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

Abstract

Provided are a curable resin composition, an adhesive, a sealing material, a cured product having a low Tg, and a semiconductor device and an electronic device including the cured product, the curable resin composition, the adhesive, and the sealing material being capable of being cured at a low temperature, being capable of obtaining a cured product having a low Tg, and having excellent followability to an adherend. 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, the component (A) includes at least one selected from the group consisting of (A1) an epoxy resin having a ring skeleton in the molecule and (A2) an oxetane resin.

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 devices.

[0003] For example, Patent Document 1 discloses that for a thermally cationically polymerizable composition that can be used in the field of adhesives, etc., 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 addition amount of a thermal cationic initiator in the composition is adjusted, and which can maintain a high glass transition temperature (Tg) of greater than 100°C, thereby reducing the outgas amount. 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, low-temperature curing is required, and an adhesive capable of obtaining a cured product having a low Tg is desired. In addition, in the case of frequently bonding dissimilar materials such as camera modules and sensor modules, in order to alleviate the expansion and contraction caused by the difference in the linear expansion coefficients of the respective different materials, there are also cases where the adhesive is required to have followability to follow the expansion and contraction of the adherend.

[0006] Therefore, an object of the present invention is to provide a curable resin composition, an adhesive, a sealing material, a cured product obtained by curing them, a semiconductor device, and an electronic device that can be cured by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, wherein the cured product has a low Tg and excellent followability to the adherend. Technical Means for Solving the Technical Problem

[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, wherein the curable resin composition comprises: (A) A cation-curable resin, (B) An acid generator containing an iodonium salt, and (C) An organic peroxide of the diperoxydicarbonate type. [2] The curable resin composition according to [1] above, wherein the component (A) includes at least one selected from the group consisting of (A1) An epoxy resin having a ring skeleton in the molecule, and (A2) An oxetane resin in the group. [3] The curable resin composition according to [2] above, wherein the component (A1) has an aromatic ring skeleton. [4] The curable resin composition according to any one of [1] to [3] above, wherein the 1-hour half-life temperature of the component (C) is 50°C to 80°C. [5] The curable resin composition according to any one of [1] to [4] above, wherein the iodonium salt contained in the component (B) is an iodonium salt compound represented by the following formula (1). [Chemical Formula 1] Ar 1 -I + -Ar 2 ·Z - (1) (In the formula (1), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion) [6] The curable resin composition according to [5] above, wherein Z in the formula (1) - 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 3Each independently represents 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 Rs present 3 may be the same as or different from each other). [7] The curable resin composition according to the above [2] or [3], wherein the component (A1) contains an epoxy resin having an epoxy equivalent of 100 g / eq to 1000 g / eq. [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] or 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 100°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 the cured product has a low Tg and excellent followability to an adherend. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 A diagram showing a method for manufacturing a test piece for a thin-film cured product test. DETAILED DESCRIPTION OF THE INVENTION

[0011] 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 device 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 device. 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 of the component uses the term "resin" which generally means a polymer (especially a synthetic polymer).

[0012] 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 diperoxycarbonate type organic peroxide (hereinafter also referred to as "component (C)").

[0013] 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.

[0014] However, the free radicals generated by organic peroxides are easily hindered by curing due to oxygen. The free radicals generated by organic peroxides generate stable alkyl radicals such as tertiary free radicals along with hydrogen abstraction reaction. Stable alkyl radicals react with oxygen to generate relatively stable peroxide radicals. Peroxide radicals are stable, so they hardly react with compounds of iodonium salt system. Therefore, free radical redox reaction is easily hindered. The thinner the thickness of the obtained solidified material is, the easier it is to significantly occur the curing hindrance caused by oxygen. It is believed that the main reason is that the thinner the thickness of the solidified material is, the larger the area in contact with air relative to the volume. If the curing hindrance caused by oxygen is caused, there is a worry that the bonding is insufficient, the bonding strength is reduced, and it is easy to deteriorate in the insufficiently cured part. In the resin composition that can obtain the high Tg solidified material, the poor bonding caused by the curing hindrance caused by oxygen is confirmed in the resin composition that can obtain the low Tg solidified material, especially in the case of low Tg, it is easy to confirm the curing hindrance caused by oxygen. In this specification, a cured product with a low Tg refers to a cured product with a Tg of, for example, 120°C or less, and may be a cured product with a Tg of 118°C or less, preferably a cured product with a Tg of 0°C to 100°C. In the case of a thin film and insufficient curing, there is a possibility of outgassing and contamination of the surroundings. On the other hand, in the case of a thin film and sufficient curing, outgassing can be reduced and surrounding pollution can be improved. Examples of the thin film cured product include a film-like, layered, or film-like (フイルム-like) cured product with a thickness of 100 μm or less.

[0015] The curable resin composition contains a di(peroxydicarbonate) type organic peroxide as component (C). The reaction in which the carbonate radical generated from component (C) abstracts hydrogen from other compounds contained in the curable resin composition is fast, and an unstable alkyl radical such as a primary radical is generated. Since the unstable alkyl radical easily causes a radical redox reaction, 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, since the hydrogen abstraction reaction of the carbonate radical is faster than that of the alkoxy radical, it is considered that the instantaneous radical concentration in the system of the curable resin composition becomes higher than that of the organic peroxide other than component (C). Therefore, even if affected by oxygen inhibition, most of the radicals remaining unhindered remain in the carbonate radical generated from component (C), can react with component (B), and can cause the curing reaction of the cation-curable resin to proceed rapidly. Compared with causing curing inhibition by oxygen, the polymerization reaction of the curable resin composition proceeds rapidly even when a thin film-like cured product is formed. Therefore, it can be cured by heating at a low temperature of, for example, 100 °C or lower, preferably 90 °C or lower, more preferably 85 °C or lower, and further preferably 80 °C or lower, and a cured product having a low Tg can be obtained. Further, even when a thin film-like cured product having a thickness of 100 μm or less, preferably a thickness of 0.5 μm or more and 100 μm or less is obtained, curing inhibition caused by oxygen is suppressed, and it can be cured by heating at a low temperature of, for example, 100 °C or lower, preferably 80 °C or lower, to obtain a cured product having a low Tg. When the thickness of the cured product is 0.5 μm to 100 μm, it is called a thin film-like cured product. The thickness of the cured product can be 90 μm or less, can be 80 μm or less, can be 70 μm or less, and can be 1 μm or more.

