Alkali generator, hardening resin composition, hardened product thereof, and printed wiring board

Abstract

This invention provides an alkali-generating agent and a curable resin composition that exhibit excellent storage stability in a liquid, high catalytic activity at the desired curing temperature, and induce a curing reaction in a short time. An alkali-generating agent comprises a pyridinium cation and an anionic residue of an organic or inorganic acid, and is represented by the following formula (a). (In formula (a), A represents a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain heteroatoms; R1 to R5 independently represent hydrogen atoms or electron-donating groups; R1 and R2, R2 and R3, R3 and R4, and R4 and R5 can be bonded to form a ring structure. R6 to R5...) 10 Each of the following groups independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfinic acid group, sulfonyl group, sulfonic acid group, phosphono group, oxophosphono group, phosphonyl group, phosphonate group, amino group, or ammonium group, R6 and R7, R7 and R8, R8 and R9, R9 and R 10 They can be bonded separately to form a ring structure.

Description

Technical Field

[0001] This invention relates to an alkali-generating agent, a curable resin composition containing the alkali-generating agent, and a cured product thereof. Background Technology

[0002] Previously, phosphorus-based or imidazole-based curing accelerators were known as curing accelerators for thermosetting resins, particularly epoxy resins. Phosphorus-based curing accelerators can produce cured products with high curing strength and high electrical reliability. Potential curing accelerators among phosphorus-based curing accelerators include, for example, phosphonium borate (Patent Document 1), phosphonium carboxylate (Patent Documents 2-6), phosphonium thiocyanate (Patent Document 7), and 1,2-bis(diphenylphosphine)acetylene (Patent Document 8), but these are not sufficient from the viewpoint of potentiality.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent No. 3638258

[0006] Patent Document 2: International Publication No. 2010 / 087526

[0007] Patent Document 3: International Publication No. 2009 / 014270

[0008] Patent Document 4: Japanese Patent Application Publication No. 3-20065

[0009] Patent Document 5: Japanese Patent Application Publication No. 2016-113475

[0010] Patent Document 6: Japanese Patent Application Publication No. 11-158251

[0011] Patent Document 7: Japanese Patent Application Publication No. 2010-209150

[0012] Patent Document 8: Japanese Patent Application Publication No. 2015-172136 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The purpose of this invention is to provide an alkali-generating agent and a curing resin composition that exhibit excellent storage stability in a liquid, high catalytic activity at the desired curing temperature, and induces a curing reaction in a short time.

[0015] Technical means to solve the problem

[0016] That is, the present invention relates to the following [1] to

[16] . In addition, in this application, "(numerical value 1) to (numerical value 2)" indicates that it includes upper and lower limits. [1]

[0018] A base generating agent comprising a pyridinium cation and an anionic residue of an organic or inorganic acid, and represented by the following formula (a).

[0019] [Chemistry 1]

[0020]

[0021] In formula (a), A represents a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain heteroatoms; R1 to R5 represent hydrogen atoms or electron-donating groups, respectively; R1 and R2, R2 and R3, R3 and R4, and R4 and R5 can be bonded to form ring structures. R6 to R 10 Each of the following groups independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfinic acid group, sulfonyl group, sulfonic acid group, phosphono group, oxophosphono group, phosphonyl group, phosphonate group, amino group, or ammonium group, R6 and R7, R7 and R8, R8 and R9, R9 and R 10 (They can be bonded separately to form a ring structure) [2]

[0023] According to the base generating agent described in the preceding item [1], wherein R1, R2, R4, and R5 in formula (a) are hydrogen atoms, and R3 is a hydrogen atom or a dimethylamino group. [3]

[0025] According to the base generating agent described in the preceding item [1] or [2], wherein A in the formula (a) is an unsubstituted divalent hydrocarbon group having 1 to 8 carbons, or a divalent hydrocarbon group having 1 to 8 carbons containing a carbonyl group, an ether group, an ester group, an amide group or a sulfide group. [4]

[0027] According to any one of the preceding [1] to [3] base generating agents, wherein the anionic residue X in formula (a) - It contains halogen atoms, boron atoms, or silicon atoms. [5]

[0029] According to any one of the preceding [1] to [3] base generating agents, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-1).

[0030] [Chemistry 2]

[0031]

[0032] (In equation (b-1), R) 11 ~R 14 Each of the following can be independently represented as a straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted aromatic ring. [6]

[0034] According to the alkali-generating agent described above [5], wherein R of formula (b-1) 11 ~R 14 All are phenyl. [7]

[0036] According to any one of the preceding [1] to [3] base generating agents, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-2).

[0037] [Chemistry 3]

[0038]

[0039] (In formula (b-2), Y1 and Y2 are organic groups, which may be the same or different from each other. Z1 represents a substituted or unsubstituted aromatic ring or an organic group with a heterocyclic structure, or a substituted or unsubstituted aliphatic group.) [8]

[0041] According to any one of the preceding [1] to [3] base generating agents, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-3) or the following formula (b-4).

[0042] [Chemistry 4]

[0043]

[0044] [Chemistry 5]

[0045] [9]

[0047] A curable resin composition comprising an alkali-generating agent according to any one of the preceding items [1] to [8].

[10]

[0049] The curable resin composition according to the preceding item [9] also contains an epoxy resin.

[11]

[0051] The curing resin composition according to the preceding item [9] or

[10] further contains a curing agent.

[12]

[0053] The curable resin composition according to any one of the preceding items [9] to

[11] further comprises at least one selected from the group consisting of maleimide compounds, polyphenylene ether compounds, compounds having vinyl unsaturated bonds, cyanate compounds, polybutadiene and its modifications, polystyrene and its modifications, and polyethylene and its modifications.

[13]

[0055] The curing resin composition according to any one of the preceding items [9] to

[12] further comprises at least one selected from thermal polymerization initiators, photopolymerization initiators, anionic curing accelerators, and cationic curing accelerators.

[14]

[0057] The curable resin composition according to any one of the preceding items [9] to

[13] is used in any one of semiconductor sealants, adhesives, adhesive films, prepregs, interlayer insulating materials and heat conduction and heat dissipation materials.

[15]

[0059] A hardener is a hardener of a hardening resin composition according to any one of the preceding items [9] to

[14] .

[16]

[0061] A printed wiring board having a hardened material as described in the preceding item

[15] .

[0062] The effects of the invention

[0063] The present invention provides an alkali-generating agent and a curable resin composition that exhibit excellent storage stability in a liquid, high catalytic activity at the desired curing temperature, and induces a curing reaction in a short time. Attached Figure Description

[0064] [ Figure 1 [This is from] Synthesis Example 1 1 H-NMR chart.

[0065] [ Figure 2 [This is from] Synthesis Example 2 1 H-NMR chart.

[0066] [ Figure 3 [This is from] Synthesis Example 3 1 H-NMR chart.

[0067] [ Figure 4 [This is from synthetic example 4] 1 H-NMR chart.

[0068] [ Figure 5 [This is from] Synthesis Example 5 1 H-NMR chart.

[0069] [ Figure 6 [This is a comparison of Example 1] 1 H-NMR chart.

[0070] [ Figure 7 [This is from synthetic example 6] 1 H-NMR chart.

[0071] [ Figure 8 [This is from] Synthesis Example 7 1 H-NMR chart.

[0072] [ Figure 9 [This is from synthetic example 8] 1 H-NMR chart. Detailed Implementation

[0073] The alkali-generating agent of the present invention comprises a pyridinium cation and an anionic residue of an organic or inorganic acid, and is represented by the following formula (a). An alkali-generating agent is a compound that produces an alkali by irradiation with ultraviolet or visible light or by heating.

