by low-temperature heating at 100°C or lower, preferably 80°C or lower, relative to 100 parts by mass of the component (A), the component (C) in the curable resin is preferably 0.1 part by mass to 10.0 parts by mass, more preferably 0.5 part by mass to 8 parts by mass, and still more preferably 1.0 part by mass to 5 parts by mass.

[0063] The blending ratio of the component (B) and the component (C) in the curable resin ((component (B): component (C))) is preferably on the order of equal amounts, and in terms of mass ratio, it can be 25:75 to 75:25, can be 30:70 to 70:30, can be 40:60 to 60:40, and can be 50:50.

[0064] Relative to 100% by mass of the total amount of the curable resin composition, the photosensitizer of the component (D) in the curable resin composition can be 0% to 3.0% by mass, can be 0.05% to 3.0% by mass, can be 0.05% to 2.0% by mass, and can be 0.1% to 1.0% by mass.

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

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

[0067] The above-mentioned optional component 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 the total amount of the curable resin composition (100% by mass). As described above, the optional component may include at least one selected from the group consisting of (G) a coupling agent, (H) an ion trapping agent, and (I) a coloring agent.

[0068] Method for producing curable resin composition The curable resin composition can be manufactured by mixing component (A), component (B) and component (C). The curable resin composition can be further manufactured by mixing component (D), component (E), component (F), component (G), component (H), component (I), and other arbitrary components as needed. The curable resin composition can be manufactured by mixing each component with an additive as needed. Each component can be introduced into a suitable mixer simultaneously or separately, and if necessary, it is stirred and mixed while being melted by heating, so as to obtain the curable resin composition. The manufacturing method of the curable resin composition is not particularly limited. The curable resin composition can be manufactured by mixing the raw materials of each component by a mixer such as a pounding machine (life machine), a Henschel mixer (Henschel mixer), a roller mill, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. equipped with a stirring device and a heating device. In addition, it is also possible to appropriately combine two or more devices to manufacture the curable resin composition.

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

[0070] Binder or sealant The curable resin composition can be used as a binder or sealant for fixing, joining, or protecting components constituting an electronic device, a camera module, or a sensor module to each other, and can also be used as a binder or sealant containing the curable resin composition.

[0071] Supply method of curable resin composition The curable resin composition can be supplied using an ejection dispenser, an air dispenser, etc. In addition, it can be supplied by known coating methods (dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, etc.) and known printing methods (lithography, carton printing, metal printing, offset printing, screen printing, gravure printing, flexographic printing, inkjet printing, etc.).

[0072] Curing conditions of 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, further preferably 70°C or more, preferably 45°C or more, more preferably 55°C or more. The heating time for curing the curable resin composition is preferably 15 minutes or more and 4 hours or less, more preferably 30 minutes or more and 2 hours or less, further preferably 30 minutes or more and 60 minutes or less.

[0073] Cured product A cured product can be obtained by curing a curable resin composition, a binder or a sealing material containing the curable resin composition. The curable resin composition is cured at, for example, at least 100°C or lower, preferably 80°C for 60 minutes to obtain a cured product. For the cured product, the glass transition temperature (Tg) measured using a dynamic viscoelasticity measuring device (such as DMA7100 manufactured by Hitachi High-Technologies Science Co., Ltd.) is preferably 0°C to 200°C, more preferably 1°C to 150°C, further preferably 2°C to 130°C, and even more preferably 3°C to 120°C. If the Tg of the obtained cured product is 200°C or lower, a cured product that can be cured at a low temperature can be obtained. For the measurement of the glass transition temperature, it is measured by the tensile method in the range of -20°C to 250°C, at a frequency of 10 Hz, a heating rate of 3°C / min, and a strain amplitude of 5 μm. Regarding Tg, the storage elastic modulus (E') and the loss elastic modulus (E") of the cured product are measured, and the peak temperature of the dielectric loss tangent (tanδ) obtained by E" / E' is taken as Tg.

[0074] Semiconductor device, electronic device Regarding the curable resin composition, in the case where a binder or a sealing material containing the curable resin composition is used for fixing, bonding, or protecting an electronic component, an electronic device containing a cured product can be obtained, and the cured product is a cured product obtained by curing the curable resin composition, the binder or the sealing material containing the curable resin composition. The electronic device may be a semiconductor device containing a semiconductor element. Examples of the electronic device include a mobile phone, a smart phone, a laptop computer, a tablet terminal, a camera module, and the like. When the curable resin composition, the binder or the sealing material containing the curable resin composition is used for fixing, bonding, or protecting an electronic component, an electronic device can be provided using a binder that can be cured by low-temperature heating at 100°C or lower, preferably 80°C or lower. Examples

[0075] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

[0076] The following shows the respective components used in the curable resin compositions of the examples and the comparative examples.