[0016] In cases where a curable resin composition is used as an adhesive for bonding dissimilar materials, such as in a camera module or a sensor module, in order to alleviate the expansion and contraction caused by the difference in the linear expansion coefficients of the respective different materials, there are also cases where the adhesive is required to have followability to follow the expansion and contraction of the adherend. In order to obtain a cured product having followability, it can be considered that the curable resin composition contains a resin having a large functional group equivalent as a cation-curable resin. Here, the functional group equivalent refers to the ratio of the reactive groups, i.e., functional groups, in one molecule. For example, in the case of an epoxy resin, it refers to the molecular weight per equivalent of the epoxy groups in the compound, i.e., the epoxy equivalent. For example, in the case of an oxetane resin, it refers to the molecular weight per equivalent of the oxetanyl groups in the compound, i.e., the oxetanyl equivalent. The epoxy equivalent number, oxetanyl equivalent number, etc., which are functional group equivalent numbers, represent the number of functional groups (equivalent numbers) per mass (input amount) of the compound. Compared with a resin or compound having a low functional group equivalent, the reaction rate of a resin or compound having a large functional group equivalent in the curable resin composition is slow. Therefore, in the case of containing a resin or compound having a large functional group equivalent as a cation-curable resin, the cation reactivity is insufficient, and if there is an insufficiently cured portion, there is a case where the adhesion becomes poor. The curable resin composition containing a resin or compound having a large functional group equivalent has a low storage elastic modulus (E') and a low Tg, and a cured product having followability to follow the expansion and contraction of the adherend can be obtained.

[0017] The curable resin composition of the present invention contains (B) an acid generator containing an iodonium salt and (C) an organic peroxide of the peroxydicarbonate type. Therefore, even when a resin having a large functional group equivalent is used as the cation-curable resin, curing failure is not likely to occur. The peroxydicarbonate type organic peroxide has a relatively low half-life temperature and excellent reactivity at low temperatures. It is considered that the reaction rate of the radicals generated from component (C) with the curing inhibition caused by oxygen is faster than the reaction rate of the generated radicals with component (B). Therefore, a radical redox reaction easily occurs, and an acid (cation: H + ) can be efficiently generated. Even when heated at a low temperature of, for example, 100 °C or lower, preferably 80 °C or lower, the curing reaction of the cation-curable resin can proceed rapidly, partial curing failure can be suppressed, and a cured product having a low Tg can be obtained.

[0018] In order to obtain a cured product with followability, it can be considered that the curable resin composition contains, for example, a resin having a linear alkyl or alkylene group with a large number of carbon atoms as the cation-curable resin. Compared with a resin having a linear alkyl or alkylene group with a small number of carbon atoms, a resin having a long-chain alkyl or alkylene group with a large number of carbon atoms tends to have low cation reactivity.

[0019] The curable resin composition of the present invention contains (B) an acid generator containing an iodonium salt and (C) an organic peroxide of the diperoxydicarbonate type. Therefore, even when a resin with a large functional group equivalent is used as the cation-curable resin, it can be cured. By heating at a low temperature of, for example, 100 °C or lower, preferably 80 °C or lower, even a cation-curable resin with a large functional group equivalent shows cation reactivity, and the curing reaction proceeds rapidly, and a cured product with followability can be obtained.

[0020] In addition, a cured product with followability that follows the expansion and contraction of the adherend can be obtained from a curable resin composition containing a resin, wherein the resin is a resin having a ring skeleton such as an aromatic ring in the molecule. However, a resin having a ring skeleton such as an aromatic ring in the molecule tends to have low cation reactivity.

[0021] The curable resin composition of the present invention contains (B) an acid generator containing an iodonium salt and (C) an organic peroxide of the diperoxydicarbonate type. Therefore, even when a resin having a ring skeleton in the molecule is used as the cation-curable resin, free radicals can be efficiently generated from the organic peroxide of the diperoxydicarbonate type, and a radical redox reaction easily occurs. By heating at a low temperature of, for example, 100 °C or lower, preferably 80 °C or lower, a cation-curable resin having an aromatic ring in the molecule can be rapidly cured, and a cured product with excellent followability to the adherend can be obtained.

[0022] 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, and a vinyl ether group. 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 be cured at a low temperature of 100 °C or lower, preferably 80 °C or lower, so as to obtain a cured product with a low Tg and excellent followability to the adherend, the cation-curable resin of component (A) preferably has a molecular weight of 100 to 800, and may also be 110 to 780.

[0023] The cation-curable resin of component (A) preferably contains at least one selected from the group consisting of (A1) an epoxy resin 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)"). Regarding the curable resin composition, by including at least one selected from the group consisting of the epoxy resin having a ring skeleton in the molecule of component (A1) and the oxetane resin of (A2) in component (A), a cured product having a low Tg and excellent followability with a low elastic modulus can be obtained. Component (A) may contain component (A1) alone or may contain both component (A1) and component (A2).

[0024] Examples of the epoxy resin include an aliphatic epoxy resin and (A1) an epoxy resin having a ring skeleton in the molecule. The epoxy resin preferably contains (A1) 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 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, and more preferably contains an epoxy resin having an aromatic ring skeleton.

[0025] As an epoxy resin having an aromatic ring skeleton, as a polyfunctional epoxy resin, specifically, bisphenol A type epoxy resins (such as EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067 manufactured by DIC Corporation), special epoxy resins formed by adding a polyalkylene oxide structure to the bisphenol A skeleton (such as AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4010S manufactured by ADEKA Corporation), bisphenol F type epoxy resins (such as EPICRON (registered trademark) 830-S, EXA-830LVP manufactured by DIC Corporation), bisphenol AD type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins (such as EPICRON (registered trademark), HP-4032D, HP-720H manufactured by DIC Corporation), phenol novolac type epoxy resins (such as EPICLON (registered trademark) N-740, N-770 manufactured by DIC Corporation), cresol novolac type epoxy resins (such as EPICRON (registered trademark), N-660, N-670, N-655-EXP-S manufactured by DIC Corporation), etc. As the polyfunctional epoxy compound contained in the polyfunctional epoxy resin, specifically, glycidyl ethers of tetra(hydroxyphenyl)alkane, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, etc. can be cited. Regarding the monofunctional epoxy resin, as the compound contained in the monofunctional epoxy resin, specifically, p-tert-butylphenyl glycidyl ether (such as Adeka Glycilol (registered trademark), ED-509E, ED-509S manufactured by ADEKA Corporation) can be cited. In addition, since the bisphenol A type epoxy resin contains an aromatic ring in the molecule, there is a tendency for low reactivity and a high Tg, and thus there are cases where the followability with the adherend is impaired. Therefore, from the viewpoint of Tg, when the total amount of component (A) is set to 100% by mass, the bisphenol A type epoxy resin having an epoxy equivalent of 200 g / eq or less is preferably 20% by mass or less.

