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

Abstract

To provide a resin composition which can at least perform photocuring or curing at low temperature (e.g., 100°C or lower) and which can produce a cured product excellent in high-temperature high-humidity reliability, and further provide an adhesive or sealing material containing the resin composition, a cured product of the resin composition, a semiconductor device and an electronic component containing the cured product. A resin composition comprising: (A) an alicyclic epoxy compound; (B) an oxetane compound; (C) a filler; and (D) an acid generator which is a salt of an anion represented by the following formula (1) and a counter cation other than an iodonium cation, (in the formula, R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms.). An adhesive or sealing material containing the resin composition, a cured product of the resin composition, a semiconductor device and an electronic component containing the cured product are also provided.

Description

Technical Field

[0001] This invention relates to resin compositions, adhesives or sealants comprising the resin compositions, cured products thereof, semiconductor devices comprising the cured products, and electronic components. Background Technology

[0002] Currently, in the assembly and installation of semiconductor devices and electronic components, such as semiconductor chips, adhesives and sealants containing curable resin compositions, especially epoxy resin compositions, are frequently used to maintain reliability. As IoT (Internet of Things) applications, including smartphones, various devices are being developed. During this process, issues such as the inability to manufacture at high temperatures due to component problems have become a challenge.

[0003] The development of adhesives capable of photocuring and / or low-temperature curing is underway. For example, Patent Document 1 discloses a composition that meets the following requirements as a UV / thermal curing adhesive composition: it does not use antimony compounds as thermal cationic polymerization initiators, thus having low toxicity; it can be cured at low temperatures below 120°C; and the cured product has excellent heat resistance. The composition contains, in specific proportions, an oxetane compound, an alicyclic epoxy compound, an aromatic glycidyl ether epoxy compound, a photocationic polymerization initiator, and a thermal cationic polymerization initiator containing a tetra(pentafluorophenyl)borate compound.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-147584 Summary of the Invention

[0007] Semiconductor devices and electronic components are exposed to high-temperature and high-humidity environments under certain operating conditions. Therefore, the cured adhesives used in the manufacture of semiconductor devices and electronic components require excellent reliability under high-temperature and high-humidity conditions. In particular, since the glass transition temperature (Tg) of the adhesives used in semiconductor devices and electronic components is the temperature at which physical properties affecting the reliability of semiconductor devices and electronic components, such as the coefficient of linear expansion, elastic modulus, and bond strength, change is required, even after prolonged exposure to high-temperature and high-humidity environments, to have a small change in Tg relative to the initial Tg of the cured adhesive.

[0008] It was found that the cured adhesive composition disclosed in Patent Document 1 exhibited a significant change in Tg before and after the pressure cooker test (PCT) for evaluating high temperature and high humidity resistance.

[0009] The present invention aims to provide a resin composition that is at least capable of photocuring or low-temperature (e.g., below 100°C) curing, and produces a cured product with excellent high-temperature and high-humidity reliability. It also provides an adhesive or sealant containing the resin composition, the cured product thereof, a semiconductor device and electronic component containing the cured product.

[0010] The specific methods used to solve the above problems are as follows.

[0011] The present invention includes curable resin compositions, adhesives or sealants, cured products, and semiconductor devices or electronic components.

[0012] [1] A resin composition comprising:

[0013] (A) Alicyclic epoxy compounds;

[0014] (B) Oxycyclic butane compounds;

[0015] (C) Packing material; and

[0016] (D) An acid-producing agent, which is a salt formed by an anion represented by the following formula (1) and a counter cation other than iodonium cation.

[0017] [Chemistry 1]

[0018]

[0019] (In the formula, R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms.)

[0020] [2] According to the resin composition described in [1] above, wherein the acid-producing agent (D) is a (D1) thermal acid-producing agent.

[0021] [3] According to the resin composition described in [1] above, wherein the acid-producing agent (D) is a photoacid-producing agent (D2).

[0022] [4] According to the resin composition described in [1] above, wherein the acid-producing agent (D) is a combination of (D1) thermal acid-producing agent and (D2) photo-acid-producing agent.

[0023] [5] The resin composition according to any one of [1] to [4] above, wherein the counter cation in the acid-producing agent (D) above is a sulfonium cation or an ammonium cation.

[0024] [6] The resin composition according to any one of [1] to [5] above, wherein the content of the acid-producing agent (D) above is 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the resin composition.

[0025] [7] The resin composition according to any one of [1] to [6] above further comprises an acid-producing agent other than component (D) (E).

[0026] [8] According to the resin composition described in [7] above, the acid-producing agent other than component (D) of (E) above contains sulfonium cation or ammonium cation.

[0027] [9] The resin composition according to any one of [1] to [8] above further comprises (F) an epoxy compound other than an alicyclic epoxy compound.

[0028]

[10] According to the resin composition described in [9] above, the epoxy compound other than the above (F) alicyclic epoxy compound contains an epoxy compound with an epoxy equivalent of 90 to 1000 g / eq.

[0029]

[11] According to the resin composition described in [9] or

[10] above, the content of the epoxy compound other than the alicyclic epoxy compound described above (F) is 50 to 200 parts by weight relative to 100 parts by weight of the alicyclic epoxy compound (A).

[0030]

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

[11] above, wherein the content of all epoxy compounds contained in the resin composition is 100 to 1300 parts by weight relative to 100 parts by weight of the (B) oxetane compound.

[0031]

[13] The resin composition described in any one of [1] to

[12] above is configured such that the above components (A) to (D) are packaged into a single container.

[0032]

[14] The resin composition described in any one of [1] to

[12] above is configured such that the above components (A) to (D) are packaged in two or more containers.

[0033]

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

[14] above.

[0034]

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

[14] above, or the adhesive or sealant described in

[15] above.

[0035]

[17] A semiconductor device or electronic component comprising the cured material described in

[16] above.

[0036] According to the present invention, a resin composition is provided that is at least capable of photocuring or low-temperature (e.g., below 100°C) curing, and produces a cured product with excellent high-temperature and high-humidity reliability. In addition, an adhesive or sealant comprising the resin composition, a cured product thereof, a semiconductor device comprising the cured product, and an electronic component are also provided. Detailed Implementation

[0037] In accordance with convention in the field of synthetic resins, the term "resin," which generally refers to a polymer (especially a synthetic polymer), is sometimes used for components constituting a curable resin composition before curing, even if the components are not polymers, such as prepolymer compounds before curing.

[0038] [Resin Composition]

[0039] As one aspect of the present invention, the resin composition comprises:

[0040] (A) Alicyclic epoxy compounds;

[0041] (B) Oxycyclic butane compounds;

[0042] (C) Packing material; and

[0043] (D) An acid-producing agent, which is a salt formed by an anion represented by the following formula (1) and a counter cation other than iodonium cation.

[0044] [Chemistry 2]

[0045]

[0046] (In the formula, R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms.)

[0047] According to this method, a resin composition can be provided that is at least capable of photocuring or low-temperature curing (e.g., below 100°C), and produces a cured product with excellent high-temperature and high-humidity reliability.

[0048] (A) Alicyclic epoxides

[0049] The resin composition of this method comprises (A) an alicyclic epoxy compound (hereinafter also referred to as "component (A)"). One type of alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in the molecule, i.e., a cycloolefin epoxide structure. Regarding the cycloolefin epoxide structure, as with the cyclohexene epoxide structure and cyclopentene epoxide structure obtained by epoxidizing a compound containing a cyclohexene ring or a compound containing a cyclopentene ring with an oxidizing agent, it is a structure in which the aliphatic ring and the epoxy ring share part of the ring structure. From the viewpoint of ensuring heat resistance, the alicyclic epoxy compound is more preferably having 2 to 6 alicyclic epoxy groups, and more preferably having 2 alicyclic epoxy groups. There is no particular limitation on the number of carbon atoms in the aliphatic ring. The aliphatic ring in the cycloolefin epoxide structure is preferably, for example, a 5-membered to 8-membered ring, more preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring.

[0050] In this specification, alicyclic epoxides may also have epoxy groups other than alicyclic epoxy groups. Furthermore, even compounds with aromatic rings are considered alicyclic epoxides as long as they have alicyclic epoxy groups.