[0074] [Chemistry 6]

[0075]

[0076] In formula (a), A represents a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain heteroatoms, preferably an unsubstituted divalent hydrocarbon group with 1 to 8 carbon atoms, or a divalent hydrocarbon group with 1 to 8 carbon atoms that contains a carbonyl group, ether group, ester group, amide group, or sulfide group. More preferably, the number of carbon atoms is 1 to 5, particularly preferably, the number of carbon atoms is 1 to 3, and most preferably, the number of carbon atoms is methylene. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Formula (a) may be represented, for example, as formula (a-1) or formula (a-2) below. Furthermore, R1 to R2 in formulas (a-1) and (a-2)... 10 and X - This indicates the same meaning as equation (a).

[0077] [Chemistry 7]

[0078]

[0079] [Chemistry 8]

[0080]

[0081] In formula (a), R1 to R5 independently represent hydrogen atoms or electron-donating groups, and R1 can be bonded to R2, R2 to R3, R3 to R4, and R4 to R5 to form a ring structure. The electron-donating group is preferably alkyl, alkylamino, or alkoxy. R1, R2, R4, and R5 are preferably hydrogen atoms, and R3 is preferably a hydrogen atom or a dimethylamino atom, particularly preferably a dimethylamino atom.

[0082] In equation (a), R6~R 10 Each of the following groups independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfinic acid group, sulfonyl group, sulfonic acid group, phosphono group, oxophosphono group, phosphonyl group, phosphonate group, amino group, or ammonium group, R6 and R7, R7 and R8, R8 and R9, R9 and R 10 They can be bonded separately to form a ring structure.

[0083] The anion residue X in formula (a) - Preferably, it contains halogen atoms, boron atoms, or silicon atoms, and more preferably it is represented by any of the following formulas (b-1) to (b-4).

[0084] [Chemistry 9]

[0085]

[0086] In equation (b-1), R 11 ~R 14 Each of the above can be independently represented as a straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted aromatic ring, preferably a substituted or unsubstituted aromatic ring.

[0087] [Chemistry 10]

[0088]

[0089] In formula (b-2), Y1 and Y2 are organic groups, which may be the same or different from each other, and are preferably substituted or unsubstituted aromatic rings. Z1 represents a substituted or unsubstituted aromatic ring, an organic group having a heterocyclic ring, or a substituted or unsubstituted aliphatic group, preferably a substituted or unsubstituted aromatic ring.

[0090] [Chemistry 11]

[0091]

[0092] [Chemistry 12]

[0093]

[0094] The compound represented by formula (a) can be used as a curing accelerator for curable resin compositions. The compound represented by formula (a) has the potential to exhibit low catalytic activity at low temperatures (e.g., around 50°C) without curing the curable resin composition, but to exhibit high catalytic activity at the desired curing temperature (e.g., around 150°C) and to cure within a short time (e.g., around 300 to 500 seconds). Therefore, curable resin compositions containing the compound represented by formula (a) exhibit excellent storage stability in a liquid.

[0095] When the curable resin composition is in liquid form, storage stability can be confirmed by viscosity measurement. In this invention, storage stability is confirmed by dividing the viscosity of the curable resin composition after being placed at 25°C for 24 hours by the initial viscosity, preferably by 1.8 times or less, and more preferably by 1.5 times or less. When the curable resin composition is in solid form, storage stability can be confirmed by gel time measurement. In this invention, the gel time retention rate is calculated by dividing the gel time of the curable resin composition after being placed at 50°C for 6 hours by the initial gel time. The closer the gel time retention rate is to 100%, the better the storage stability. Specifically, the gel time retention rate is preferably 80% or more, and more preferably 90% or more.

[0096] Furthermore, curability can be confirmed by gel time and DSC (differential scanning calorimetry). Generally, curability and storage stability are often a trade-off, making it difficult to satisfy both properties. Therefore, comparing curability among curable resin compositions with similar storage stability allows for comparison of differences in properties.

[0097] When the alkali generating agent of the present invention is used as an electrical / electronic component, it is preferable that the hardened material contains few conductive impurities.

[0098] The method of synthesizing the compound represented by formula (a) is not particularly limited, and it can be obtained as follows.

[0099] The compound represented by formula (a) can be obtained, for example, by an addition reaction of a pyridine derivative with an alkyl halide and a subsequent anion exchange reaction with sodium borate or sodium silicate, but is not limited to that described. The reaction is preferably carried out without a catalyst, but a catalyst may be used if necessary.

[0100] Specific examples of organic solvents that can be used in the addition reaction include alcohols such as methanol and ethanol; alkanes such as hexane, cyclohexane, and heptane; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and esters such as ethyl acetate, butyl acetate, and methyl formate.

[0101] Regarding the addition reaction, the reaction proceeds sufficiently even at temperatures around 20°C. As for the reaction time, the reaction temperature is preferably 30°C to 200°C, more preferably 40°C to 200°C, and particularly preferably 40°C to 150°C.

[0102] Next, the curable resin composition of the present invention will be described.

[0103] [Epoxy Resin]

[0104] The curable resin composition of the present invention may also contain epoxy resin. Preferred epoxy resins are exemplified below, but are not limited to these. Furthermore, the epoxy resin may be in liquid or solid form, and one type or multiple types may be used.

[0105] Examples of liquid epoxy resins include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, and epoxy resin with butadiene structure. Specific examples include: “RE310S”, “RE410S” (manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), “RE303S”, “RE304S”, “RE403S”, “RE404S” (manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), “HP4032”, “HP4032D”, “HP4032SS” (manufactured by DIC Corporation, naphthalene type epoxy resin), “828”, “828US”, “828EL”, “825”, “828X” "A" (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenolic varnish type epoxy resin), "630", "630LSD" (manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel Chemical & Materials Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (manufactured by Nagase Chemical Co., Ltd.) The following epoxy resins are manufactured by ChemteX: glycidyl ester type epoxy resin, Celloxide 2021P (manufactured by Daicel, an alicyclic epoxy resin with an ester backbone), PB-3600 (manufactured by Daicel, an epoxy resin with a butadiene structure), ZX1658, and ZX1658GS (both manufactured by Nippon Steel Chemicals & Materials Co., Ltd., liquid 1,4-glycidylcyclohexane type epoxy resins). These can be used individually or in combination of two or more.

[0106] As a solid epoxy resin, preferred types include, for example, xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthyl ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin. Examples include naphthol-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin.Specific examples include: "HP4032H" (manufactured by DIC, a naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both manufactured by DIC, naphthalene-type tetrafunctional epoxy resins), "N-690" (manufactured by DIC, a cresol-phenolic varnish type epoxy resin), "N-695" (manufactured by DIC, a cresol-phenolic varnish type epoxy resin), "HP-7200", "HP-7200HH", etc. HP-7200H (manufactured by DIC, dicyclopentadiene type epoxy resin), EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000 (manufactured by DIC, naphthalene ether type epoxy resin), EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., triphenol type epoxy resin), NC-7000L, NC-7300 (and other epoxy resins) The above are epoxy resins manufactured by Nippon Kayaku Co., Ltd., including naphthol-cresol phenolic resin (varnish type), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (both are biphenyl aralkyl type epoxy resins manufactured by Nippon Kayaku Co., Ltd.), "XD-1000-2L", "XD-1000-L", "XD-1000-H" (dicyclopentadiene type epoxy resins manufactured by Nippon Kayaku Co., Ltd.), and "ESN475V" (naphthol type epoxy resin manufactured by Nippon Steel Chemicals & Materials Co., Ltd.). Epoxy resins), "ESN485" (manufactured by Nippon Steel Chemicals & Materials Co., Ltd., naphthol phenolic resin type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd.), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd.), "YX-4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin), "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd.), "YX-4000H", "YX-40 ...8000", "YX-8000", "YX-8000", "YX-8 Gas Chemicals manufactures a variety of epoxy resins, including fluorene-based epoxy resins, "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin), "CNE-195LL" (manufactured by Changchun Artificial Resin Co., Ltd., o-cresol phenolic varnish type epoxy resin), and "TEPIC-S" (manufactured by Nissan Chemical Co., Ltd., isocyanurate type epoxy resin), etc. These can be used individually or in combination of two or more.