[0026] 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 (Celoxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), (3,3',4,4'-diepoxy)bicyclohexane (Celoxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, and an adduct of 1,2-epoxy-4-(2-oxiranyl)cyclohexane with 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.) can be cited.

[0027] As the aliphatic epoxy resin, polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts can be cited. As the aliphatic epoxy compound 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 (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd., etc.), and polyethylene glycol diglycidyl ether can be cited. In addition, as the aliphatic cyclic epoxy resin, for example, hydrogenated bisphenol A diglycidyl ether (jERYX8000 manufactured by Mitsubishi Chemical Corporation, etc.) can be cited.

[0028] As specific examples of the vinyl ether compound, hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexanedimethanol, triethylene glycol divinyl ether, dodecyl vinyl ether, and cyclohexyl vinyl ether can be cited.

[0029] When component (A) contains an epoxy resin, the epoxy equivalent weight of the epoxy resin is preferably 100 g / eq to 1000 g / eq. When component (A) contains an epoxy resin (A1) having a cyclic skeleton in the molecule, the epoxy equivalent weight of component (A1) is preferably 100 g / eq to 1000 g / eq. When the epoxy equivalent weight of the epoxy resin contained in component (A) is 100 g / eq to 1000 g / eq, a cured product having a low Tg can be obtained when cured by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower. When component (A) contains an epoxy resin, the epoxy equivalent weight of the epoxy resin 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, can be 200 g / eq or more. In addition, an epoxy resin having an epoxy equivalent weight of 200 g / eq or less has a small number of epoxy equivalent weights, and there is a tendency for the Tg to become high, so there are cases where the followability to the adherend is impaired. Therefore, when an epoxy resin having an epoxy equivalent weight of 200 g / eq or less is included, when the total amount of component (A) is 100% by mass, the epoxy resin having an epoxy equivalent weight of 200 g / eq or less is preferably 20% by mass or less, can be 18% by mass or less, can be 0% by mass, can be 1% by mass or more, can be 3% by mass or more. From the viewpoint of obtaining a cured product having a low Tg, when the total amount of component (A) is 100% by mass, the epoxy resin having an epoxy equivalent weight greater than 200 g / eq is preferably 10% by mass or more, more preferably 20% by mass, further preferably 30% by mass, and particularly preferably 40% by mass or more. In addition, from the viewpoint of the followability to the adherend, a special epoxy resin obtained by adding a polyalkylene oxide structure to a bisphenol A skeleton is particularly preferred. When the total amount of component (A) is 100% by mass, its blending amount is preferably 10% by mass or more, more preferably 20% by mass or more.

[0030] Although the polymerization initiation reaction of the oxetane resin of component (A2) is slower than that of epoxy resin, if the polymerization initiation species reaches a certain concentration or more, it will polymerize at high speed. Therefore, a cured product can be obtained by a reaction at a low temperature for a short time. Specifically, regarding the oxetane resin, 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.) can be cited.

[0031] 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 having a low Tg can be obtained when it is cured by heating at a low temperature of, for example, 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.

[0032] 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 (1). [Chemical formula 2] Ar 1 -I + -Ar 2 ·Z - (1) (In the formula (1), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion)

[0033] An 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 anthryl group. Ar in formula (1)1 and Ar 2 Each is independent, and preferably phenyl or naphthyl is preferred. The aryl group may be unsubstituted or may be 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, etc.

[0034] The anion only needs to be a monovalent counter anion, and a non-antimony-based anion is preferred. In formula (1), Z - The anion shown 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 Each is independently an alkyl group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and a is an integer from 0 to 5; when a is an integer of 2 or more, multiple R 3 present may be the same as or different from each other). In formula (1), preferably the anion shown by Z - has relatively low nucleophilicity. If the nucleophilicity of the anion contained in the iodonium salt is low, the rate of the growth reaction of the cation-curable resin becomes fast, and a cured product can be obtained by heating at a low temperature of 100 °C or lower, preferably 80 °C or lower, for a short time.

[0035] ​Regarding component (B), as specific examples, 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® 250 manufactured by BASF Corporation), bis(C 10～14 -alkylphenyl)iodonium hexafluorophosphate (for example, WPI-113 manufactured by Fujifilm Wako Pure Chemical Corporation), 4-methylphenyl-4-(1-methylethyl)phenyl iodonium hexafluoroantimonate (for example, WPI-116 etc. manufactured by Fujifilm Wako Pure Chemical Corporation), other IK-1FG (manufactured by San Apro Ltd.), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (for example, Bluesil® PI2074 etc. manufactured by Elkem Silicones). Such iodonium salts can be used, for example, as commercially available products as cationic initiators or as iodonium salts contained in acid generators.

[0036] Component (C): Peroxydicarbonate-type organic peroxide The peroxydicarbonate-type organic peroxide of component (C) is a radical source. As described above, even if the carbonate radicals generated from component (C) are affected by oxygen hindrance, a majority of the radicals that remain unhindered will remain and can react with component (B), so that the curing reaction of the cation-curable resin can proceed rapidly. Compared with peroxydicarbonate-type organic peroxides, organic peroxides other than peroxydicarbonate-type (for example, alkyl peroxide ester-type organic peroxides) have low activity. Therefore, the reaction rate for generating alkyl radicals is slow, and it is difficult for electrons to move to the acid generator containing the iodonium salt, so that the iodonium salt becomes difficult to decompose. As a result, it is considered that it becomes difficult to generate an acid (cation: H + ), so that the polymerization reaction is difficult to proceed. In addition, the curable resin composition preferably does not contain a thermal cationic polymerization initiator. By containing component (B) and component (C), the curable resin composition can promote the polymerization reaction by heating at a low temperature of 100 °C or lower, preferably 80 °C or lower. Further considering the environmental impact such as reducing PFAS (meaning per- and polyfluoroalkyl substances), it is preferably free of a thermal cationic polymerization initiator.