[0051] Examples of the aforementioned alicyclic epoxides include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (CELLOXIDE 2021P manufactured by Daicel Co., Ltd., etc.), 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, and 3,4-cyclohexanecarboxylate. Oxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl) adipic acid, 3,4-epoxy-6-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexane) Cyclohexyl propane, dicyclopentadiene diester, ethylene bis(3,4-epoxycyclohexane carboxylate), limonene diester (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl (CELLOXIDE 8010 manufactured by Daicel Co., Ltd., etc., a registered trademark), dioctyl hexahydrophthalate, di(2-ethylhexyl) hexahydrophthalate, 1-epoxy Ethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl) ether, etc., but not limited to them.

[0052] In this specification, alicyclic epoxy compounds may include, in addition to compounds having a cyclic olefin epoxide structure as described above, compounds containing epoxy groups other than alicyclic epoxy groups and aliphatic rings, and compounds having epoxy groups in which two carbon atoms in the aliphatic chain are bonded to oxygen atoms. Examples of such alicyclic epoxy compounds include 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (such as EHPE3150 manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (such as EPOLEAD PB manufactured by Daicel Co., Ltd.), and compounds in which part or all of the double bonds of styrene-butadiene copolymers are epoxidized (such as EPOFRIEND manufactured by Daicel Co., Ltd.), but are not limited to these.

[0053] The epoxy equivalent of the alicyclic epoxy compound is preferably 90-1000 g / eq, more preferably 100-800 g / eq, even more preferably 100-500 g / eq, and particularly preferably 110-300 g / eq.

[0054] Alicyclic epoxy compounds can be used in combination with any one type or two or more types.

[0055] In this embodiment, the content of (A) alicyclic epoxy compound in the resin composition is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, further preferably 10 to 50% by weight, and particularly preferably 10 to 40% by weight, relative to the total weight of the resin composition. Furthermore, the content of (A) alicyclic epoxy compound in the resin composition is preferably 10 to 1000 parts by weight, more preferably 30 to 800 parts by weight, and further preferably 40 to 600 parts by weight, relative to 100 parts by weight of (B) oxetane compound (described later).

[0056] (B) Oxycyclic butane compounds

[0057] The resin composition of this embodiment includes (B) an oxetane compound (hereinafter also referred to as "component (B)"). The oxetane compound is a compound having at least one oxetane ring (e.g., 3-oxetane) within its molecule. Although the polymerization initiation reaction of oxetane compounds is slower than that of alicyclic epoxy compounds, high-speed polymerization occurs when the initiator concentration reaches a certain level or higher, thus contributing to the short-term curing reaction of the resin composition at low temperatures. Furthermore, by including the oxetane compound in the resin composition, the change in the Tg of the cured product is reduced even after prolonged exposure to high temperature and humidity. In one embodiment, the oxetane compound preferably has 1 to 6 oxetane rings within its molecule, more preferably 1 to 2 oxetane rings within its molecule.

[0058] Examples of oxetane compounds include bis[1-ethyl(3-oxetane)] methyl ether (also known as (3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane)), phenylenediethylene dioxetane, 4,4'-bis[3-ethyl-(3-oxetane)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetane)methoxy)methylbenzene, (bis[(3- (Ethyl-3-oxetane)methyl isophthalate), 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexoxy)methyl]oxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, etc., but not limited to them. Other examples of oxetane compounds include oxetane alkyl sesquioxane (such as OXT-191 manufactured by Toa Synthetic Co., Ltd.), 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane (such as OXT-221 manufactured by Toa Synthetic Co., Ltd.), and phenolic linear phenolic oxetane (such as PHOX manufactured by Toa Synthetic Co., Ltd.). Any one type of oxetane compound can be used, or two or more can be used in combination.

[0059] The oxetane equivalent of the oxetane compound is preferably 90–500 g / eq, but can also be 100–300 g / eq.

[0060] The content of (B)oxetane compound in the resin composition is preferably 1 to 50% by weight relative to the total weight of the resin composition, more preferably 2 to 40% by weight, and even more preferably 3 to 30% by weight.

[0061] Regarding the content of (B) oxetane compounds in the resin composition, from the viewpoint of low-temperature curing properties, it is preferably 1 to 100 parts by weight, and more preferably 5 to 85 parts by weight, relative to 100 parts by weight of the total content of all epoxy compounds contained in the resin composition. "All epoxy compounds" refers to the total of epoxy compounds other than (A) alicyclic epoxy compounds and (F) alicyclic epoxy compounds described later.

[0062] (C) Packing

[0063] The resin composition of this method includes (C) filler (hereinafter also referred to as "component (C)"). By including filler in the resin composition, the flowability, injection properties, coatability, and adhesion of the resin composition can be improved. In particular, when the resin composition is cured by heating at a low temperature below 100°C, a cured product with good adhesion to the substrate can be obtained. Fillers are broadly classified into inorganic fillers and organic fillers.

[0064] Inorganic fillers include granular bodies formed from inorganic materials. There are no particular limitations on any inorganic filler that reduces the coefficient of linear expansion through addition. Suitable inorganic materials include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium dioxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one type of inorganic filler can be used, or two or more can be used in combination. Silica filler is preferred as it increases the filler volume. Amorphous silica is preferred. The surface of the inorganic filler may also be treated with coupling agents such as silane coupling agents.

[0065] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane backbone, fillers with a butadiene backbone, and styrene fillers. Organic fillers can also be surface-treated.

[0066] The shape of the filler is not particularly limited; it can be spherical, scaly, needle-like, or irregular.

[0067] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the term "average particle size" refers to the median diameter (d50) of the volume reference determined by laser diffraction according to ISO-13320 (2009). By setting the average particle size of the filler to the upper limit or below, filler sedimentation can be suppressed, and the formation of coarse particles can be suppressed, thereby suppressing wear of the nozzle of the jet dispensing machine and the dispersion of the resin composition ejected from the nozzle of the jet dispensing machine outside the desired area. The lower limit of the average particle size of the filler is not particularly limited; however, from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, more preferably 0.01 μm or more. In one embodiment of this method, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes can also be used in combination. For example, fillers with an average particle size of 0.005 μm or more but less than 0.1 μm and fillers with an average particle size of 0.1 μm to 6.0 μm can be used in combination.

[0068] Any one type of filler can be used, or two or more types can be used in combination.

[0069] The filler content in the resin composition of this method is preferably 15 to 50% by weight relative to the total weight of the resin composition, more preferably 20 to 45% by weight, and even more preferably 30 to 45% by weight.

[0070] (D) Acid-producing agent

[0071] The resin composition of this method contains an acid-generating agent (hereinafter also referred to as "(D) acid-generating agent", "(D) gallate-based acid-generating agent" or "component (D)"), which is a salt formed by an anion represented by the following formula (1) and a counter cation other than iodonium cation.

[0072] [Chemistry 3]

[0073]

[0074] (In the formula, R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, wherein at least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms.)

[0075] An acid-generating agent generates acid as an active species under the action of light or heat, causing the cationic polymerizable compound to polymerize. By including an acid-generating agent as a salt of an anion represented by formula (1) (hereinafter also referred to as "gallate anion") and a counter cation other than iodonium cation, a resin composition capable of at least photocuring or low-temperature (e.g., below 100°C) curing and producing a cured product with excellent high-temperature and high-humidity reliability can be provided.

[0076] By including the aforementioned acid-generating agent with a specific structure in the resin composition, at least photocuring or low-temperature (e.g., below 100°C) curing is possible. Furthermore, the inventors have discovered that by including this acid-generating agent with a specific structure in the resin composition, even after the cured product has been placed in a high-temperature and high-humidity environment for an extended period, specifically before and after a pressure cooker test (PCT) at 2 atm, 121°C, 100% RH for 20 hours, the change in the Tg of the cured product is relatively small. While not limited to the following, the reasoning is as follows: The cationic portion of the acid-generating agent decomposes due to the reaction, while the anionic portion remains in the cured product of the composition. When the cured product is placed in a high-temperature and high-humidity environment for an extended period, acid is generated due to the intrusion of moisture into the cured product. The generated acid moves in the water, which is a polar solvent, and may thereby interrupt the crosslinking in the cured product. The gallate anion in the acid-generating agent of this method is considered to be unable to move in the cured product due to its large ionic radius and molecular weight, and is therefore unlikely to undergo a reaction that interrupts crosslinking. In addition, the counter cation in the acid-generating agent of this method is an ion other than iodonium cation. Therefore, when the cured composition is placed in a high temperature and high humidity environment for a long time, iodic acid caused by iodonium cation will not be generated, and thus the cross-linking cleavage reaction caused by iodic acid will not occur.