[0107] Among these epoxy resins, epoxy resins with high heat resistance are preferred, and therefore preferably xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol phenolic varnish-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthalene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and tetraphenylethane-type epoxy resins. More preferably, glycidyl ether-type epoxy resins such as naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins are preferred.

[0108] The compound represented by formula (a) is preferably used in the range of 0.001 parts by mass to 15 parts by mass relative to 100 parts by mass of epoxy resin, and more preferably in the range of 0.01 parts by mass to 5 parts by mass.

[0109] [hardener]

[0110] The curable resin composition of the present invention may also incorporate a curing agent. Examples of curing agents that may be incorporated include: amine compounds, acid anhydride compounds, amide compounds, phenolic compounds, carboxylic acid compounds, and reactive ester compounds. Among these, amine compounds, acid anhydride compounds, phenolic compounds, carboxylic acid compounds, and reactive ester compounds are preferred.

[0111] [Amine compounds]

[0112] As amine compounds, compounds having two or more amino groups within the molecule are preferred. Examples include: 4,4'-methylenebis(2-ethyl-6-methylaniline) (MDEA), diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, diaminodiphenyl sulfone, isophorone diamine, naphthyldiamine, aniline phenolic varnish (the reaction product of aniline and formalin), N-methylaniline phenolic varnish (the reaction product of N-methylaniline and formalin), o-ethylaniline phenolic varnish (the reaction product of o-ethylaniline and formalin), 2-methylaniline and formalin, 2,6-diisopropylaniline and formalin, 2,6-diethylaniline and formalin, 2-ethyl-6-ethylaniline and formalin, 2,6-dimethylaniline and formalin, and aniline reacting with α,α'-dichloroxylene (xylylene). Aniline resins obtained by reacting aniline with chloride, reaction products of aniline with substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, as described in Japanese Patent No. 6429862, reaction products of aniline with substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, 4,4'-(1,3-phenylene diisopropylidene)bisaniline, reaction products of aniline with diisopropylidenebenzene, dimerized diamines, etc., are not limited to these. Furthermore, one or more of these may be used.

[0113] [Acid anhydride compounds]

[0114] Examples of anhydride compounds include: phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, and methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride. Among commonly available anhydride compounds is "KAYAHARD MCD" (manufactured by Nippon Kayaku Co., Ltd.). The product names include, but are not limited to, "Rikacid MH-700" (manufactured by New Japan Rika Co., Ltd., 4-methylhexahydrophthalic anhydride), "Rikacid TH" (manufactured by New Japan Rika Co., Ltd., tetrahydrophthalic anhydride), "Rikacid HH" (manufactured by New Japan Rika Co., Ltd., hexahydrophthalic anhydride), and "Rikacid MH-T" (manufactured by New Japan Rika Co., Ltd.; main component is 4-methylhexahydrophthalic anhydride), etc. Furthermore, one or more of these products may be used.

[0115] [Phenolic compounds]

[0116] As phenolic compounds, compounds having two or more phenolic hydroxyl groups within the molecule are preferred. Examples include: reaction products of phenols and aldehydes (phenol-formaldehyde varnish hardeners), reaction products of phenols and dienes, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyl groups, and reaction products of bisphenols and aldehydes. Examples of generally available phenolic compounds include phenol-formaldehyde varnish hardener H-1 (manufactured by UBE Corporation) and cresol-formaldehyde varnish hardener KA-1160 (manufactured by DIC Corporation), but these are not limited to these. Furthermore, one or more of these compounds may be used.

[0117] The following are specific examples of the raw materials, but are not limited to these.

[0118] <Phenolic compounds>

[0119] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0120] Aldehydes

[0121] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthal, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0122] <Diene Compounds>

[0123] Dicyclopentadiene, terpenes, vinylcyclohexene, norbornene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0124] Ketones

[0125] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.

[0126] <Substituted biphenyls>

[0127] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0128] <Substituted Phenyl>

[0129] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0130] [Carboxylic acid compounds]

[0131] As a carboxylic acid compound, it is preferred to be a compound having two or more carboxyl groups within its molecule. Examples include: aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, and furan dicarboxylic acid; succinic acid; adipic acid; dodecanoic acid; sebacic acid; thiodipropionic acid; cyclohexanedicarboxylic acid; tris(2-carboxymethyl)isocyanurate; tris(2-carboxyethyl)isocyanurate; tris(2-carboxypropyl)isocyanurate; and bis(2-carboxyethyl)isocyanurate, but it is not limited to these. Furthermore, one or more of these compounds may be used.

[0132] [Active ester compounds]

[0133] An active ester compound is a compound whose structure contains at least one ester bond and on both sides of the ester bond are aliphatic chains, aliphatic rings, or aromatic rings. Examples of active ester compounds include phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds, which are compounds having two or more highly reactive ester groups in one molecule. These compounds can be obtained through a condensation reaction of at least one carboxylic acid compound, acyl chloride, or thiocarboxylic acid compound with at least one hydroxyl compound or thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to obtain the compound from a carboxylic acid compound or acyl chloride and a hydroxyl compound; the hydroxyl compound is preferably a phenolic compound or a naphthol compound. An active ester compound can be used alone or in combination of two or more.

[0134] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0135] Examples of such acyl chlorides include: acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diglycolyl chloride, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipicoyl dichloride, dodecanedioyl dichloride, azelaoyl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0136] Examples of the phenol and naphthol compounds mentioned above include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, pyroglucinol, dicyclopentadiene-type diphenol compounds, phenolic varnishes, and phenolic resins described later. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two molecules of phenol in one molecule of dicyclopentadiene.

[0137] Preferred examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated form of phenolic varnish, active ester compounds containing a benzoylated form of phenolic varnish, compounds described in Example 2 of International Publication No. 2020 / 095829, and compounds disclosed in International Publication No. 2020 / 059625. More preferably are active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit containing a phenylene-dicyclopentylene-phenylene group.

[0138] Commercially available examples of active ester compounds include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" (manufactured by DIC Corporation), which is an active ester compound containing a naphthalene structure; and active ester compounds containing acetylated phenolic varnishes. Ester compound "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as benzoyl compounds containing phenolic varnishes; active ester curing agent "DC808" (manufactured by Mitsubishi Chemical Corporation) as acetylated compounds for phenolic varnishes; active ester curing agent "EXB-9050L-62M" manufactured by DIC Corporation as a phosphorus-containing active ester curing agent; and active ester compound "unifiner W-575" containing a bisphenol A structure, etc.