[0037] The organic peroxide of the peroxydicarbonate type as component (C) has a structure represented by -O-C(=O)-O-O-C(=O)-O-. It serves as a radical source and generates carbonate radicals without accompanying decarbonation reaction. The organic peroxide of the peroxydicarbonate type as 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 as component (C) is 50°C to 80°C, then even in the case of generating radicals by heating at a low temperature of 100°C or lower, preferably 80°C or lower, and reductively decomposing the iodonium salt to obtain a cured product in the form of a thin film with a thickness of 100 μm or less, the curing hindrance caused by oxygen can be inhibited and the polymerization reaction of the cation-curable resin can be promoted. The organic peroxide of the peroxydicarbonate type as component (C) preferably has a molecular weight of 180 to 1000, can be 200 to 800, and can be 220 to 700 or less. If the molecular weight of the organic peroxide of the peroxydicarbonate type as component (C) is 180 to 1000, the polymerization reaction can be carried out by heating at a low temperature of 100°C or lower, preferably 80°C or lower.

[0038] The organic peroxide of the peroxydicarbonate type as component (C) is preferably one with a self-accelerating decomposition temperature (SADT) greater than 10°C (>10°C), more preferably 12°C or higher (≥12°C), and further preferably 15°C or higher (≥15°C). The organic peroxide of the peroxydicarbonate type as component (C) preferably has a self-accelerating decomposition temperature (SADT) of 50°C or lower (≤50°C), can be 48°C or lower (≤48°C), and is more preferably 45°C or lower (≤45°C). The curable resin composition containing the organic peroxide of the peroxydicarbonate type with an SADT greater than 10°C and 50°C or lower has good storage stability and can obtain a cured product with a low Tg by heating at a low temperature of 100°C or lower, preferably 80°C or lower. The self-accelerating decomposition temperature (SADT) refers to the lowest temperature at which heat generation or self-accelerating decomposition of 6°C or higher occurs within 7 days in a state of being filled into a container of a certain amount. The self-accelerating decomposition temperature of the organic peroxide represents the temperature at which self-accelerating decomposition occurs. The test methods for SADT include the American SADT test, adiabatic storage test, isothermal storage test, heat storage storage test, etc., and can be the values measured by applying any test method. In addition, in the case of using the commercially available products described later as the organic peroxide of the peroxydicarbonate type as component (C), the SADT can be the catalog value. Regarding component (C), from the viewpoint of the pot life at normal temperature, the shape of component (C) at normal temperature (about 20°C to about 25°C) is more preferably a solid (powder) rather than a liquid.

[0039] Regarding the organic peroxide of the peroxydicarbonate type as component (C), examples thereof include bis(sec-butyl) peroxydicarbonate (e.g., Lupersol 225 manufactured by Arkema Kishu Co., Ltd.), dicetyl peroxydicarbonate (e.g., Perkadox 24L manufactured by Nouryon), bis(4-tert-butylcyclohexyl) peroxydicarbonate (e.g., Peroyl TCP manufactured by NOF Corporation), ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry), and distearyl peroxydicarbonate (manufactured by SAGECHEM LIMITED).

[0040] 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 included as an optional component.

[0041] (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, polysulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible pigments, etc., and thioxanthone derivatives are preferred. Specific examples of the thioxanthone derivative include isopropyl thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthone ammonium salt, etc., and 2,4-diethylthioxanthone is preferred.

[0042] (E) Photo radical generator The photo radical generator, together with the organic peroxide of the peroxydicarbonate type as component (C), is a radical source, generates radicals upon 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, and 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.

[0043] (F) Filler The filler is a component for improving the fluidity, injectability, coatability, adhesion, etc. of the curable resin composition. When the curable resin composition contains a filler, whether it is cured into a thin film form such that the thickness becomes 100 μm or less, preferably 50 μm or less, or cured by low-temperature heating at 100 °C or less, preferably 80 °C or less, a thin film-like cured product with good curability and a low Tg 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. The filler is preferably in powder or particle form.

[0044] As inorganic fillers, 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 can be mentioned. The filler can also be added as a thixotropy imparting agent. When the filler is added as a thixotropy imparting agent, fumed silica is preferred. Fumed silica can be surface-treated. As surface treatment agents for inorganic thixotropy imparting agents, monoalkyltrialkoxysilane, dimethyldichlorosilane, polydimethylsiloxane, hexamethyldisilazane, etc. can be mentioned. Commercially available products of surface-treated or untreated fumed silica can be used. From the viewpoint of adhesion to the adherend, the inorganic filler is preferably silica, glass beads, and talc, and from the viewpoint of improving fluidity, injectability, and coatability, silica is more preferred. Silica can 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 sizes can be used in combination, or one type can be used alone.

[0045] As organic fillers, at least one selected from the group consisting of 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) can be mentioned. The organic filler can have a core-shell structure. The polysiloxane resin particles can 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 organic, 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).

[0046] The average particle diameter of the filler is not particularly limited. In order to improve fluidity, injectability, coatability, adhesiveness, 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.

[0047] (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 the inorganic material, and the other is a functional group that chemically bonds to the organic material. The curable resin composition contains a coupling agent, so that the adhesiveness of the curable resin composition can be improved in cases where dissimilar materials are bonded, such as in camera modules, sensor modules, etc.

[0048] 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.

[0049] 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.

[0050] (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.

[0051] (I) Colorant A colorant can be used for the purpose of coloring the curable resin composition. As the colorant, for example, pigments, dyes, coloring matters, etc. can be used. Known colorants such as red, blue (cyan), green, yellow, black, white, etc. can 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. can 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. can be cited.

[0052] In addition to (G) coupling agent, (H) ion scavenger, or (I) colorant, other optional components can include additives, leveling agents, antioxidants, defoaming agents, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents, etc.