[0077] In one embodiment, the above-mentioned (D) acid-producing agent is (D1) thermal acid-producing agent.

[0078] In one embodiment, the above-mentioned (D) acid-producing agent is (D2) photo-acid-producing agent.

[0079] In one embodiment, the above-mentioned (D) acid-producing agent is a combination of (D1) thermal acid-producing agent and (D2) photo-acid-producing agent.

[0080] In formula (1), R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, however, at least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms. That is, R1, R2, R3 and R4 in formula (1) are any combination of the following.

[0081] (i) A combination in which one of R1, R2, R3 and R4 is aryl and the remaining three are alkyl.

[0082] (ii) A combination in which two of R1, R2, R3 and R4 are aryl and the remaining two are alkyl.

[0083] (iii) A combination in which three of R1, R2, R3 and R4 are aryl and the remaining one is alkyl.

[0084] (iv) R1, R2, R3 and R4 are all combinations of aryl groups.

[0085] Of the above combinations, anions of (iii) or (iv) are preferred, and anion of (iv) is more preferred.

[0086] The alkyl groups represented by R1, R2, R3 and R4 in formula (1) having 1 to 18 carbon atoms can be any of straight-chain, branched or cyclic alkyl groups. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, sec-pentyl, n-hexyl, isohexyl, n-heptyl, sec-heptyl, n-octyl, n-nonyl, sec-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclopentyl and cyclohexyl, etc.

[0087] Alkyl groups with 1 to 18 carbon atoms represented by R1, R2, R3, and R4 in formula (1) may also have substituents. As used herein, "alkyl group with substituents" means an alkyl group in which the hydrogen atoms of the alkyl group are replaced by substituents, and the position and number of substituents are not particularly limited. It should be noted that when the substituents have carbon atoms, the number of carbon atoms in the alkyl groups represented by R1, R2, R3, and R4 does not include the number of carbon atoms in the substituents. Specifically, for example, in the case of an ethyl group with a phenyl substituent, it is an alkyl group with 2 carbon atoms.

[0088] The substituents that the alkyl groups representing carbons 1 to 18 represented by R1, R2, R3 and R4 in formula (1) may have are not particularly limited (but do not include alkyl groups). Examples of such substituents include alkoxy groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, mercapto groups, nitro groups, alkyl-substituted amino groups, aryl-substituted amino groups, unsubstituted amino groups (NH2 groups), cyano groups, isocyano groups, etc.

[0089] The alkoxy group that can be a substituent among the alkyl groups having 1 to 18 carbon atoms represented by R1, R2, R3 and R4 in formula (1) refers to a substituent formed by the bonding of an oxygen atom to an alkyl group. For example, alkyl groups that are the same as the alkyl groups described in the alkyl group having 1 to 18 carbon atoms represented by R1, R2, R3 and R4 in formula (1) can be cited as examples of alkyl groups.

[0090] The aromatic groups represented by R1, R2, R3, and R4 in formula (1), which are alkyl groups with 1 to 18 carbon atoms, can be used as substituents. There is no particular limitation as long as they are residues obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound. Examples of such aromatic groups include phenyl, biphenyl, terphenyl, tetraphenyl, tolyl, indene, naphthyl, anthracene, fluorenyl, pyrene, phenanthryl, and mesitylene.

[0091] The heterocyclic groups represented by R1, R2, R3 and R4 in formula (1) that can be substituents are not particularly limited as long as they are residues obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound. Examples of such heterocyclic groups include furanyl, thienyl, thienothienyl, pyrroleyl, imidazolyl, N-methylimidazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl, pyrimidinyl, quinolinyl, indolyl, benzopyrazinyl, benzopyrimidinyl, benzothienyl, naphthothienyl, benzofuranyl, benzothiazolyl, pyridothiazolyl, benzoimidazolyl, pyridoimidazolyl, N-methylbenzimidazolyl, pyrido-N-methylimidazolyl, benzoxazolyl, pyridooxazolyl, benzothiadiazoleyl, pyridothiadiazoleyl, benzoxiadiazoleyl, carbazoleyl, phenoxazinyl, and phenthiazolyl.

[0092] Halogen atoms that can be used as substituents in alkyl groups having 1 to 18 carbon atoms, represented by R1, R2, R3 and R4 in formula (1), include fluorine, chlorine, bromine and iodine atoms.

[0093] The alkyl-substituted amino groups that can be substituents among the alkyl groups having 1 to 18 carbon atoms represented by R1, R2, R3, and R4 in formula (1) can be either monoalkyl-substituted amino groups or dialkyl-substituted amino groups. For example, alkyl groups that are the same as the alkyl groups described in the alkyl group having 1 to 18 carbon atoms represented by R1, R2, R3, and R4 in formula (1) can be cited as alkyl groups.

[0094] The aryl substituted amino groups that can be substituents in the alkyl groups having 1 to 18 carbons represented by R1, R2, R3, and R4 in formula (1) can be either monoaryl substituted amino groups or diaryl substituted amino groups. As aryl groups in these aryl substituted amino groups, examples can be aryl groups that are the same as the aromatic groups that can be substituents in the alkyl groups having 1 to 18 carbons represented by R1, R2, R3, and R4 in formula (1).

[0095] As specific examples of aryl groups with 6 to 14 carbons represented by R1, R2, R3 and R4 in formula (1), aryl groups that are the same as the aromatic groups that can be substituted by substituents of alkyl groups with 1 to 18 carbons represented by R1, R2, R3 and R4 in formula (1).

[0096] The aryl groups represented by R1, R2, R3, and R4 in formula (1), having 6 to 14 carbon atoms, can also have substituents. The term "aryl group with substituents" here refers to an aryl group in which the hydrogen atoms of the aryl group in its structure are replaced by substituents; the position and number of substituents are not particularly limited. It should be noted that when the substituents have carbon atoms, the number of carbon atoms in the aryl groups represented by R1, R2, R3, and R4 does not include the number of carbon atoms in the substituents. Specifically, for example, in the case of a phenyl group having an ethyl group as a substituent, it is an aryl group with 6 carbon atoms.

[0097] The aryl groups represented by R1, R2, R3, and R4 in formula (1) having carbon numbers of 6 to 14 may have no particular limitation on the substituents. Examples of such substituents include alkyl, alkoxy, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl, mercapto, nitro, alkyl-substituted amino, aryl-substituted amino, unsubstituted amino (NH2 group), cyano, isocyano, etc.

[0098] Alkyl groups that can be substituents among the aryl groups having 6 to 14 carbons represented by R1, R2, R3 and R4 in formula (1), for example, can be alkyl groups that are the same as the alkyl groups described in the alkyl group having 1 to 18 carbons represented by R1, R2, R3 and R4 in formula (1).

[0099] As specific examples of substituents that can be alkoxy groups, aromatic groups, heterocyclic groups, halogen atoms, alkyl-substituted amino groups, and aryl-substituted amino groups in the aryl groups having carbon numbers of 6 to 14 represented by R1, R2, R3, and R4 in formula (1), the same groups as those that can be substituents in the alkyl groups having carbon numbers of 1 to 18 represented by R1, R2, R3, and R4 in formula (1) can be given.

[0100] R1, R2, R3 and R4 in formula (1) are preferably phenyl groups having perfluoroalkyl groups as substituents or phenyl groups having fluorine atoms as substituents, and more preferably pentafluorophenyl or bis(trifluoromethyl)phenyl.

[0101] As specific examples of the gallate anion in formula (1), the following examples can be given, but are not limited to them.

[0102] [Chemistry 4]

[0103]

[0104] The counter cation that forms a salt with the gallate anion represented by (1) is not particularly limited to any monovalent cation other than the iodonium cation, and examples include sulfonium cation, ammonium cation, and phosphonium cation. In one embodiment, the counter cation is preferably a sulfonium cation or an ammonium cation, and more preferably a sulfonium cation.