[0139] Regarding the formulation ratio of the reactive ester compound and the epoxy resin, the ratio (α / β) of the reactive ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If the ratio deviates from this range, there is a possibility that excessive epoxy groups or reactive ester groups may remain in the system, potentially leading to property degradation during high-temperature storage tests (150°C, 1000 hours, etc.) or long-term reliability tests under high-temperature and high-humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[0140] Regarding the mixing ratio of epoxy resin and hardener, relative to 1 equivalent of epoxy groups in the epoxy resin, the active group (such as anhydride or hydroxyl group) in the hardener capable of reacting with the epoxy groups is preferably 0.5 to 1.5 equivalents (carboxylic acid is considered as one functional group, and anhydride as another functional group), and particularly preferably 0.5 to 1.2 equivalents. If the amount is less than 0.5 equivalents relative to 1 equivalent of epoxy groups, or exceeds 1.5 equivalents, there is a possibility of incomplete curing and failure to obtain good cured properties.

[0141] [Carboxylic acid compounds]

[0142] Examples of the aforementioned carboxylic acid compounds include: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, sodium isophthalate-5-sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyl dicarboxylic acid, naphthalenedicarboxylic acid, benzophenone dicarboxylic acid, furan dicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dicarboxylic acid diphenyl sulfide, etc. A commercially available example is G4-142MHR (manufactured by Nippon Kayaku Co., Ltd.).

[0143] [Hardening Accelerator]

[0144] In addition to using the compound represented by formula (a), a curing accelerator may also be used in the curing resin composition of the present invention. As a curing accelerator, anionic curing accelerators that promote the curing reaction by generating anions through irradiation or heating with ultraviolet or visible light are preferred, or cationic curing accelerators that promote the curing reaction by generating cations through irradiation or heating with ultraviolet or visible light are preferred.

[0145] [Anionic hardening accelerator]

[0146] Examples of anionic hardening accelerators include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, tetrabutylammonium salts, triisopropylmethylammonium salts, trimethyldecylammonium salts, cetyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but these are not limited to these. Furthermore, one or more of these can be used together.

[0147] [Catonic hardening accelerator]

[0148] Examples of cationic hardening accelerators include, but are not limited to, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ions of quaternary salts are halogens, organic acid anions, hydroxide ions, etc., without specific designation, but organic acid anions and hydroxide ions are particularly preferred), tin octoate, zinc octope (2-ethylhexanoate), zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc benzylate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc. Furthermore, one or more of these can be used in combination.

[0149] The curing accelerator is preferably used in the range of 0.001 parts by weight to 15 parts by weight relative to 100 parts by weight of epoxy resin, and more preferably in the range of 0.01 parts by weight to 5 parts by weight.

[0150] [Thermal polymerization initiator]

[0151] The curable resin composition of the present invention may also contain a thermal polymerization initiator. A thermal polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylene unsaturated bonds, and examples include: olefin metathesis polymerization initiators, thermal anionic polymerization initiators, thermal cationic polymerization initiators, and thermal free radical polymerization initiators. Preferably, a thermal free radical polymerization initiator with curing properties and moderate stability is used. A thermal free radical polymerization initiator is a compound that generates free radicals and initiates a chain polymerization reaction by heating. Examples of thermal free radical polymerization initiators include: organic peroxides, azo compounds, and benzopinnatols. Organic peroxides are preferred because they control the curing temperature or suppress gas escape and have little impact on the electrical properties of the decomposition products.

[0152] [Organic peroxides]

[0153] Examples of organic peroxides include: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxy ketals such as tert-butyl peroxide and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxide, tert-butyl peroxide, tert-butyl peroxide, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, and 2-ethyl peroxide-2-ethylhexanoate. Alkyl peroxide esters such as tert-amyl hexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-amyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxide-3,5,5-trimethylhexanoate, and tert-amyl peroxybenzoate; peroxy carbonate esters such as di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl isopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctanoate, and lauroyl peroxide, but not limited to these. Furthermore, one or more of these may be used. Among the organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxide esters, and peroxy carbonates are preferred, and dialkyl peroxides are more preferred.

[0154] [Azo compounds]

[0155] Examples of azo compounds include azobisisobutyronitrile, 4,4'-azobis(4-cyanopentaic acid), and 2,2'-azobis(2,4-dimethylpentanonitrile), but these are not limited to. Furthermore, one or more of these compounds may be used.

[0156] [Photopolymerization initiator]

[0157] The curable resin composition of the present invention may also contain a photopolymerization initiator. Examples of photopolymerization initiators include: free radical photopolymerization initiators, cationic photopolymerization initiators, and photobase initiators. Among these, free radical photopolymerization initiators with high curability are preferred.

[0158] [Free radical photopolymerization initiator]

[0159] Examples of free radical photopolymerization initiators include: 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (manufactured by BASF Japan, "IRGACURE OXE-01"), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (manufactured by BASF Japan). (Manufactured in Japan), including oximes such as "IRGACURE OXE-02"; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one, etc.; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, etc. Anthraquinones such as 2-pentylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"), 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-dimethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc., are known general free radical photopolymerization initiators.

[0160] [Catonic photopolymerization initiator]

[0161] Examples of cationic photopolymerization initiators include: diazonium salts of Lewis acids, monium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine photopolymerization initiators, borate photopolymerization initiators, and other photoacid generators.

[0162] <Diazoonium salts of Lewis acids>

[0163] Examples of diazonium salts that are Lewis acids include p-methoxyphenyldiazonium fluorophosphate and N,N-diethylaminophenyldiazonium hexafluorophosphate (such as Sun Aid SI-60L / SI-80L / SI-100L manufactured by Sanxin Chemical Industry Co., Ltd.). Examples of monium salts that are Lewis acids include diphenylmonium hexafluorophosphate and diphenylmonium hexafluoroantimonate. Examples of sulfonium salts that are Lewis acids include triphenylsulfonium hexafluorophosphate (such as Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.) and triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.). Examples of phosphonium salts that are Lewis acids include triphenylphosphonium hexafluoroantimonate.

[0164] <Other halides>

[0165] Other halides that can be listed include: 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl] ethyl ketone (Trigonal PI, etc. manufactured by Akzo), 2,2-dichloro-1-4-(phenoxyphenyl) ethyl ketone (Sandray 1000, etc. manufactured by Sandoz), and α,α,α-tribromomethylphenyl sulfone (BMPS, etc. manufactured by Iron Chemical Company). Examples of triazine initiators include: 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (Triazine A manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (Triazine PMS manufactured by Panchim, etc.), and 2,4-trichloromethyl-(piperyl)-6-triazine (Panchim, etc.). Triazine PP (manufactured by m) company, 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B (manufactured by Panchim) company), 2[2'(5-methylfuranyl)ethylidene]-4,6-bis(trichloromethyl)-triazine (manufactured by SANWA Chemical) company, 2(2'-furanylethylidene)-4,6-bis(trichloromethyl)-triazine (manufactured by SANWA Chemical) company, etc.

[0166] <Borate-based photopolymerization initiators>

[0167] Examples of borate-based photopolymerization initiators include NK-3876 and NK-3881 manufactured by Nippon Photosensitive Pigments. Examples of other photoacid generators include: 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis(2-amino-propane) dihydrochloride (V50 manufactured by Fujifilm and Kojin Chemical Co., Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (VA044 manufactured by Fujifilm and Kojin Chemical Co., Ltd.), [η-5-2-4-(cyclopentadecanyl)(1,2,3,4,5,6,η)-(methylethyl)-benzene]iron(II) hexafluorophosphate (CibaGeigy). Products manufactured by Geigy include Irgacure 261, bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium (CGI-784 manufactured by Ciba Geigy), etc.

[0168] [Photoalkali initiator]

[0169] Examples of photoalkali initiators include: TRD-001 (manufactured by Nippon Kayaku Co., Ltd.), TRD-008 (manufactured by Nippon Kayaku Co., Ltd.), WPBG-300 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), WPBG-345 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), PBG-266 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), WPBG-018 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), WPBG-027 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), WPBG-140 (manufactured by Fujifilm and Koji Chemical Co., Ltd.), and WPBG-165 (manufactured by Fujifilm and Koji Chemical Co., Ltd.).