[0053] In order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg, relative to the total amount of 100% by mass of component (A), component (B), and component (C), component (A) in the curable resin composition is preferably 90% by mass or more, can be 91% by mass or more, can be 92% by mass or more. Relative to 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, can be 9% by mass or less, can be 8% by mass or less, preferably 1% by mass or more, can be 2% by mass or more, can be 3% by mass or more.

[0054] In order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg, relative to the total amount of 100% by mass 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 further preferably 60% by mass to 90% by mass.

[0055] 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 cyclic 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 the total amount of the component (A1) and the component (A2) may be 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 not having a cyclic skeleton in the molecule (such as an aliphatic epoxy resin, etc.), a polystyrene-based compound, and a vinyl ether compound.

[0056] 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 cure it by low-temperature heating at, for example, 100 °C or lower, preferably 80 °C or lower, to obtain a cured product, 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, wherein the cured product has a low Tg, has a low elastic modulus, and is a cured product in the form of a thin film of, for example, 100 μm or less.

[0057] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains an epoxy resin (component (A1)) having an aromatic ring skeleton and an epoxy equivalent of 200 g / eq or less, in order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg and a low elastic modulus, the ratio 1 of the epoxy equivalent number of component (A1) to the functional group equivalent number in component (A) (functional group equivalent ratio 1 = [epoxy equivalent number of component (A1) having an epoxy equivalent of 200 g / eq or less] / [functional group equivalent number of component (A)]) is preferably 0.001 to 0.8, more preferably 0.01 to 0.6, and still more preferably 0.05 to 0.4. The functional group equivalent number in component (A) refers to the total number of functional group equivalents contained in component (A). For example, when 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.

[0058] When component (A) in the curable resin composition contains an epoxy resin, and the epoxy resin contains an epoxy resin (component (A1)) having an aromatic ring skeleton and an epoxy equivalent greater than 200 g / eq, in order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg and a low elastic modulus, the ratio (functional group equivalent ratio 2 = [epoxy equivalent number of component (A1) having an epoxy equivalent greater than 200 g / eq] / [functional group equivalent number of component (A)]) of the epoxy equivalent number of component (A1) to the functional group equivalent number in component (A) is preferably 0.01 to 1.0, more preferably 0.1 to 0.9, and still more preferably 0.2 to 0.8.

[0059] When component (A) in the curable resin composition contains an epoxy resin, in order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg and a low elastic modulus, 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% by mass to 50% by mass, more preferably 0% by mass to 40% by mass, and still more preferably 1% by mass to 30% by mass.

[0060] When component (A) in the curable resin composition contains an epoxy resin and the epoxy resin contains an alicyclic skeleton-containing epoxy resin of component (A1), in order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg and a low elastic modulus, the ratio of the epoxy equivalent number of the alicyclic skeleton-containing epoxy resin of component (A1) to the functional group equivalent number of component (A) (functional group equivalent ratio 3 = [epoxy equivalent number of the alicyclic skeleton-containing epoxy resin of component (A1)] / [functional group equivalent number of component (A)]) is preferably 0.001 to 0.5, more preferably 0.01 to 0.5, and still more preferably 0.05 to 0.3.

[0061] Component (A) in the curable resin composition contains an epoxy resin. When the total amount of component (A) is set to 100% by mass, the alicyclic skeleton-containing epoxy resin in component (A) can be 0% to 70% by mass, and can be 0% to 60% by mass.

[0062] When component (A) in the curable resin composition contains an epoxy resin and component (A1) contains an aliphatic cyclic epoxy resin, in order to cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to obtain a cured product having a low Tg, the ratio of the epoxy equivalent number of the aliphatic cyclic epoxy resin, that is, the epoxy resin of component (A1), to the functional group equivalent number of component (A) (functional group equivalent ratio 4 = [epoxy equivalent number of the aliphatic cyclic epoxy resin, that is, the epoxy resin of component (A1)] / [functional group equivalent number of component (A)]) is preferably 0.01 to 0.8, more preferably 0.1 to 0.6, and still more preferably 0.1 to 0.4.

[0063] 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 cure it by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, to accelerate the curing rate and efficiently obtain a cured product having a low Tg, 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.

[0064] When the component (A) in the curable resin composition contains an oxetane resin as the component (A2), in order to cure it by low-temperature heating at, for example, 100 °C or lower, preferably 80 °C or lower, to obtain a cured product with a low Tg, 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 5 = [oxetane group equivalent number of the oxetane resin of the component (A2)] / [functional group equivalent number of the component (A)]) is preferably 0.01 to 0.5, more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.3.

[0065] The mixing 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 mixing ratio of the component (A1) and the component (A2) in the component (A) is 100:0 to 60:40, it is possible to cure it by low-temperature heating at, for example, 100 °C or lower, preferably 80 °C or lower, to obtain a cured product with a low Tg.

[0066] In order to cure by low-temperature heating at, for example, 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.

[0067] In order to cure by low-temperature heating at, for example, 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.

[0068] The mixing 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.

[0069] 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% by mass to 3.0% by mass, can be 0.05% by mass to 3.0% by mass, can be 0.05% by mass to 2.0% by mass, and can be 0.1% by mass to 1.0% by mass.

[0070] 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.

[0071] 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 of the curable resin composition (100% by mass). In order to obtain a thin film-shaped cured product of, for example, 100 μm or less, preferably 50 μm or less, and to cure it by low-temperature heating, for example, 100° C. or less, preferably 80° C. or less, thereby obtaining a cured product having a low Tg, 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 of the curable resin composition (100% by mass).

[0072] 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.

[0073] 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, melted by heating and stirred and mixed at the same time, so as to obtain a 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, two or more devices can also be appropriately combined to manufacture a curable resin composition.

[0074] 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 production (for example, within 30 minutes) and after being left at room temperature, for example, at 20°C to 30°C for a specified time. The measured 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 method can be 3 Pa·s to 10 Pa·s.

[0075] 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.

[0076] Supply method of the curable resin composition The curable resin composition can be supplied using an ejector 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.).

[0077] Curing conditions of the curable resin composition The resin composition is thermosetting and can be cured by heating at 100°C or less, preferably 80°C or less, more preferably 75°C or less, further preferably 70°C or less, preferably 45°C or more, more preferably 55°C or more, and further preferably 60°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, and further preferably 30 minutes or more and 60 minutes or less. The curable resin composition can be heated using a hot air dryer or a hot plate.