[0105] When the acid-producing agent (D) is a thermal acid-producing agent (D1), from the viewpoint of efficiently producing acid by heat, a matte cation represented by the following formula (2) is preferred, in relation to the counter cation other than the iodonium cation that forms a salt with the gallium anion represented by formula (1):

[0106] [Chemistry 5]

[0107]

[0108] (In the formula,

[0109] R5 and R6 are alkyl or aralkyl groups.

[0110] R7 represents hydrogen, alkyl, hydroxyl, carboxyl, alkoxy, aryloxy, alkyl carbonyl, aryl carbonyl, aralkyl carbonyl, alkoxy carbonyl, aryloxy carbonyl, arylalkoxy carbonyl, alkyl carbonyloxy, aryl carbonyloxy, arylalkyl carbonyloxy, alkoxy carbonyloxy, aryloxy carbonyloxy, arylalkoxy carbonyloxy, aryl thiocarbonyl, acyloxy, aryl thio, alkyl thio, aryl, heterocyclic hydrocarbon, alkyl sulfinyl, aryl sulfinyl, alkyl sulfonyl, aryl sulfonyl, hydroxyl (poly)alkoxy, substituted silyl and amino, cyano, nitro or halogen atom.

[0111] n represents the number of R7s, where n is an integer from 0 to 5.

[0112] When n is 2 to 5, each of the R7 atoms can be the same or different from the others. Two or more R7 atoms can form a ring structure containing the element S, either directly or separated by -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene, or phenylene.

[0113] In formula (2), the alkyl groups represented by R5, R6 and R7 can be the same as the alkyl groups described in the alkyl group with 1 to 18 carbon atoms represented by R1, R2, R3 and R4 in formula (1).

[0114] In formula (2), the aralkyl groups represented by R5 and R6 can be lower alkyl groups substituted with aryl groups having 6 to 10 carbon atoms. Specific examples of aralkyl groups include benzyl, 2-methylbenzyl, 1-naphthylmethyl, 2-naphthylmethyl, etc.

[0115] In formula (2), the alkoxy group represented by R7 can be a straight-chain alkoxy group with 1 to 18 carbon atoms or a branched-chain alkoxy group with 3 to 18 carbon atoms. Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexoxy, decoxy, dodecyloxy, and octadecyloxy.

[0116] In formula (2), aryloxy groups represented by R7 can be aryloxy groups with 6 to 10 carbon atoms, and specific examples include phenoxy and naphthoxy groups.

[0117] In formula (2), the alkyl carbonyl group represented by R7 can be a straight-chain alkyl carbonyl group with 2 to 18 carbon atoms or a branched alkyl carbonyl group with 4 to 18 carbon atoms. Specific examples of alkyl carbonyl groups include acetyl, propionyl, butyryl, 2-methylpropionyl, heptanoyl, 2-methylbutyryl, 3-methylbutyryl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl.

[0118] In formula (2), the aryl carbonyl group represented by R7 can be an aryl carbonyl group with 7 to 11 carbon atoms. Specific examples include benzoyl and naphthyl.

[0119] In formula (2), the aryl carbonyl group represented by R7 can be a lower alkyl carbonyl group substituted with an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl carbonyl, 2-methylbenzyl carbonyl, 1-naphthylmethyl carbonyl, 2-naphthylmethyl carbonyl, etc.

[0120] In formula (2), the alkoxycarbonyl group represented by R7 can be a straight-chain alkoxycarbonyl group with 2 to 19 carbon atoms or a branched-chain alkoxycarbonyl group with 4 to 19 carbon atoms. Specific examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octoxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl.

[0121] In formula (2), the aryloxy carbonyl group represented by R7 can be aryloxy carbonyl groups with 7 to 11 carbon atoms. Specific examples include phenoxy carbonyl and naphthoxy carbonyl.

[0122] In formula (2), the arylalkoxycarbonyl group represented by R7 can be a lower alkoxycarbonyl group substituted with an aryl group having 6 to 10 carbon atoms. Specific examples include benzyloxycarbonyl, 2-methylbenzyloxycarbonyl, 1-naphthylmethoxycarbonyl, and 2-naphthylmethoxycarbonyl.

[0123] In formula (2), the alkyl carbonyloxy group represented by R7 can be a straight-chain or branched alkyl carbonyloxy group having 2 to 19 carbon atoms. Specific examples include acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, octyl carbonyloxy, tetradecyl carbonyloxy, and octadecyl carbonyloxy.

[0124] In formula (2), aryl carbonyloxy groups represented by R7 can be aryl carbonyloxy groups with 7 to 11 carbon atoms. Specific examples include benzoyloxy and naphthyloxy.

[0125] In formula (2), the aralkyl carbonyl group represented by R7 can be a lower alkyl carbonyl group substituted with an aryl group having 6 to 10 carbon atoms. Specific examples include benzyl carbonyl group, 2-methylbenzyl carbonyl group, 1-naphthylmethyl carbonyl group, 2-naphthylmethyl carbonyl group, etc.

[0126] In formula (2), the alkoxycarbonyl group represented by R7 can be a straight-chain or branched alkoxycarbonyl group having 2 to 19 carbon atoms. Specific examples include methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy, isopropoxycarbonyloxy, butoxycarbonyloxy, isobutoxycarbonyloxy, sec-butoxycarbonyloxy, tert-butoxycarbonyloxy, octyloxycarbonyloxy, tetradecyloxycarbonyloxy, and octadecyloxycarbonyloxy.

[0127] In formula (2), aryloxycarbonyloxy, represented by R7, can be aryloxycarbonyloxy with 7 to 11 carbon atoms. Specific examples include phenoxycarbonyloxy and naphthoxycarbonyloxy.

[0128] In formula (2), the arylalkoxycarbonyloxy group represented by R7 can be a lower alkoxycarbonyloxy group substituted with an aryl group having 6 to 10 carbon atoms. Specific examples include benzyloxycarbonyloxy, 2-methylbenzyloxycarbonyloxy, 1-naphthylmethoxycarbonyloxy, and 2-naphthylmethoxycarbonyloxy.

[0129] In formula (2), aryl thiocarbonyl groups represented by R7 can be aryl thiocarbonyl groups with 7 to 11 carbon atoms. Specific examples include phenyl thiocarbonyl and naphthoxy thiocarbonyl.

[0130] In formula (2), the acyloxy group represented by R7 can be a straight-chain acyloxy group with 2 to 19 carbon atoms or a branched-chain acyloxy group with 4 to 19 carbon atoms. Specific examples of acyloxy groups include acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, octyl carbonyloxy, tetradecyl carbonyloxy, and octadecyl carbonyloxy.

[0131] In formula (2), arylthio groups represented by R7 can be arylthio groups with 6 to 20 carbon atoms. Specific examples of arylthio groups include phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthio, 2-naphthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[ [4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio, etc.

[0132] In formula (2), the alkylthio group represented by R7 can be a straight-chain alkylthio group with 1 to 18 carbon atoms or a branched alkylthio group with 3 to 18 carbon atoms. Specific examples of alkylthio groups include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isoctadecylthio.

[0133] In formula (2), aryl groups represented by R7 can be aryl groups with 6 to 10 carbon atoms, and specific examples include phenyl, tolyl, dimethylphenyl and naphthyl.

[0134] In formula (2), the heterocyclic hydrocarbon group represented by R7 can be a heterocyclic hydrocarbon group with 4 to 20 carbon atoms. Specific examples include thiophene, furanyl, pyranyl, pyrrole, oxazolyl, thiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothiophene, quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, carbazolyl, acridineyl, phenthiazinyl, phenazinyl, xanthonyl, thianyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochoryl, dibenzothiophene, xanthonone, thioxanthonone, and dibenzofuranyl.

[0135] In formula (2), the alkyl sulfinyl group represented by R7 can be a straight-chain alkyl sulfinyl group having 1 to 18 carbon atoms or a branched alkyl sulfinyl group having 3 to 18 carbon atoms. Specific examples include methyl sulfinyl, ethyl sulfinyl, propyl sulfinyl, isopropyl sulfinyl, butyl sulfinyl, isobutyl sulfinyl, sec-butyl sulfinyl, tert-butyl sulfinyl, pentyl sulfinyl, isopentyl sulfinyl, neopentyl sulfinyl, tert-pentyl sulfinyl, octyl sulfinyl, and isooctadecyl sulfinyl.