[0170] The amount of photopolymerization initiator added is preferably 0.01 to 5 parts by weight, and particularly preferably 0.01 to 3 parts by weight, relative to 100 parts by weight of the curing resin composition. A single photopolymerization initiator may be used, or two or more may be used simultaneously.

[0171] [Polymerization Inhibitor]

[0172] The curable resin composition of the present invention may also contain polymerization inhibitors. By containing polymerization inhibitors, storage stability can be improved, and the reaction initiation temperature can be controlled. Controlling the reaction initiation temperature makes it easier to ensure flowability, and facilitates B-stage processes such as prepreg forming without compromising impregnation in glass fiber cloth, etc. If the polymerization reaction proceeds excessively during prepreg forming, adverse conditions such as difficulty in lamination can easily occur during the lamination process.

[0173] The amount of polymerization inhibitor used relative to 100 parts by weight of the curing resin composition of the present invention is 0.008 parts by weight to 1 part by weight, preferably 0.01 parts by weight to 0.5 parts by weight.

[0174] Examples of polymerization inhibitors include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitryl radical-based inhibitors. Furthermore, one or more polymerization inhibitors may be used. In this embodiment, phenolic, hindered amine-based, nitroso-based, and nitryl radical-based inhibitors are preferred.

[0175] [Phenolic polymerization inhibitor]

[0176] Examples of monophenols that act as inhibitors of phenolic polymerization include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylphenylamino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; 2,2'-methylenebis(4-methyl 6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 2,2-thio-diethylene... Bisphenols such as bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, and bis(3,5-di-tert-butyl-4-hydroxybenzyl sulfonate ethyl ester) calcium; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]ethylene glycol ester, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and other high molecular weight phenols, but not limited to these.

[0177] [Diamond-based polymerization inhibitor]

[0178] Examples of sulfur-based polymerization inhibitors include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearate 3,3'-thiodipropionate, but are not limited to these.

[0179] [Phosphorus-based polymerization inhibitor]

[0180] Examples of phosphorus-based polymerization inhibitors include: triphenyl phosphite, diphenyl isodel phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, pentaerythritol diisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis(octadecyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrayl bis(2,4-di-tert-butyl-4-methylphenyl) phosphite, and bis[2-tert-butylphenyl] phosphite. Phosphites such as butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and oxaphosphaphenanthrene oxides, but not limited to these.

[0181] [Hindered amine polymerization inhibitor]

[0182] Examples of inhibitors for hindered amine polymerization include: Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, and Adekastab L. A-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, Tinuvin 791FB, etc., but not limited to these.

[0183] [Nitrosyl polymerization inhibitor]

[0184] Examples of nitrosyl polymerization inhibitors include, but are not limited to, ammonium salts of p-nitrosophenol, N-nitrosodiphenylamine, and N-nitrosophenylhydroxyamine (cupferron). Among these, ammonium salts of N-nitrosophenylhydroxyamine (cupferron) are preferred.

[0185] [Nitroacyl radical polymerization inhibitor]

[0186] Examples of inhibitors for nitryl radical polymerization include di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidine-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxy, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxy, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxy, but these are not limited to.

[0187] [Flame retardant]

[0188] The curable resin composition of the present invention may also contain a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred.

[0189] The phosphorus-based flame retardants described herein can be reactive or additive. Specific examples include: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trimethylxyl phosphate, trimethylxyl phosphate, toluene diphenyl phosphate, toluene-2,6-dimethylxyl phosphate, 1,3-phenylenebis(dimethylxyl phosphate), 1,4-phenylenebis(dimethylxyl phosphate), 4,4'-biphenyl(dimethylxyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the aforementioned phosphanes; red phosphorus, etc., but are not limited to these. Furthermore, one or more of these can be used together. The exemplary substances are preferably phosphate esters, phosphines, or phosphorus-containing epoxy compounds, and particularly preferably 1,3-phenylenebis(dimethylbenzyl phosphate), 1,4-phenylenebis(dimethylbenzyl phosphate), 4,4'-biphenyl(dimethylbenzyl phosphate), or phosphorus-containing epoxy compounds.

[0190] The flame retardant content is preferably in the range of 0.1 to 0.6 parts by weight relative to 100 parts by weight of the curing resin composition. If it is less than 0.1 parts by weight, the flame retardancy may become insufficient; if it is more than 0.6 parts by weight, it may adversely affect the hygroscopicity and dielectric properties of the cured material.

[0191] [Light stabilizer]

[0192] The curable resin composition of the present invention may also contain a light stabilizer. As a light stabilizer, a hindered amine light stabilizer is preferred, and a hindered amine light stabilizer (HALS) is particularly preferred. Examples of HALS include: the reaction product of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine with N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, the reaction product of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinyl succinate, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl- Examples of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, etc., but not limited to these. Furthermore, one or more of these may be used.

[0193] The content of light stabilizer is preferably in the range of 0.001 parts by weight to 0.1 parts by weight relative to 100 parts by weight of the curing resin composition. If it is less than 0.001 parts by weight, there is a possibility that the light stabilizing effect will not be sufficient; if it is more than 0.1 parts by weight, there is a possibility that it will have an adverse effect on the hygroscopicity and dielectric properties of the cured material.

[0194] [Adhesive Resin]

[0195] The curable resin composition of the present invention may also contain an adhesive resin. Examples of adhesive resins include, but are not limited to, polyphenylene ether compounds, polyamide resins, polyimide resins, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy-NBR resins, and silicone resins. Furthermore, one or more of these resins may be used.

[0196] [Polyphenylene ether compounds]

[0197] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds having vinyl unsaturated bonds are preferred, and more preferably polyphenylene ether compounds having acrylic, methacrylic, or styrene structures. Commercially available examples include SA-9000 (manufactured by SABIC, a polyphenylene ether compound with methacrylic groups) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical, a polyphenylene ether compound with a styrene structure).

[0198] The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. Furthermore, if the molecular weight is greater than 5000, the melt viscosity becomes high, resulting in insufficient flowability and a tendency for poor molding. Additionally, reactivity decreases, the curing reaction requires a longer time, and the amount of unreacted material that does not enter the curing system tends to decrease the glass transition temperature of the cured product, thus reducing its heat resistance.

[0199] If the number-average molecular weight of the polyphenylene ether compound is 500 to 5000, it can exhibit excellent heat resistance and formability while maintaining excellent dielectric properties. Furthermore, the number-average molecular weight can be specifically determined using methods such as gel permeation chromatography.

[0200] Polyphenylene ether compounds can be obtained through polymerization reactions or through redistribution reactions of high molecular weight polyphenylene ether compounds with a number average molecular weight of approximately 10,000 to 30,000. Alternatively, they can be given free radical polymerizability by reacting these compounds with compounds containing vinyl unsaturated bonds, such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene. Polyphenylene ether compounds obtained through redistribution reactions can be obtained, for example, by heating high molecular weight polyphenylene ether compounds in a solvent such as toluene in the presence of a phenol compound and a free radical initiator. Polyphenylene ether compounds obtained through redistribution reactions thus possess hydroxyl groups derived from phenolic compounds at both ends of the molecular chain, which contribute to hardening. Therefore, they not only maintain higher heat resistance but also allow for the introduction of functional groups at both ends of the molecular chain after modification with compounds containing vinyl unsaturated bonds, which is preferred in this respect. Furthermore, polyphenylene ether compounds obtained through polymerization reactions exhibit excellent flowability, which is also preferred in this respect.