[0078] 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. For the cured product obtained by curing the curable resin composition at 80°C for 60 minutes, 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 100°C, more preferably 1°C to 90°C, further preferably 2°C to 80°C, still further preferably 3°C to 70°C, and particularly preferably 5°C to 60°C. Even if the Tg of the obtained cured product is 100°C or lower, a film-like cured product that can be cured at a low temperature and has a thickness of 100 μm or less can be obtained. The measurement of the glass transition temperature can refer to the method in the examples described later. For the cured product obtained by curing the curable resin composition at 80°C for 60 minutes, the storage elastic modulus (E') measured using a dynamic viscoelasticity measuring device (such as DMA7100 manufactured by Hitachi High-Technologies Science Co., Ltd.) is preferably 5 GPa or less, can be 4.5 GPa or less, preferably 0.01 GPa or more, and more preferably 0.02 GPa or more. Regarding the cured product, the smaller the value of the storage elastic modulus (E'), the softer it is, and it has followability even when bonding adherends of different materials, and this followability is the followability of the expansion and contraction of the adherend caused by the difference in the linear expansion coefficient of the adherend.

[0079] Semiconductor device, electronic device Regarding the curable resin composition, when the binder or sealing material containing the curable resin composition is used for fixing, bonding, or protecting electronic components, an electronic device containing a cured product can be obtained, and the cured product is obtained by curing the curable resin composition, the binder or the sealing material containing the curable resin composition. The electronic device can be a semiconductor device containing a semiconductor element. Examples of the electronic device can include mobile phones, smartphones, laptop computers, tablet terminals, camera modules, etc. Using the curable resin composition, the binder or the sealing material containing the curable resin composition for fixing, bonding, or protecting electronic components can provide an electronic device that can be cured by low-temperature heating at, for example, 100°C or lower, preferably 80°C or lower, and has a low Tg, a low storage elastic modulus, excellent followability, and high reliability. Examples

[0080] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

[0081] The following shows the respective components used in the respective curable resin compositions of the examples and comparative examples.

[0082] 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 obtained by adding a polyalkylene oxide structure to an epoxy resin and a bisphenol A skeleton, 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, having a molecular weight of 344 and an epoxy equivalent of 172 g / eq. (A1-3): Adeka Glycidol (registered trademark) ED-509S (manufactured by Adeka Corporation), p-tert-butylphenyl glycidyl ether, having a molecular weight of 206 and an epoxy equivalent of 206 / eq. (A1-4): jER YX8000 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A diglycidyl ether, having a molecular weight of 410 and an epoxy equivalent of 205 g / eq. (A1-5): Celoxide (registered trademark) 2021P (manufactured by Daicel Corporation), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, having a molecular weight of 260 and an epoxy equivalent of 130 g / eq.

[0083] Component (A): Cation-curable resin Component (A2): Oxetane resin (A2-1): OXT-221 (manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, having a molecular weight of 214 and an oxetanyl equivalent of 107 g / eq. (A2-2): OXT-101 (manufactured by Toagosei Co., Ltd.), 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), having a molecular weight of 116 and an oxetanyl equivalent of 116 g / eq.

[0084] Component (B): Acid generator containing an iodonium salt (B-1): Bluesil (registered trademark) PI2074 (manufactured by ELKEM SILICONES), 4-isopropyl-4'-methyldiphenyl iodonium tetrakis(pentafluorophenyl)borate (B-2): IK-1FG (manufactured by Sanyapro Corporation)

[0085] Component (C): Organic peroxide of the peroxydicarbonate type (C-1): Perkadox 24L (manufactured by Nouryon), dicetyl peroxydicarbonate, 1-hour half-life temperature of 65°C, molecular weight of 570.9, SADT of 40°C, solid (powder) at room temperature (about 20°C to about 25°C). (C-2): Paroil TCP (manufactured by NOF Corporation), di(4-tert-butylcyclohexyl) peroxydicarbonate, 1-hour half-life temperature of 58°C, molecular weight of 398.5, SADT of 45°C, solid (powder) at room temperature (about 20°C to 25°C). (C-3): Luperox 225 (manufactured by Arkema Yoshitomi Co., Ltd.), di(sec-butyl)peroxydicarbonate, 1-hour half-life temperature of 69°C, molecular weight of 234.2, SADT of 16°C, liquid at room temperature (about 20°C to about 25°C). (C-4): ditridecyl peroxydicarbonate (manufactured by Alfa Chemistry Co., Ltd.) with a molecular weight of 486.72 and a solid (powder) at room temperature (about 20°C to 25°C). (C-5): Distearoyl peroxydicarbonate (manufactured by SAGECHEM LIMITED) with a molecular weight of 626.99 and a solid (powder) at room temperature (about 20°C to 25°C)

[0086] Component (C'): Organic peroxide of alkyl peroxyester type (C'-1): Perokta O (manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-hour half-life temperature of 84°C, molecular weight of 272.4, SADT of 40°C. (C'-2): Luperox 10 (manufactured by Arkema Yoshitomi Co., Ltd.), t-butyl peroxydecanoate, 1-hour half-life temperature: 66°C, molecular weight: 430.6, SADT: 27°C. The one-hour half-life temperature, molecular weight, and SADT value of each organic peroxide are described in the catalog values.

[0087] (D) Photosensitizer (D-1): DETX, 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

[0088] (E) Photoradical Generator (E-1): Omnirad (registered trademark) 184 (manufactured by IGM Resins Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone

[0089] (F) Filler (F-1): SE5200SEE (manufactured by Aduma Technology Co., Ltd.), high-purity synthetic spherical silica. (F-2): Cab-O-Sil (registered trademark) TS720 (manufactured by Cabot Japan Ltd.), hydrophobic silica.

[0090] (G) Coupling agent (G-1): Silane coupling agent, S530 (manufactured by JNC Corporation), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0091] (H) Ion scavenger (H-1): IXEPLAS-A1 (manufactured by Toagosei Co., Ltd.), zirconium-magnesium-based ion scavenger. (H-2): IXEPLAS-A2 (manufactured by Toagosei Co., Ltd.), zirconium-magnesium-based ion scavenger.