[0136] In formula (2), the aryl sulfinyl group represented by R7 can be an aryl sulfinyl group with 6 to 10 carbon atoms. Specific examples include phenyl sulfinyl, tolyl sulfinyl, and naphthyl sulfinyl.

[0137] In formula (2), the alkyl sulfonyl group represented by R7 can be a straight-chain alkyl sulfonyl group having 1 to 18 carbon atoms or a branched alkyl sulfonyl group having 3 to 18 carbon atoms. Specific examples include methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl, isobutyl sulfonyl, sec-butyl sulfonyl, tert-butyl sulfonyl, pentyl sulfonyl, isopentyl sulfonyl, neopentyl sulfonyl, tert-pentyl sulfonyl, octyl sulfonyl, and octadecyl sulfonyl.

[0138] In formula (2), the aryl sulfonyl group represented by R7 can be an aryl sulfonyl group with 6 to 10 carbon atoms. Specific examples include phenyl sulfonyl, toluene sulfonyl (toluene sulfonyl), and naphthyl sulfonyl.

[0139] In formula (2), the hydroxyl (poly)alkoxy group represented by R7 can be exemplified by the hydroxyl (poly)alkoxy group represented by the following formula (3):

[0140] HO(-AO)q- (3)

[0141] (In the formula, AO represents ethoxide and / or propoxide, and q represents an integer from 1 to 5.)

[0142] In formula (2), the substituted silyl group represented by R7 can be substituted silyl groups having 1 to 18 carbon atoms. Specific examples include silyl group, methylsilyl group, dimethylsilyl group, trimethylsilyl group, phenylsilyl group, methylphenylsilyl group, dimethylphenylsilyl group, diphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, etc.

[0143] In formula (2), the amino group represented by R7 can be an amino group (-NH2) or a substituted amino group having 1 to 15 carbon atoms. Specific examples of substituted amino groups include methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, and isopropylphenylamino.

[0144] In equation (2), the halogen atom represented by R7 can be fluorine, chlorine, bromine and iodine.

[0145] In equation (2), when n is 2 to 5, R7 are independent of each other and can be the same or different.

[0146] R7 is preferably hydroxyl, alkoxy, alkyl carbonyloxy, or arylalkoxy carbonyloxy, and more preferably hydroxyl, methoxy, acetyloxy, or benzyloxy carbonyloxy.

[0147] n represents the number of R7s, where R7 is an integer from 0 to 5, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. If R7 is within these preferred ranges, the thermosensitivity of the matte salt is further improved.

[0148] Among the groups represented by formula (2), preferred examples are shown below. More preferably:

[0149] In formula (2), R5 is a methyl group, R6 is a naphthyl group, and R7 is a hydroxyl group, which is a sulfonium cation.

[0150] In formula (2), R5 is a methyl group, R6 is a benzyl group, and R7 is a hydroxyl group, which are sulfonium cations.

[0151] In formula (2), R5 is a methyl group, R6 is a 4-nitrobenzyl group, and R7 is a hydroxyl group, forming a sulfonium cation; and

[0152] In formula (2), R5 and R6 are methyl groups and R7 is an acetoxy sulfonium cation.

[0153] [Chemistry 6]

[0154]

[0155] When the acid-producing agent (D) is the photoacid-producing agent (D2), from the viewpoint of efficiently producing acid by light, for counter cations other than the iodonium cation that forms a salt with the gallium anion represented by formula (1), examples that can be cited include triphenylsulfonium, tris(p-tolyl)sulfonium, tris(o-tolyl)sulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tris(1-naphthyl)sulfonium, tris(2-naphthyl)sulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi(p-tolyl)sulfonium, and 4-(4-methoxyphenylthio)sulfonium. ) phenyl bis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenyl bis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyl di(p-tolyl)sulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanone-thio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl] sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonyl}phenyl] sulfide, bis{4-[bis(4-fluorophenyl)sulfonyl]phenyl} sulfide, bis{4-[bis(4-methylphenyl)sulfonyl]phenyl} sulfide, bis{4-[bis( 4-Methoxyphenyl)sulfonyl]phenyl]thiosulfate, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl diphenylsulfonium, 4-(4-benzoylphenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi(p-tolyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonyl]thioxanthone, 2-[(diphenyl)sulfonyl]thioxanthone Triaryl sulfonium compounds include 4-(9-oxo-9H-thioxanth-2-yl)thiophenyl-9-oxo-9H-thioxanth-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi(p-tolyl)sulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi(p-tolyl)sulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthanethium, 5-phenylthianthianthium, 5-tolylthianthianthium, 5-(4-ethoxyphenyl)thianthianthium, and 5-(2,4,6-trimethylphenyl)thianthianthium.

[0156] Examples of ammonium cations include N,N-dimethylpyrrolidineonium, N-ethyl-N-methylpyrrolidineonium, and N,N-diethylpyrrolidineonium; N,N'-dimethylimidazolineonium, N,N'-diethylimidazolineonium, N-ethyl-N'-methylimidazolineonium, 1,3,4-trimethylimidazolineonium and 1,2,3,4-tetramethylimidazolineonium; tetrahydropyrimidineonium such as N,N'-dimethyltetrahydropyrimidineonium; and N,N'-dimethyl... Morpholinium, N,N'-diethylpiperidine, N-methylpyridinium, N-benzylpyridinium and N-benzoylmethylpyridinium, N,N'-dimethylimidazolium, N-methylquinolineium, N-benzylquinolineium and N-benzoylmethylquinolineium, N-methylisoquinolineium, benzylbenzothiazolineium and benzoylmethylbenzothiazolineium, benzyl acridineium and benzoylmethyl acridineium, etc.

[0157] In this embodiment, the content of the acid-generating agent (D) in the resin composition is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 8 parts by weight, and even more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the total amount of the resin composition. The content of the acid-generating agent (D) in the resin composition is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the total amount of components (A) and (B). Furthermore, the content of the acid-generating agent (D) in the resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the total amount of components (A), (B), and (F) described later.

[0158] (E) Acid-producing agents other than component (D)

[0159] If necessary, the resin composition of this method may also contain an acid-generating agent other than component (D) (hereinafter also referred to as "component (E)"), without impairing the effects of the present invention. Surprisingly, as long as the resin composition of this method contains the acid-generating agent of component (D), even if it contains an acid-generating agent other than component (D) of component (E), the change in Tg of the cured resin composition after being placed in a high temperature and high humidity environment for a long time is suppressed less. Examples of acid-generating agents other than component (D) of component (E) include BF4. - SbF6 - AsF6 - B(C6F5)4 - C(CF3SO2)3 - [P(R8)] a F 6-a ] - [C(R8SO2)3]- Or [N(R8SO2)2] - (In the formula, R8 is an alkyl group in which at least a portion of the hydrogen atom is replaced by a fluorine atom, and a is an integer from 0 to 5. When a is an integer greater than 2, there are multiple R8s that can be the same or different from each other.) Various ononium salts that serve as counter anions and have sulfonium cations, ammonium cations, phosphonium cations, iodonium cations, etc., as the cation part.

[0160] Regarding the acid-generating agent other than component (D) in (E), from the viewpoint of not impairing the excellent high-temperature and high-humidity reliability obtained by the acid-generating agent (D), it is preferable to include a sulfonium cation or an ammonium cation as the cationic component, and more preferably a sulfonium cation. The acid-generating agent other than component (D) in (E) may also include an iodonium cation within the scope that does not impair the effects of the present invention; however, it is preferable not to include an iodonium cation.

[0161] In one embodiment, when the acid-producing agent (D) is a thermal acid-producing agent (D1), the acid-producing agent other than component (D) in (E) is a photo-acid-producing agent.

[0162] In one embodiment, when the acid-producing agent (D) is a photo-acid-producing agent (D2), the acid-producing agent other than component (D) in (E) is a thermal acid-producing agent.