[0201] In the case of polyphenylene ether compounds obtained through polymerization, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. Furthermore, in the case of polyphenylene ether compounds obtained through redistribution reactions, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, this takes into account adjusting the amount of phenolic compounds used in the redistribution reaction, etc. That is, the more phenolic compounds are used, the lower the molecular weight of the obtained polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether), etc., can be used as the high molecular weight polyphenylene ether compound subjected to the redistribution reaction. Furthermore, there are no particular limitations on the phenolic compounds used in the redistribution reaction; polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in their molecules, such as bisphenol A, phenolic varnish, cresol varnish, etc., are preferably used. These can be used alone or in combination of two or more.

[0202] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by weight, more preferably 10 to 750 parts by weight, relative to 100 parts by weight of the curing resin composition. If the content of the polyphenylene ether compound is within the aforementioned range, not only are the heat resistance and other properties excellent, but also a cured product that fully utilizes the excellent dielectric properties of the polyphenylene ether compound can be obtained, which is preferred in this respect.

[0203] [Polyamide resin]

[0204] Examples of polyamide resins include: reaction products of diamines, diisocyanates, oxazolines, and dicarboxylic acids; reaction products of diamines and acyl chlorides; and ring-opening polymers of lactam compounds. Furthermore, one or more of these may be used.

[0205] The following are specific examples of the raw materials, but are not limited to these.

[0206] <Diamine>

[0207] Ethylenediamine, Trimethylenediamine, Tetramethylenediamine, Pentamethylenediamine, Hexamethylenediamine, Heptamethylenediamine, Octamethylenediamine, Nonamethylenediamine, Decanediamine, Undecanediamine, Dodecanediamine, Tridecanediamine, Tetradecanediamine, Pentadecanediamine, Hexadecanediamine, Heptadecanediamine, Octadecanediamine, Nonadecanediamine, Eicosanediamine, 2-Methyl-1,5-diaminopentane, 2-Methyl-1,8-diaminooctane, Dimer diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylenediamine, norbornenediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthyldiamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-toluidine 4,4'-Methylenebis-o-ethylaniline, 4,4'-Methylenebis-2-ethyl-6-methylaniline, 4,4'-Methylenebis-2,6-diisopropylaniline, 4,4-Ethylenediphenylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)benzene [4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.

[0208] <Diisocyanate>

[0209] Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanomethyl)benzene, 1,3-bis(isocyanomethyl)cyclohexane, bis(4-isocyanophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyano-2-propyl)benzene, 2,2-bis(4-isocyanophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc.

[0210] <Dicarboxylic acid>

[0211] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, sodium isophthalic acid-5-sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, benzophenone dicarboxylic acid, furan dicarboxylic acid, 4,4'-dicarboxylic acid diphenyl ether, 4,4'-dicarboxylic acid diphenyl sulfide, etc.

[0212] <Acyl chloride>

[0213] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl oxide, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipyl dichloride, dodecyl dichloride, azelaic chloride, 2,5-furan dicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azobisbenzoyl dichloride, etc.

[0214] <lactam>

[0215] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0216] [Polyimide resin]

[0217] Examples of polyimide resins that can be cited include the reaction products of the diamine with the tetracarboxylic acid dianhydrides exemplified below, but are not limited to these. LDFI089 (a polyimide compound obtained by the method described in WO2023013224A1) is a specific example. Furthermore, one or more of these can be used.

[0218] <Tetracarboxylic dianhydride>

[0219] 4,4'-(hexafluoroisopropylidene) phthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 2,2',3,3'-benzophenonetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, methylene-4,4'-phthalic anhydride, 1,1-ethylidene-4,4'-phthalic anhydride, 2,2'-propylidene-4,4'-phthalic anhydride, 1,2-ethylidene -4,4'-Diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 4,4'-oxydiphthalic anhydride, thio-4,4'-diphthalic anhydride, sulfonyl-4,4'-diphthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2- [Propyl]phenyl dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracitetetracarboxylic acid dianhydride, 1,2,7 8-Phenylacetetrate dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid)2-Dicarboxylic acid dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3, [2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenylbis(triphenyltriacrylic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dihydride, etc.

[0220] [Allyl compounds]

[0221] Examples of allyl compounds include monoallyl isocyanurate, diallyl isocyanurate, and triallyl isocyanurate. Specific examples include "TAIC" (manufactured by Mitsubishi Chemical Corporation), "MA-DGIC", and "DA-MGIC" (manufactured by Shikoku Chemical Industry Co., Ltd.).

[0222] Polybutadiene and its modified forms

[0223] Polybutadiene and its modified forms are polybutadiene or compounds having a structure derived from polybutadiene within their molecules. The structure derived from polybutadiene can be converted, partially or completely, of unsaturated bonds into single bonds through hydrogenation. Examples of polybutadiene and its modified forms include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. Furthermore, one or more of these can be used. From the viewpoint of dielectric properties, polybutadiene or styrene-butadiene rubber is preferred. Examples of styrene butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Corporation). Examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Corporation). The molecular weight of both polybutadiene and styrene butadiene rubber is preferably 500 to 10,000 by weight average, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. If the molecular weight is below the lower limit of this range, the volatile content is high, making it difficult to adjust the solid composition during prepreg preparation. If the molecular weight is above the upper limit of this range, the compatibility with other curing resins deteriorates. Generally, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, compatibility with low-polarity compounds, such as compounds mainly containing hydrocarbons or compounds containing only hydrocarbons, is difficult to guarantee due to their polarity. On the other hand, the compound of this embodiment, since it is not designed with a framework that actively introduces heteroatoms such as oxygen or nitrogen, also exhibits excellent compatibility with materials having low polarity and low dielectric properties, or compounds containing only hydrocarbons.

[0224] Polystyrene and its modified forms

[0225] Polystyrene and its modified forms are polystyrene or compounds that have a structure derived from polystyrene within their molecules.

[0226] Examples of polystyrene and its modified forms include: polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocros RPS-1005 and RP-61, both manufactured by Nippon Catalyst Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), and SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104). All are manufactured by Kuraray Corporation. SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymers: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Corporation), SEBS (styrene-ethylene-butene-styrene block copolymers: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Corporation), SEEPS-OH (a compound with hydroxyl groups at the end of the styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252). Polystyrene and its modified forms include, but are not limited to, polystyrene (manufactured by Kuraray Corporation), SIS (styrene-isoprene-styrene block copolymers: Septon 5125 and Septon 5127, both manufactured by Kuraray Corporation), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: Hybrar 7125F and Hybrar 7311F, both manufactured by Kuraray Corporation), SIBS (styrene-isobutylene-styrene block copolymers: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T, all manufactured by Kaneka Corporation, and Septon V9827, manufactured by Kuraray Corporation), and others. Furthermore, one or more of these can be used. Polystyrene and its modified forms have higher heat resistance and are less prone to oxidative degradation; therefore, the absence of unsaturated bonds is preferred.In addition, there are no particular restrictions if the weight average molecular weight of polystyrene and its modified products is 10,000 or more. However, if it is too large, in addition to the deterioration of compatibility with polyphenylene ether compounds, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also be deteriorated, making it difficult to mix and ensure solvent stability. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0227] Polyethylene and its modified forms

[0228] Polyethylene and its modified forms are polyethylene or compounds having a structure derived from polyethylene within their molecules. Examples of polyethylene and its modified forms include: ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylene norbornene copolymers (such as EBT: K-8370EM, K-9330M manufactured by Mitsui Chemicals), ethylene-propylene-vinyl norbornene copolymers (such as VNB-EPT: PX-006M, PX-008M, PX-009M manufactured by Mitsui Chemicals), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers, but are not limited to these. From the viewpoint of improving heat resistance, ethylene-propylene-ethylene norbornene copolymers and ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure are preferred. Furthermore, one or more of these can be used. There are no particular restrictions if the weight average molecular weight of polyethylene and its modified products is above 10,000. However, if it is too large, in addition to the deterioration of compatibility with polyphenylene ether compounds, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also be deteriorated, making it difficult to mix and ensure solvent stability. Therefore, a weight average molecular weight of about 10,000 to 300,000 is preferred.