[0092] (I) Colorant (I-1): Titanium black 13M (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0093] Examples 1 to 12, Comparative Examples 1 to 6 According to the compounding ratios shown in Tables 1 to 2, each amount of each component was mixed using a three-roll mill to prepare a curable resin composition. In Tables 1 to 2, the numbers representing the compounding ratios of the respective components contained in the curable resin composition represent mass % relative to 100 mass % of the total amount of the curable resin composition, unless otherwise specified. In the tables, the main symbols of the product names or trade names are described for each component.

[0094] In the examples and comparative examples, the properties of the curable resin compositions and cured products were measured in the following manner. The results are shown in Tables 1 to 3. In the tables, the symbol "-" indicates that the corresponding component is not contained in the curable resin composition. In addition, Table 3 shows examples and comparative examples of curable resin compositions without a filler. There are also examples and comparative examples that are repeatedly described in Table 2 or Table 3.

[0095] Production of cured product The curable resin compositions of Examples 1 to 12 and Comparative Examples 1 to 6 were heated at 80 °C for 60 minutes using a hot air dryer to obtain cured products.

[0096] Examples 13 and 14 The resin compositions of Example 13 and Example 14 were each produced in the same manner as in Example 1, except that the component (C-1) used in Example 1 was replaced with component (C-4) and component (C-5), respectively. The properties of the resin compositions of Example 13 and Example 14, and the cured products obtained by curing the resin compositions, were measured in the same manner as in Example 1. Similarly to Example 13 and Example 14, it is also contemplated that they can be cured to the thinnest end of the test piece for the thin film-like cured product test, and partial curing defects can be suppressed.

[0097] Shear strength The resin composition was coated on the lower substrate (a smooth plate of liquid crystal polymer (LCP): 74 mm in length, 20 mm in width, 2 mm in thickness) by screen printing in a size of φ2 mm and a thickness of 125 μm. An alumina sheet with a thickness of 3.2 mm × 1.6 mm × 0.45 mm was laminated on the coated resin composition, and the resin composition was cured under a slightly applied load to produce a test piece. The curing conditions at this time were set at 80 °C for 60 minutes in a blow dryer. The shear strength of the obtained test piece was measured at 23 °C using a universal type adhesion tester (Series 4000: manufactured by Nordson Advanced Technology Co., Ltd.). Specifically, the stress (unit: N) was measured using the universal type adhesion tester at a test speed of 200 μm / s. The shear strength when using liquid crystal polymer (LCP) as the lower substrate and the upper substrate was taken as the LCP shear strength. This measurement was performed on 10 test pieces, and the average value of the obtained stress was calculated. This average value was taken as the shear strength (unit: N) of the cured product. In addition, as the lower substrate and the upper substrate, replacing the liquid crystal polymer (LCP), the shear strength when using polyphthalamide (PPA) as the lower substrate of the same size as the liquid crystal polymer was taken as the PPA shear strength.

[0098] Curing property at 80 °C First, a Teflon (registered trademark) sheet is attached to the surface of a glass plate with a thickness of 3 mm, and spacers (spacers) (with heat-resistant tapes overlapped) are arranged at two positions thereon such that the film thickness during curing becomes 400 ± 150 μm. Then, a curable resin composition is coated between the spacers and clamped with another glass plate having a Teflon (registered trademark) sheet attached to its surface in a manner to avoid entrapment of air bubbles, and cured by heating with a hot air dryer at 80°C for 60 minutes. By clamping with glass, the curability can be judged without considering the influence of oxygen inhibition. The case where the curable resin composition is cured and has no stickiness is regarded as Good (“G”), the case where it is cured but has stickiness is regarded as Poor (“P”), and the case where it is in a liquid state and uncured is regarded as Bad (“B”). The stickiness is confirmed by finger touch.

[0099] Curing length and curing film thickness of test piece for thin film-like cured product Figure 1 The manufacturing method of a test piece for testing a thin film-like cured product of a curable resin composition is shown. As Figure 1 shown, tapes 2 with a thickness of 50 μm are arranged at intervals of 10 mm from the end portion 1a of the substrate 1 to form a step difference in the thickness of the tapes 2. The tapes 2 are adhered to the substrate 1 in a non-movable manner. The substrate 1 is a substrate made of liquid crystal polymer (LCP) with a thickness of 2 mm, a width of 20 mm, and a length of 74 mm. The tapes 2 are made of polyimide. A squeegee is moved from the tapes 2 toward one end portion 1a of the substrate 1 to coat the curable resin composition such that the end face of the curable resin composition becomes a slightly rounded shape (fillet shape) that is slightly triangular, thereby producing a coated material. The produced coated material is heated with a hot air dryer at 80°C for 60 minutes to produce a test piece 3 for testing a thin film-like cured product with a slightly triangular end face. After heating at 80°C for 60 minutes, the produced test piece 3 is visually confirmed, and the cured length of the test piece 3 is measured from the tapes 2 toward one end portion 1a of the substrate 1 as the curing length (mm) of the test piece. The thinner the thickness of the test piece 3, the slower the progress of the polymerization reaction in the curable resin composition and the more difficult it is to cure. For the thin film-like test piece 3, the cured portion and the uncured portion can be visually confirmed. The end face of the test piece 3 for testing a thin film-like cured product is slightly triangular. Therefore, the thickness curing film thickness, which is the thinnest thickness in the cured portion, is measured using the following conversion formula based on the curing length of the test piece 3. The curing length of the test piece 3 is the curing length of the test piece 3 from the side of the tapes 2 with the thickest thickness of the test piece 3 toward the end portion 1a of the substrate 1 with the thinnest thickness of the test piece 3. Curing film thickness (μm) = 5 × (maximum curing length of test piece 10 mm - curing length of test piece (mm)) In Tables 1 to 2, in the above conversion formula, when the cured film thickness is 0 μm, it is regarded as cured to the end and is recorded as A. The value is the cured film thickness (μm) measured in the above conversion formula. For those that are not cured, it is recorded as F.