[0163] (E) Acid-generating agents other than those in component (D) may be commercially available products. Examples of commercially available products include photoacid-generating agents as borate sulfonate salts (products manufactured by San-Apro Co., Ltd.: CPI-110B, CPI-310B, CPI-410B, etc.), photoacid-generating agents as sulfonate salts with PF3(C2F5)3 (products manufactured by San-Apro Co., Ltd.: CPI-210S, VC-1S, CPI-410S, etc.), thermal acid-generating agents as sulfonate salts with PF3(C2F5)3 (products manufactured by San-Apro Co., Ltd.: TA-100, etc.), and thermal acid-generating agents as quaternary ammonium salts of borates (products manufactured by King Industries, Inc.: CXC-1821, etc.), but are not limited to these. Any one of the acid-generating agents other than those in component (D) may be used, or two or more may be used in combination.

[0164] The content of the acid-producing agent other than component (D) in the resin composition is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to the total of 100 parts by weight of components (A), (B) and (F) described later.

[0165] (F) Epoxy compounds other than alicyclic epoxides

[0166] The resin composition of this method may also contain epoxy compounds other than (F) alicyclic epoxy compounds (hereinafter also referred to as "(F) other epoxy compounds" or "component (F)"). Examples of epoxy compounds other than alicyclic epoxy compounds include monofunctional epoxy compounds having one non-alicyclic epoxy group and polyfunctional epoxy compounds having two or more non-alicyclic epoxy groups. (F) other epoxy compounds are broadly classified into epoxy compounds having an aromatic ring skeleton and aliphatic epoxy compounds.

[0167] Examples of epoxy compounds with aromatic ring skeletons, in the case of multifunctional epoxy resins, include:

[0168] -Bisphenol A type epoxy resins (such as EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc. manufactured by DIC Corporation),

[0169] - Polyalkylene oxide modified bisphenol A type epoxy resins, such as polypropylene oxide modified bisphenol A type epoxy resins (e.g., AER9000 manufactured by Asahi Kasei Corporation, EP-4000S manufactured by ADEKA Corporation, EP-4003S manufactured by ADEKA Corporation, EP-4005 manufactured by ADEKA Corporation, and EP-4010S manufactured by ADEKA Corporation), and polyethylene oxide modified bisphenol A type epoxy resins (e.g., Rikaresin BEO-60E manufactured by Shin Nippon Rikka Corporation).

[0170] -Bisphenol F type epoxy resin (such as EPICLON (registered trademark) 830-S, EXA-830LVP, etc. manufactured by DIC Corporation),

[0171] -Bisphenol AD ​​type epoxy resin,

[0172] -Bisphenol S-type epoxy resin,

[0173] - Naphthalene-type epoxy resins (such as EPICLON (registered trademark) manufactured by DIC Corporation, HP-4032D, HP-720H, etc.)

[0174] - Phenolic linear phenolic epoxy resins (such as EPICLON (registered trademark) N-740, N-770, etc. manufactured by DIC Corporation),

[0175] - Cresol linear phenolic epoxy resins (such as EPICLON (registered trademark), N-660, N-670, N-655-EXP-S, etc. manufactured by DIC Corporation)

[0176] Multifunctional epoxy compounds such as glycidyl ether of tetra(hydroxyphenyl)alkane and glycidyl ether of tetrahydroxybenzophenone.

[0177] -Epoxidized polyvinylphenol;

[0178] etc., but not limited to them.

[0179] Examples of monofunctional epoxides with an aromatic ring skeleton include p-tert-butylphenyl glycidyl ether (such as ADEKA GLYCIROL (registered trademark), ED-509E, ED-509S, etc. manufactured by ADEKA Co., Ltd.) and 2-phenylphenol glycidyl ether (such as OPP-G manufactured by Sanko Co., Ltd.), but are not limited to these.

[0180] Aliphatic epoxy compounds are epoxy compounds that have neither an aromatic ring skeleton nor an alicyclic epoxy group. Examples include glycidyl ethers of aliphatic alcohols (including chain alcohols and alicyclic alcohols) or their polyepoxyalkane adducts, and hydrogenated bisphenol type epoxy resins obtained by hydrogenating bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin. Examples of aliphatic epoxides include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether (e.g., EPOLITE 100MF manufactured by Kyoei Chemical Co., Ltd.), polyethylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether (e.g., jER YX7400N manufactured by Mitsubishi Chemical Co., Ltd.), lauryl alcohol polyethylene glycol diglycidyl ether (e.g., DENACOL EX-171 manufactured by Nagase ChemteX Co., Ltd.), and diglycidyl ethers of alicyclic diols (e.g., AdekaResin EP-4088S manufactured by ADEKA Co., Ltd., and Adeka Resin manufactured by ADEKA Co., Ltd.). EP-4088L), diglycidyl ethers of polyepoxyalkane adducts of alicyclic diols, and hydrogenated bisphenol A diglycidyl ethers (such as jER YX8000 manufactured by Mitsubishi Chemical Corporation), but are not limited to them.

[0181] (F) The epoxy equivalent of other epoxy compounds is preferably 90 to 1000 g / eq, more preferably 120 to 800 g / eq, and even more preferably 150 to 500 g / eq.

[0182] (F) Any one of the other epoxy compounds may be used, or two or more may be used in combination.

[0183] The content of epoxy compounds other than (F) alicyclic epoxy compounds in the resin composition is preferably 5 to 50% by weight relative to the total weight of the resin composition, more preferably 10 to 40% by weight, and even more preferably 15 to 35% by weight.

[0184] The content of epoxy compounds other than (F) alicyclic epoxy compounds in the resin composition is preferably 50 to 200 parts by weight relative to 100 parts by weight of (A) alicyclic epoxy compounds, more preferably 100 to 150 parts by weight.

[0185] In this method, regarding the content of all epoxy compounds in the resin composition, from the viewpoint of low-temperature curing properties, it is preferably 100 to 1300 parts by weight relative to 100 parts by weight of (B) oxobutane compound, more preferably 110 to 1200 parts by weight, and even more preferably 120 to 1100 parts by weight. The term "all epoxy compounds" refers to the total amount of epoxy compounds other than (A) alicyclic epoxy compounds and (F) alicyclic epoxy compounds.

[0186] (G) Coupling agent

[0187] If desired, the resin composition of this method may also contain a coupling agent (G) (hereinafter also referred to as "component (G)") without impairing the effects of the present invention. The coupling agent has two or more different functional groups in its molecule, one of which is chemically bonded to an inorganic material and the other to an organic material. By including a coupling agent in the resin composition, the adhesive strength of the resin composition to a substrate, etc., is improved.

[0188] Examples of coupling agents, depending on the type of functional group that is chemically bonded to inorganic materials, include silane coupling agents, aluminum coupling agents, titanium coupling agents, etc., but are not limited to these.

[0189] Examples of coupling agents include epoxy, amino, vinyl, methacrylic, acrylic, and mercapto coupling agents, depending on the type of functional groups that chemically bond with organic materials; however, they are not limited to these. Among them, epoxy coupling agents containing epoxy groups are preferred from the viewpoint of moisture resistance reliability.

[0190] Any one coupling agent can be used, or two or more can be used in combination.

[0191] When a coupling agent is added, the amount of coupling agent added, from the viewpoint of improving adhesive strength, is preferably 0.01% to 10% by weight, more preferably 0.1% to 5% by weight, relative to the total weight of the resin composition.

[0192] (H) Pigment

[0193] The resin composition of this method may also contain (H) pigment (hereinafter also referred to as "component (H)") without impairing the effects of the present invention.

[0194] Depending on the intended use of the cured resin composition, light-blocking properties are sometimes required. In such cases, the resin composition of this type may contain pigments. Examples of pigments include inorganic pigments such as carbon black, graphite-based, iron oxide-based, titanium black, anthraquinone-based, cobalt oxide-based, copper oxide-based, manganese-based, antimony oxide-based, nickel oxide-based, perylene oxide-based, aniline-based, molybdenum sulfide, and bismuth sulfide, as well as organic pigments such as azo, cyanine, phthalocyanine, and quinacridone-based pigments. Examples of commercially available products include titanium black 13M, 13M-C, and 13MT manufactured by Mitsubishi Materials Electronics Chemicals Co., Ltd. The amount of pigment added can be appropriately determined according to the intended use of the cured resin composition.

[0195] Other additives

[0196] If necessary, the resin composition of this method may further contain other additives, such as organic peroxides, photosensitizers, conductive fillers, stabilizers, ion traps, leveling agents, antioxidants, defoamers, viscosity modifiers, flame retardants, colorants, plasticizers, solvents, etc., without prejudice to the main principles of this method. The types and amounts of each additive are as shown in the conventional method.