[0229] The amount of adhesive resin used is preferably 0.05 to 50 parts by weight relative to 100 parts by weight of the curing resin composition, within a range that does not impair the flame retardancy and heat resistance of the cured product, and more preferably 0.05 to 20 parts by weight as needed. Among these compounds, polyphenylene ether compounds, polybutadiene and its modified forms, and polystyrene and its modified forms are preferred in terms of the balance of heat resistance, adhesion, and dielectric properties. The presence of these compounds improves the brittleness of the cured product and enhances its adhesion to metals, suppressing cracking of the encapsulation during reflow soldering or reliability tests such as thermal cycling.

[0230] [Inorganic filler material]

[0231] The curable resin composition of the present invention may also contain inorganic fillers. Examples of inorganic fillers include: fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, glass powder, etc., or inorganic fillers formed into spherical or fragmented shapes, but are not limited to these. Furthermore, one or more of these fillers may be used.

[0232] Regarding the inorganic filler, when obtaining a curable resin composition for semiconductor sealants, thermal conductivity and heat dissipation materials, etc., the amount used is preferably 80 to 92 parts by weight, and more preferably 83 to 90 parts by weight, out of 100 parts by weight of the curable resin composition. Furthermore, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper-clad laminates or prepregs, RCC and other substrate materials, the amount of the inorganic filler used is preferably 5 to 80 parts by weight, and more preferably 10 to 60 parts by weight, out of 100 parts by weight of the curable resin composition.

[0233] The curable resin composition of this embodiment may further use compounds having ethylene unsaturated bonds, isocyanate compounds, maleimide compounds, cyanate compounds, etc., one of which may be used or multiple of which may be used in combination.

[0234] [Compounds containing ethylene-like unsaturated bonds]

[0235] Compounds with vinyl unsaturated bonds are those that can be polymerized by heat or light regardless of whether a polymerization initiator is used, and which have more than one vinyl unsaturated bond in their molecule.

[0236] Examples of compounds containing vinyl unsaturated bonds include: isobornyl acrylate, acryloylmorpholine and other (meth)acrylate compounds; reaction products of the aforementioned phenolic compounds with halogenated compounds containing vinyl unsaturated bonds (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, methacryloyl chloride, etc.); phenols containing vinyl unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric trichlorophenone, etc.). The reaction products of chloride, etc.; reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.) and their acid-modified derivatives; styrene resins; allyl-containing compounds; acenaphthenic acid-containing compounds (acenaphthenic acid, etc.); isocyanuric acid derivatives (TAIC manufactured by Mitsubishi Chemical Corporation, MA-DGIC, DA-MGIC, MeDAIC, L-DAIC, DD-1, etc. manufactured by Shikoku Chemical Corporation), etc., but not limited to these. Furthermore, one or more of these may be used.

[0237] As (meth)acrylate compounds, commercially available products can be used, such as: STR-2000 (manufactured by Nippon Kayaku Co., Ltd., a neophenol (Xyloc) type styrene resin), KAYARAD (registered trademark) R-604, KAYARAD (registered trademark) R-684, KAYARAD (registered trademark) HX-220, KAYARAD (registered trademark) HX-620, KAYARAD (KA... KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) DPCA-60, KAYARAD (registered trademark) DPEA-12, KAYARAD (registered trademark) PET-30, KAYARAD (registered trademark) ZXR-1801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), KAYARAD (registered trademark) ZXR-1806H (trade name) Product Name), KAYARAD (Registered Trademark) ZXR-1810H (Trade Name), KAYARAD (Registered Trademark) ZXR-1889H (Trade Name), KAYARAD (Registered Trademark) ZCR-6001H, KAYARAD (Registered Trademark) ZCR-6002H, KAYARAD (Registered Trademark) ZCR-8001H, KAYARAD (Registered trademarks) ZCR-8002H, KAYARAD (Registered trademarks) ZAR-2001H, KAYARAD (Registered trademarks) ZAR-2002H, KAYARAD (Registered trademarks) UXE-3000, KAYARAD (Registered trademarks) PCR-1222H, CCR-1171H, KAYARAD (Registered trademarks) ZFR-1494H, etc. These compounds with ethylene unsaturated bonds can be used alone or in combination of two or more.

[0238] [Isocyanate compounds]

[0239] An isocyanate compound is a compound having two or more isocyanate groups within its molecule. Examples of isocyanate compounds include: aromatic diisocyanates such as terephthalic diisocyanate, isophthalic diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as biuret bodies of one or more isocyanate monomers or isocyanates formed by trimerization of the aforementioned diisocyanate compounds; and polyisocyanates obtained by carbamate reaction of the aforementioned isocyanate compounds with polyol compounds, but are not limited to these examples. In addition, one of these can be used, or multiple can be used together.

[0240] [Maleimide compounds]

[0241] Maleimide compounds are compounds that have one or more maleimide groups within their molecules. Examples of maleimide compounds include: phenylmaleimide, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and neophenolic maleimide compounds. (Anilix maleimide, manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), biphenyl aralkyl maleimide compounds (those solidified by solvent distillation of the resin solution containing maleimide compound (M2) described in Example 4 under reduced pressure, as disclosed in Japanese Patent Application Publication No. 2009-001783), diaminocumylbenzene maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compounds having an indane structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, "Material Stage" The maleimide compounds described in “Epoxy Resin CAS Number Story ~ Curing Agent CAS Number Memorandum No. 31 (1)” or “Material Stage (MATERIAL STAGE)” Vol. 19, No. 2 2019 “Epoxy Resin CAS Number Story ~ Curing Agent CAS Number Memorandum No. 32 (2)” include commercially available products such as MIR-3000-70MT (biphenyl aralkyl maleimide compound, manufactured by Nippon Kayaku Co., Ltd.) and MIZ-001 (manufactured by Nippon Kayaku Co., Ltd.), but are not limited to these. In addition, one or more of these can be used.

[0242] [Cyanate ester compounds]

[0243] Cyanate ester compounds are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: dicyanophenyl, tricyanophenyl, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl) sulfide, phenolic varnish cyanate ester, and compounds formed by converting the hydroxyl groups of phenol-dicyclopentadiene cocondensates to cyanate ester groups, etc. Commercially available products include SYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd., a bisphenol A cyanate ester resin), but are not limited to these. Furthermore, one or more of these can be used.

[0244] Furthermore, the cyanate ester compound described in Japanese Patent Application Publication No. 2005-264154 is particularly preferred as a cyanate ester compound due to its excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0245] To induce the trimerization of cyanate groups to form a sym-triazine ring, cyanate compounds may contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetylacetone, and dibutyltin maleate, as needed.

[0246] The catalyst is preferably used in amounts of 0.0001 to 0.10 parts by mass, more preferably 0.00015 to 0.0015 parts by mass, relative to 100 parts by mass of the cyanate compound and the curing resin composition.