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

[0078] Component (A): Cation-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, oxetanyl equivalent 107 g / eq. (A2-2): OXT-101 (manufactured by Toagosei Co., Ltd.), 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), molecular weight 116, oxetanyl equivalent 116 g / eq.

[0079] Component (B): Acid generator containing an iodonium salt (B-1): Bluesil (registered trademark) PI2074 (manufactured by ELKEM SILICONES), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (B-2): IK-1FG (manufactured by Sanyapro Corporation)

[0080] Component (C): The organic peroxide of the peroxy dicarbonate type represented by the formula (1) (C-1): Perkadox 24L (manufactured by Nouryon), dicetyl peroxydicarbonate, 1-hour half-life temperature 65 °C, molecular weight 570.9, R in the formula (1) 1 and R 2 are each a hexadecyl group having 16 carbon atoms (-(CH2) 15 -CH3), and is a solid (powder) at normal temperature (about 20 °C to 25 °C). [Chemical Formula 6] (C-2): Perkadox 26 (manufactured by Nouryon), dilauroyl peroxide carbonate, with a molecular weight of 514.8, and R in formula (1) 1 and R 2 are respectively tetradecyl groups having 14 carbon atoms (-(CH2) 13 -CH3). [Chemical Formula 7] (C-3): Peroyl TCP (manufactured by NOF Corporation), bis(4-tert-butylcyclohexyl) peroxide carbonate, with a 1-hour half-life temperature of 58 °C, a molecular weight of 398.5, and is a solid (powder) at room temperature (about 20 °C to 25 °C). [Chemical Formula 8] (C-4): Ditridecyl peroxide carbonate (manufactured by Alfa Chemistry), with a molecular weight of 486.72, and is a solid (powder) at room temperature (about 20 °C to 25 °C) (C-5): Distearoyl peroxide carbonate (manufactured by SAGECHEM LIMITED), with a molecular weight of 626.99, and is a solid (powder) at room temperature (about 20 °C to 25 °C)

[0081] Component (C'): An organic peroxide of the peroxide carbonate type. For the organic peroxide of the peroxide carbonate type, in the formula (1), R 1 and R 2 are respectively alkyl groups having less than 10 carbon atoms (C'-1): Lupersol 225 (manufactured by Arkema Kishu Co., Ltd.), bis(sec-butyl) peroxide carbonate, with a 1-hour half-life temperature of 69 °C, a molecular weight of 234.2, and is a liquid at room temperature (about 20 °C to 25 °C). [Chemical Formula 9]

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

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

[0084] (F) Filler (F-1): SE5200SEE (manufactured by Adma Technologies Co., Ltd.), high-purity synthetic spherical silica, with an average particle diameter of 1.5 μm (catalog value) at the cumulative 50% in the volume-based particle size distribution obtained by the laser diffraction scattering method. (F-2): Cab-O-Sil (registered trademark) TS720 (manufactured by Cabot Japan Ltd.), hydrophobic silica, with an average particle diameter of 0.012 μm (catalog value) at the cumulative 50% in the number-based particle size distribution obtained by the laser diffraction scattering method.

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

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

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

[0088] Examples 1 to 11, Comparative Example 1 According to the compounding ratios shown in Table 1 and Table 2, each amount of each component was mixed using a three-roll mill to prepare a curable resin composition. In Table 1 and Table 2, the numbers representing the compounding ratios of the respective components contained in the curable resin composition represent mass percentages relative to the total amount of the curable resin composition of 100 mass% unless otherwise specified. In the table, the main notations of the product names or trade names are described for each component. In addition, in the table, the notation "-" indicates that the corresponding component is not included in the curable resin composition.

[0089] Examples 12 and 13 Except that the component (C-1) used in Example 1 was replaced with component (C-4) and component (C-5) respectively, the resin compositions of Examples 12 and 13 were manufactured in the same manner as in Example 1. For the resin compositions of Examples 12 and 13 and the properties of the cured products obtained by curing the resin compositions, the measurements were carried out in the same manner as in Example 1. Examples 12 and 13 are also similarly assumed to be curable by low-temperature heating at 80°C or lower and have a long pot life.

[0090] In the examples and comparative examples, the properties of the curable resin composition and the cured product were measured in the following manner. The results are shown in Tables 1 and 2.