[0197] From the viewpoint of preventing a decrease in curing strength and sealing, and preventing gas leakage and seepage, the resin composition of this method preferably does not contain liquid components such as water, solvents, and ionic liquids (excluding liquid components (A), (B), (D), and (F)). For example, the content of liquid components is preferably 3% by weight or less relative to the total weight of the resin composition, and more preferably 1% by weight or less. Examples of solvents include hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, butyrolactone, propylene carbonate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogen solvents (dichloromethane, chloroform, etc.), which are commonly used organic solvents in the field of curable compositions.

[0198] The method for manufacturing the resin composition of this method is not particularly limited. For example, components (A) to (D) and any other components used as needed can be simultaneously or separately introduced into a suitable mixer, and if necessary, mixed by heating and stirring to form a homogeneous composition, thereby obtaining the resin composition of this method. The mixer is not particularly limited, and a mortar and pestle mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill equipped with a stirring and heating device can be used. In addition, these devices can be used in appropriate combinations.

[0199] The resin composition of this method can be formulated as a one-liquid resin composition that is packaged in a single container, or as a two-liquid (or multi-liquid) resin composition that is packaged in two or more containers, depending on its intended use. When formulating a two-liquid (or multi-liquid) resin composition, the aforementioned components (A) to (D) and any other components used as needed can be selected in the same manner as in the one-liquid composition. Furthermore, when formulating a two-liquid (or multi-liquid) resin composition, the aforementioned components (A) to (D) and any other components used as needed can be divided into two or more liquids in any dispensing manner without particular restriction. When divided into two or more liquids in any dispensing manner, each liquid may contain one or more components selected from the aforementioned components (A) to (D) and any other components used as needed; a single liquid may contain the aforementioned components (A) to (D); or a liquid may consist only of the aforementioned components (A) to (D) and / or any other components used as needed. For example, when the composition consists of liquid A and liquid B, the distribution can be as follows: liquid A: component (A), liquid B: component (B), component (C), and component (D); liquid A: component (A) and component (C), liquid B: component (B) and component (D); liquid A: component (A) and component (D), liquid B: component (B) and component (C); liquid A: component (B), liquid B: component (A), component (C), and component (D); or liquid A: component (A), component (B), and component (C), liquid B: component (A), component (C), and component (D). When components (A) to (D) are included in liquid A, and all other components are included in liquid B, liquid A alone, or liquid A and liquid B together, can be considered as the resin composition of this method. On the other hand, when components (A) to (D) are each included in different liquids, each liquid can be considered as the resin composition of this method. As an example of a case where the above-mentioned components (A) to (D) are contained in different liquids, a resin composition can be provided in which the above-mentioned components (A) to (D) are dispensed into two or more containers. More specifically, a kit formed from multiple liquids containing any one of the above-mentioned components (A) to (D) can be provided.

[0200] The resin composition obtained in this way is photocurable, thermocurable, or photo-and-thermocurable depending on the type of acid-producing agent contained in the resin composition. In the case of a photocurable resin composition, photocuring is performed, for example, by irradiating the resin composition with UV light. In the case of a thermocurable resin composition, curing is preferably performed within 5 hours at a temperature of 100°C, more preferably within 3 hours, and even more preferably within 1 hour. In one embodiment, for example, the resin composition of this type is heat-cured at a temperature of 70–100°C for 30–120 minutes. In the case of a photo-and-thermocurable resin composition, it can be further cured by heat, for example, after pre-curing by light (UV) or under light irradiation.

[0201] The resin composition of this method can be used, for example, as an adhesive or sealant for fixing, joining or protecting semiconductor devices or electronic components or components constituting them, or as a raw material thereof.

[0202] The coating method for the resin composition is not particularly limited. For example, it can be applied to the desired portion of a component, such as a substrate, using known printing, dispensing, or coating methods. Examples of printing methods include inkjet printing, screen printing, offset printing, carton printing, metal printing, flexographic printing, gravure printing, and so on, but are not limited to these. Examples of dispensing methods include using a jet dispensing machine, a pneumatic dispensing machine, etc., but are not limited to these. Examples of coating methods include dip coating, spray coating, bar coating, gravure coating, reverse gravure coating, spin coating, etc., but are not limited to these.

[0203] [Adhesive or sealant]

[0204] As another aspect of the present invention, the adhesive or sealing material comprises the resin composition described above. This adhesive or sealing material can achieve good fixation, bonding, or protection for general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, polyphthalamide, polybutylene terephthalate, etc.), glass, ceramics, metals (e.g., copper, nickel, etc.), and organic substrates (e.g., FR4, etc.), and can be used for fixing, bonding, or protecting components constituting semiconductor devices or electronic parts. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, image sensor modules, TOF sensor modules, other semiconductor modules, integrated circuits, etc.

[0205] The adhesive or sealant of this method can be formulated as a one-component adhesive or sealant that can be contained in a single container, or as a two-component (or multi-component) adhesive or sealant that can be contained in two or more containers, depending on its intended use. When formulating a two-component (or multi-component) adhesive or sealant, the aforementioned components (A) to (D), and any other components used as needed, can be selected in the same manner as in the one-component type. Furthermore, when formulating a two-component (or multi-component) adhesive or sealant, the aforementioned components (A) to (D), and any other components used as needed, can be divided into two or more components in any distribution manner without particular restriction. When divided into two or more components in any distribution manner, each liquid may contain one or more components selected from the aforementioned components (A) to (D) and any other components used as needed; a single liquid may contain the aforementioned components (A) to (D); or a liquid may consist only of the aforementioned components (A) to (D) and / or any other components used as needed. For example, when the mixture consists of liquid A and liquid B, the distribution can be as follows: liquid A: component (A), liquid B: component (B), component (C), and component (D); liquid A: component (A) and component (C), liquid B: component (B) and component (D); liquid A: component (A) and component (D), liquid B: component (B) and component (C); liquid A: component (B), liquid B: component (A), component (C), and component (D); liquid A: component (A), component (B), and component (C), liquid B: component (A), component (C), and component (D). When components (A) to (D) are included in liquid A, and all other components are included in liquid B, liquid A alone, or liquid A and liquid B together, can be considered as the adhesive or sealing material of this method. On the other hand, when components (A) to (D) are each included in different liquids, each liquid can be considered as the adhesive or sealing material of this method. Examples of the above components (A) to (D) being contained in different liquids include adhesives or sealing materials in which the above components (A) to (D) are packaged in two or more containers. More specifically, examples include kits formed from multiple liquids containing any one of the above components (A) to (D).

[0206] [Cure of resin composition, adhesive, or sealant]

[0207] Another aspect of the present invention is a cured product obtained by curing the resin composition, adhesive, or sealant described above. This cured product exhibits excellent high-temperature and high-humidity reliability. That is, even after prolonged exposure to a high-temperature and high-humidity environment, specifically, the change in Tg of the cured product before and after a pressure cooker test (PCT) at 2 atm, 121°C, 100% RH for 20 hours is relatively small. In this aspect, the change in Tg of the cured product before and after the PCT at 2 atm, 121°C, 100% RH for 20 hours is preferably less than 10.3°C, more preferably less than 8°C, and even more preferably less than 6°C.

[0208] [Semiconductor devices, electronic components]

[0209] As another aspect of the present invention, a semiconductor device or electronic component includes a cured product of the above-described manner. Here, "semiconductor device" refers to any device capable of functioning by utilizing the properties of semiconductors, including electronic components, semiconductor circuits, modules assembled thereon, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, image sensor modules, sensor modules such as TOF sensor modules, other semiconductor modules, integrated circuits, etc.

[0210] Example

[0211] The present invention will be further described in detail below through embodiments and comparative examples; however, the present invention is not limited to these embodiments. It should be noted that in the following embodiments, unless otherwise specified, parts and percentages refer to parts by weight and percentage by weight.

[0212] [Preparation of the resin composition]

[0213] The resin compositions of the Examples and Comparative Examples were prepared by mixing the given amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by weight (in g). The components used in the Examples and Comparative Examples are shown below.