[0100] Storage elastic modulus (E') and glass transition temperature (Tg) of the cured product The measurement is carried out in accordance with Japanese Industrial Standard JIS C6481. Specifically, first, a Teflon (registered trademark) sheet is attached to the surface of a glass plate with a thickness of 3 mm, and spacers (where heat-resistant tapes are overlapped) are arranged at two places thereon so that the film thickness during curing becomes 400 ± 150 μm. Then, the curable resin composition is coated between the spacers and clamped with another glass plate with a Teflon (registered trademark) sheet attached to its surface so as not to entrap air bubbles, and heated at 80 °C for 60 minutes by a blast dryer to obtain a cured product after curing the curable resin composition. Finally, after peeling this cured product from the glass plate with the Teflon (registered trademark) sheet attached, it is cut into a specified size (10 mm in length and 40 mm in width) with a cutter to obtain a test piece. In addition, the cut surface is smoothed with sandpaper. For this cured product, the initial Tg is measured by the tensile method using a dynamic viscoelasticity measuring device (DMA) (manufactured by Hitachi High-Technologies Science Co., Ltd.) 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. Regarding Tg, the storage elastic modulus (E') and 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 and calculated.

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] As shown in Tables 1 to 3, compared with the cured products of the curable resin compositions of Comparative Example 1 and Comparative Example 2, the cured products of the curable resin compositions of Examples 1 to 11 have high LCP shear strength and PPA shear strength, and excellent adhesiveness to adherends. In addition, regarding Examples 1 to 3 and Examples 5 to 11, the curing length of the test for the film-like cured product is as long as 10 mm, and curing is performed up to the thinnest end of the test piece for the film-like cured product having a substantially triangular end face, and partial curing defects are suppressed. Regarding the cured product of the curable resin composition of Example 4, the curing length is 6 mm and the cured film thickness is 20 μm. This is considered to be because the organic peroxide of the peroxydicarbonate type of component (C-3) is a liquid at normal temperature and remains as a low molecule in the resin composition after decomposition by reaction, resulting in poor curability of the resin composition. On the other hand, it is considered that the organic peroxides of the peroxydicarbonate type of component (C-1) or component (C-2) are solids at normal temperature, and therefore remain as solids even after decomposition during the reaction and do not hinder the film curability of the resin composition after decomposition. As a result, curing proceeds up to the end of the cured film thickness where curing is difficult. In addition, regarding the cured products of the curable resin compositions of Examples 1 to 9 and Example 11, the Tg is as low as 0°C to 100°C, and a cured product having a low Tg can be obtained by curing with low-temperature heating at 80°C or lower. Regarding the cured product of the curable resin composition of Example 10, although the Tg is slightly higher at 117°C, a cured product having a Tg of 120°C or lower is obtained. Regarding the cured products of the curable resin compositions of Examples 1 to 11, they have a low storage elastic modulus (E') of 0.02 GPa to 5.0 GPa, and a cured product having followability to the expansion and contraction of the adherend can be obtained.

[0105] As shown in Table 3, the coatability and adhesion of the curable resin composition of Example 12 without the (F) filler and the curable resin composition of Comparative Example 3 were reduced, and a coating with a triangular end face could not be formed, and the cured film thickness could not be measured. Therefore, as another test for evaluating the curability of the thin film, a coating was formed in the form of a strip (rectangular strip) with a film thickness of 50 μm and a width of 5 mm to produce a cured product. The curability was judged by touching the cured product formed in the form of a strip. Table 2 shows the results of the thin film curability test. When touching the cured product formed in the form of a strip, if it is cured, it is regarded as Good ("G"), and if it is not cured and is in a liquid state, it is regarded as Bad ("B"). The cured product of the curable resin composition of Example 12 could obtain the curability of a cured product of a thin film with a film thickness of 50 μm even without the (F) filler. Regarding the cured products of the curable resin compositions of Example 11 and Example 12, their Tg was as low as 0°C to 100°C, and they could be cured by low-temperature heating below 80°C to obtain a cured product with a low Tg. Regarding the cured products of the curable resin compositions of Example 11 and Example 12, they had a low storage elastic modulus (E') of 0.1 GPa to 1.0 GPa, and a cured product with followability to the expansion and contraction of the adherend could be obtained.

[0106] As shown in Tables 2 and 3, regarding the cured products of the curable resin compositions of Comparative Examples 1 to 6, the LCP shear strength and PPA shear strength of the cured products of Comparative Examples 1 and 2 were low. It was speculated that they were affected by oxygen inhibition and could not be fully cured, and no strength was exhibited. Among Comparative Examples 1 to 6, an organic peroxide other than the peroxydicarbonate type was contained as the organic peroxide. In addition, regarding the cured products of Comparative Examples 1, 2, 4, and 5, the cured length of the test for the thin film curability test was 0 mm, and they were not cured in the thin film state. The storage elastic modulus (E') of the cured product of Comparative Example 2 was greater than 5.0 GPa, and it was speculated that the followability to the expansion and contraction of the adherend was reduced. In addition, the cured product of Comparative Example 6 without the (F) filler was not cured even when formed into a strip. Industrial Applicability

[0107] 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 according to the embodiment of the present invention can be used for, for example, mobile phones, smartphones, laptop computers, tablet terminals, camera modules, sensor modules, and the like. Symbol Explanation

[0108] 1: Substrate, 2: Tape, 3: Test piece.

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.

2. The curable resin composition according to claim 1, wherein the component (A) includes at least one selected from the group consisting of (A1) An epoxy resin having a ring skeleton in the molecule, and (A2) An oxetane resin in the group.

3. The curable resin composition according to claim 2, wherein the component (A1) has an aromatic ring skeleton.

4. The curable resin composition according to any one of claims 1 to 3, wherein the 1-hour half-life temperature of the component (C) is 50°C to 80°C.

5. The curable resin composition according to any one of claims 1 to 4, wherein the iodonium salt contained in the component (B) is an iodonium salt compound represented by the following formula (1), [Chemical formula 1] Ar 1 -I + -Ar 2 ·Z - (1) In the formula (1), Ar 1 and Ar 2 are each independently a substituted or unsubstituted aryl group, and Z - is an anion.

6. The curable resin composition according to claim 5, wherein Z in the formula (1) - 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] - ; wherein, 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 from 0 to 5; when a is an integer of 2 or more, multiple R 3 present may be the same or different from each other.​ 7. The curable resin composition according to claim 2 or 3, wherein the component (A1) includes an epoxy resin having an epoxy equivalent of 100 g / eq to 1000 g / eq.

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 100°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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