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

[0092] Pot life Using a Brookfield rotational viscometer (HBDV-I type or RVDV-I type, spindle: SC4-14 spindle, rotation speed: 50 rpm, measurement temperature: 25 °C), the viscosity of the curable resin composition was measured at 25 °C within 1 hour after preparing the curable resin composition. Then, in an environment of 25 °C and 50% humidity, after 10 hours and 24 hours, a part of the curable resin composition stored in a sealed container was taken out from the sealed container, and the viscosity of the curable resin composition was measured. When the viscosity increase ratio (viscosity after 10 hours ÷ initial viscosity) from the initial viscosity measurement to 10 hours later was 1.0 times or less, it was judged as excellent (Excellent, "E"), when it was higher than 1.0 times and 2.0 times or less, it was judged as good (Good, "G"), and when it was more than that, it was judged as poor (Bad, "B"). In addition, when the viscosity increase ratio (viscosity after 24 hours ÷ initial viscosity) until 24 hours later was 1.0 times or less, it was judged as excellent (Excellent, "E"), when it was higher than 1.0 times and 5.0 times or less, it was judged as good (Good, "G"), and when it was more than that, it was judged as poor (Bad, "B"). ">5.0" in the table means that the viscosity increase ratio until 24 hours later is greater than 5.0.

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

[0094] Curability at 80 °C First, a Teflon (registered trademark) sheet is attached to the surface of a 3-mm-thick glass plate, and spacers (spacers with overlapping heat-resistant tapes) are arranged at two positions thereon such that the film thickness during curing becomes 400 ± 150 μm. Then, a curable resin composition is applied between the spacers and clamped with another glass plate having a Teflon (registered trademark) sheet attached to its surface so as not to entrap air bubbles, and cured by heating with a hot air dryer at 80°C for 60 minutes. When the curable resin composition is solid and non-tacky, it is rated as excellent ("E"), when it is solid and tacky, it is rated as good ("G"), and when it is liquid and uncured, it is rated as bad ("B"). By clamping with glass, the curability can be judged without considering the influence of oxygen inhibition.

[0095] [Table 1]

[0096] [Table 2]

[0097] As shown in Table 1 and Table 2, the cured products of the curable resin compositions of Examples 1 to 11 have good curability, can be cured by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, and have an excellent pot life until the viscosity increase ratio is 1.0 after 10 hours. After 24 hours, the viscosity increase ratio of Example 10 is greater than 2.0 and it is cured. In addition, the Tg values obtained in the examples are all in the range of 0°C to 200°C. Further, except for Examples 4, 7, and 8, the Tg values obtained in the examples are all in the range of 0°C to 150°C.

[0098] Comparative Example 1 can be cured at 80°C, but tackiness is confirmed after 10 hours, and the effect of the pot life is impaired. Industrial Applicability

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

Claims

1. A curable resin composition, wherein, The curable resin composition contains: (A) A cation-curable resin, (B) An acid generator containing an iodonium salt, and (C) An organic peroxide of the peroxydicarbonate type represented by the following formula (1), [Chemical formula 1] In the formula (1), R 1 and R 2 are each independently an alkyl group having at least 10 carbon atoms.

2. The curable resin composition according to claim 1, wherein, In the formula (1), R 1 and R 2 are each independently an alkyl group which can be linear, branched or cyclic and has at least 11 carbon atoms, or a combination of the three thereof.

3. The curable resin composition according to claim 1 or 2, wherein, The iodonium salt contained in the component (B) is an iodonium salt compound represented by the following formula (2), [Chemical formula 2] Ar 1 -I + -Ar 2 ·Z - (2) In the formula (2), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion.

4. The curable resin composition according to claim 3, wherein, Z in formula (2) - is BF4 - , SbF6 - , AsF6 - , B(C6F5)4 - , or Ga(C6F5)4 - , C(CF3SO2)3 - , or [P(R 3 ) a F 6-a - , [C(R 3 SO2)3] - , or [N(R 3 SO2)2] - ; where R 3 are each independently an alkyl group in which at least a part of the hydrogen atoms are substituted by fluorine atoms, and a is an integer from 0 to 5; when a is an integer of 2 or more, the multiple R 3 present may be the same or different from each other.​ 5. The curable resin composition according to any one of claims 1 to 4, wherein, The component (A) includes at least one selected from the group consisting of (A1) An epoxy resin having an epoxy equivalent of 100 g / eq to 1000 g / eq and having a ring skeleton in the molecule, and (A2) An oxetane resin in the group.

6. The curable resin composition according to claim 5, wherein, The component (A1) includes an epoxy resin having an epoxy equivalent of 200 g / eq or more.

7. The curable resin composition according to any one of claims 1 to 6, wherein, When the total amount is set to 100 parts by mass, the amount of the component (C) is 0.1 part by mass to 10 parts by mass.

8. An adhesive or a sealing material, wherein, The adhesive or the sealing material contains the curable resin composition according to any one of claims 1 to 7.

9. A cured product, wherein, The cured product is a cured product obtained by curing the curable resin composition according to any one of claims 1 to 7 and the adhesive or the sealing material according to claim 8.

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

11. A semiconductor device, wherein, The semiconductor device contains the cured product according to claim 9 or 10.

12. An electronic device, wherein, The electronic device contains the cured product according to claim 9 or 10.

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