[0214] (A) Alicyclic epoxides

[0215] (A-1): 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Product name: CELLOXIDE (registered trademark) 2021P, manufactured by Daicel Co., Ltd., epoxy equivalent: 130g / eq)

[0216] (B) Oxybutane compounds

[0217] (B-1): 3-Ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane (Product name: OXT-221, manufactured by Toa Synthetic Co., Ltd., oxetane equivalent: 107 g / eq)

[0218] • (C) Packing

[0219] (C-1): Hydrophobic pyrolytic silica (Product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT, average particle size: 12nm)

[0220] (C-2): Surface-treated silica filler (product name: SE5200SEE, average particle size 2μm, manufactured by Admatechs Co., Ltd.)

[0221] • (D) as an acid-producing agent for the salt formed by the gallium anion of formula (1) and a counter cation other than iodonium cation (in the table, it is represented as "(D) gallium-based acid-producing agent (other than iodonium cation)")

[0222] (D1-1): Thermal acid-producing agent represented by the following formula

[0223] [Chemistry 7]

[0224]

[0225] The thermally generated acid agent was synthesized by the method described in WO2018 / 020974.

[0226] (D2-1): Photoacid generator represented by the following formula

[0227] [Chemistry 8]

[0228]

[0229] The photoacid generator was synthesized using the method described in WO2018 / 020974.

[0230] • Acid-producing agents other than component (D) (E)

[0231] (E-1): Thermal acid-producing agent represented by the following formula

[0232] [Chemistry 9]

[0233]

[0234] (Product name: TA-100, manufactured by San-Apro Co., Ltd.)

[0235] (E-2): Thermal acid-producing agent represented by the following formula

[0236] [Chemistry 10]

[0237]

[0238] The thermally generated acid agent was synthesized by the method described in Japanese Patent Application Publication No. 2022-080366.

[0239] (E-3): Borate quaternary ammonium salt (Product name: CXC-1821, manufactured by King Industries, Inc., thermal acid generator)

[0240] (E-4): Borate-based sulfonate salt (Product name: CPI-310B, manufactured by San-Apro Co., Ltd., photoacid generator)

[0241] • (F) Epoxy compounds other than alicyclic epoxides

[0242] (F-1): Polypropylene oxide modified bisphenol A type epoxy resin (product name: AER9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380g / eq)

[0243] (F-2): p-tert-butylphenyl glycidyl ether (product name: ADEKA GLYCIROL (registered trademark) ED-509S, manufactured by ADEKA Co., Ltd., epoxy equivalent: 205g / eq)

[0244] (G) Coupling agent

[0245] (G-1): 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Product name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0246] · (H) Pigment

[0247] (H-1): Titanium Black (Product Name: 13M, manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.)

[0248] (I) Other additives

[0249] (I-1): Dihexadecyl peroxide (brand name: Perkadox (registered trademark) 24L, manufactured by Nouryon)

[0250] [Manufacturing of solidified products]

[0251] The resin compositions of the examples and comparative examples were heated at 100°C for 60 minutes to produce cured products.

[0252] In the examples and comparative examples, the properties of the resin composition and its cured product were determined as follows.

[0253] [Determination of Tg and elastic modulus of cured products before and after PCT]

[0254] Samples coated with various resin compositions on a glass substrate to a thickness of 250 ± 100 μm were subjected to a thermosetting treatment at 100 °C for 60 minutes in a blower dryer, thereby producing cured products on the glass substrate. Dynamic thermomechanical measurements (DMA) were performed on the cured products to determine the initial Tg [°C] and the elastic modulus [GPa] at 25 °C.

[0255] Subsequently, PCT was applied to the cured material under the conditions of 2 atm, 121°C, 100% RH and 20 hours, and the Tg [°C] and elastic modulus [GPa] of the cured material after PCT were calculated respectively.

[0256] The change in Tg of the cured product before and after PCT can be calculated using the following formula.

[0257] [Change in Tg of cured product before and after PCT] = |[Initial Tg of cured product] - [Tg of cured product after PCT] |

[0258] Regarding the modulus of elasticity, the modulus of elasticity at 25°C was measured using a Hitachi Dynamic Viscoelasticity (DMA) measuring device in accordance with Japanese Industrial Standard JIS C6481.

[0259] Regarding Tg, it was measured using a Hitachi Dynamic Viscoelasticity (DMA) measuring apparatus in accordance with Japanese Industrial Standard JIS C6481.

[0260] The results are shown in Table 1.

[0261] In this specification, under PCT conditions of 2 atm, 121°C, 100% RH, and 20 hours, the change in Tg of the cured product is preferably less than 10.3°C, more preferably less than 8°C, and even more preferably less than 6°C.

[0262]

[0263]

[0264] The changes in Tg of the cured resin compositions of Examples 1 to 9, which satisfy the configuration of the present invention, before and after PCT are minimized.

[0265] On the other hand, for the cured resin compositions of Comparative Examples 1 to 4 that do not contain (D) as an acid-generating agent that forms a salt of counter cations other than gallate anion and iodonium cation in Formula (1), but contain (E) other than (D) as an acid-generating agent, the change in Tg before and after PCT is greater.

[0266] Surprisingly, for the cured resin composition of Example 9, which contains an acid-generating agent other than component (D) (as a salt of counter cations other than gallate anion and iodonium cation of formula (1), the change in Tg before and after PCT is suppressed even though it contains an acid-generating agent other than component (D).

[0267] In addition, for the cured resin composition of Comparative Example 5 that does not contain (B)oxetane compounds, the change in Tg before and after PCT is also greater.

[0268] It should be noted that, although not shown in Table 1, the two-component resin composition with liquid A (components (A), (C), (F), (G), and (H)) and liquid B (components (B) and (D)) in Example 2 was also evaluated in the same way, and the results showed the same as those of the one-component resin composition.

[0269] Industrial availability

[0270] The resin compositions of the present invention are highly practical, for example, as adhesives or sealants for fixing, joining or protecting semiconductor devices or electronic components or components constituting them.

[0271] The entire contents of the disclosure of Japanese Patent Application No. 2024-048038 (filed on March 25, 2024) are incorporated herein by reference.

[0272] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as the specific and individually described documents, patent applications and technical standards are incorporated herein by reference.

Claims

1. A resin composition comprising: (A) Alicyclic epoxy compounds; (B) Oxycyclic butane compounds; (C) Packing material; and (D) An acid-producing agent, wherein the acid-producing agent is a salt formed by an anion represented by the following formula (1) and a counter cation other than iodonium cation. In the formula, R1, R2, R3, and R4 each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms. At least one of R1, R2, R3 and R4 represents an aryl group having 6 to 14 carbon atoms.

2. The resin composition according to claim 1, wherein, The acid-producing agent (D) is a thermal acid-producing agent (D1).

3. The resin composition according to claim 1, wherein, The acid-producing agent (D) is a photoacid-producing agent (D2).

4. The resin composition according to claim 1, wherein, The acid-producing agent (D) is a combination of the thermal acid-producing agent (D1) and the photo-acid-producing agent (D2).

5. The resin composition according to any one of claims 1 to 4, wherein, The counter cation in the acid-producing agent (D) is a sulfonium cation or an ammonium cation.

6. The resin composition according to any one of claims 1 to 5, wherein, The content of the acid-producing agent (D) is 0.1 to 10 parts by weight relative to the total amount of the resin composition (100 parts by weight).

7. The resin composition according to any one of claims 1 to 6, further comprising an acid-producing agent other than component (D) in (E).

8. The resin composition according to claim 7, wherein, The acid-producing agent other than component (D) in (E) contains sulfonium cations or ammonium cations.

9. The resin composition according to any one of claims 1 to 8, further comprising (F) an epoxy compound other than an alicyclic epoxy compound.

10. The resin composition according to claim 9, wherein, The epoxy compounds other than alicyclic epoxy compounds mentioned in (F) include epoxy compounds with an epoxy equivalent of 90 g / eq to 1000 g / eq.

11. The resin composition according to claim 9 or 10, wherein, The content of the epoxy compound other than the (F) alicyclic epoxy compound is 50 to 200 parts by weight relative to 100 parts by weight of the (A) alicyclic epoxy compound.

12. The resin composition according to any one of claims 1 to 11, wherein, The total content of all epoxy compounds in the resin composition is 100 to 1300 parts by weight relative to 100 parts by weight of the (B) oxobutane compound.

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

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

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

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

17. A semiconductor device or electronic component comprising the cured material of claim 16.

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