[0247] The curable resin composition of the present invention can also be used with commonly available latent curing catalysts. Examples of commonly available latent curing catalysts include: tetraphenylphosphonium tetraphenylborate (TPP-K manufactured by Hokko Chemical Co., Ltd.), tetraphenylborate of 1,8-diazabicyclo[5,4,0]-7-undecene (DBU) benzyl modified form (U-CAT5002 manufactured by San-apro Co., Ltd.), phenolic resin salt of 1,5-diazabicyclo[4,3,0]-5-nonene (DBN) (U-CAT881 manufactured by San-apro Co., Ltd.), adduct-type latent curing agents (PN-23J manufactured by Ajinomoto Fine-Techno Co., Ltd., Fujicure FXR-1030 manufactured by T&K TOKA Co., Ltd., etc.), and thiol-based liquid latent curing agents (T&K TOKA Co., Ltd.). The products mentioned include, but are not limited to, those manufactured by TOKA (such as Fujicure 7004). Furthermore, one or more of these products may be used.

[0248] [additive]

[0249] The curable resin composition of the present invention may also contain additives. Examples of additives include: modified acrylonitrile copolymers, surface treatment agents for fillers such as polyethylene, fluororesins, silicone gels, silicone oils, and silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0250] The curable resin composition of the present invention may also contain commonly used epoxy resin additives, such as dyes, fluorescent whitening agents, reinforcing materials, white pigments or other pigments, nucleating agents, surfactants, plasticizers, viscosity modifiers, flow modifiers, antioxidants, ultraviolet absorbers, and light stabilizers, as additives other than those mentioned above.

[0251] The amount of additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, relative to 100 parts by weight of the curing resin composition.

[0252] The method for preparing the curable resin composition of the present invention is not particularly limited, and it is prepared by measuring and mixing the components in a specified amount. For example, it can also be prepared by mixing or melt-kneading using a roller mixer, kneader, or extruder after premixing.

[0253] The curing method for the curable resin composition of the present invention is not particularly limited, and existing known curing devices such as closed curing ovens or tunnel ovens capable of continuous curing can be used. There are also no particular restrictions on the heating source; existing known methods such as hot air circulation, infrared heating, and high-frequency heating can be used. The curing temperature and curing time can be set appropriately.

[0254] The use of the curable resin composition of the present invention is not particularly limited and can be applied to various fields and products that use resin materials. It can be widely used in electrical / electronic materials, construction, civil engineering, automotive, medical materials, etc.

[0255] For example, examples of applications in electrical / electronic materials include: adhesives, adhesive films, sealants, semiconductor sealants, insulating materials, heat conduction and heat dissipation materials, hot melt materials, coatings, potting compounds, etc. More specifically, examples include: printed wiring boards, copper foil, copper-clad laminates, interlayer insulation materials, wiring wrapping films, resin-coated copper foil (RCC), prepregs and other sealing materials or layer forming materials for electronic components, color filters, flexible display films, resist materials, solder resist inks, alignment films and other forming materials for display devices, resist materials, buffer coatings and other forming materials for semiconductor devices, holograms, optical waveguides, optical circuits, optical circuit components, anti-reflective films and other forming materials for optical components.

[0256] Example

[0257] The present invention will now be described in more detail with reference to embodiments, but the invention is not limited to any of the embodiments described herein. Furthermore, unless otherwise specified, “parts” and “%” are used as mass terms.

[0258] [ 1 [H-NMR measurement]

[0259] The following methods were used to determine 1 H-NMR.

[0260] Dissolve 10 mg of the sample in approximately 0.5 ml of heavy DMSO, and place it into... The measurements were performed in 5 mm sample tubes using a JNM-ECS400 manufactured by Nippon Electronics Co., Ltd. The offset values ​​were based on DMSO (δ=2.49 ppm).

[0261] [Synthetic Example 1] Synthesis of Compound C1

[0262] 13.86 parts of 4-dimethylaminopyridine (4-DMAP) and 83.14 parts of acetone were added to a 300 ml separable flask, and the mixture was heated to 45°C to dissolve it. Then, while monitoring the heating process, 20.00 parts of benzyl bromide were added dropwise, and the reaction was allowed to proceed for 2 hours. Afterward, the mixture was cooled to 30°C for crystallization. The solid was recovered by suction filtration and washed three times with excess acetone. The resulting wet filter cake was dried under reduced pressure at 45°C for 4 hours to obtain compound C1, represented by formula (1), as a white solid in 96% yield. The obtained C1 was then... 1 H-NMR spectral data are shown in Figure 1 .

[0263] [Chemistry 13]

[0264]

[0265] [Synthesis Example 2] Synthesis of Compound C2

[0266] 12.84 parts of sodium tetraphenylborate and 50 mL of methanol were placed in a 300 mL separable flask and dissolved. A solution of compound C1 (10.00 parts) pre-dissolved in 50 mL of methanol was slowly added dropwise to the solution, and the mixture was allowed to react for 2 hours, resulting in crystallization. The solid was recovered by suction filtration and washed three times with excess methanol. The obtained wet filter cake was dried under reduced pressure at 45°C for 4 hours to obtain compound C2, represented by formula (2), as a white solid in 92% yield. The obtained C2 was... 1 H-NMR spectral data are shown in Figure 2 .

[0267] [Chemistry 14]

[0268]

[0269] [Synthesis Example 3] Synthesis of Compound C3

[0270] Using 8.97 parts pyridine instead of 13.86 parts 4-DMAP, the compound C3 represented by formula (3) was obtained as a white solid in 92% yield, otherwise identical to that in Synthesis Example 1. The obtained C3 was then... 1 H-NMR spectral data are shown in Figure 3 .

[0271] [Chemistry 15]

[0272]

[0273] [Synthesis Example 4] Synthesis of Compound C4

[0274] Using compound C3 (8.53 parts) instead of compound C1 (10.00 parts), compound C4, represented by formula (4), was obtained as a white solid in 93% yield, otherwise identical to that in Synthesis Example 2. The obtained C4 was... 1 H-NMR spectral data are shown in Figure 4 .

[0275] [Chemistry 16]

[0276]

[0277] [Synthetic Example 5] Synthesis of Compound C5

[0278] 7.92 parts of phenyltrimethoxysilane, 6.40 parts of 2,3-dihydroxynaphthalene, and 50 mL of methanol were placed in a 300 mL separable flask and dissolved. A solution prepared by dissolving 1.6 parts of sodium hydroxide in 10 mL of methanol was added to the solution and stirred for 30 minutes. A solution prepared by dissolving 11.73 parts of compound C1 in 25 mL of methanol was slowly added dropwise to the solution, and the reaction was allowed to proceed for 2 hours, resulting in crystallization. The solid was recovered by suction filtration and washed three times with excess methanol. The obtained wet filter cake was dried under reduced pressure at 45°C for 4 hours to obtain compound C5, represented by formula (5), as a gray solid with a yield of 79%. The obtained C5... 1 H-NMR spectral data are shown in Figure 5 .

[0279] [Chemistry 17]

[0280]

[0281] [Comparative Synthesis Example 1] Synthesis of Compound C6

[0282] Using tetraphenylphosphonium bromide (16.80 parts) instead of compound C1 (11.73 parts), compound C6, represented by formula (6), was obtained as a gray solid in 72% yield, similar to Synthesis Example 5. The obtained C6 was then... 1 H-NMR spectral data are shown in Figure 6 .

[0283] [Chemistry 18]

[0284]

[0285] [Synthesis Example 6] Synthesis of Compound C7

[0286] 14.06 parts of 4-dimethylaminopyridine (4-DMAP) and 51.08 parts of acetone were added to a 300 ml separable flask, and the mixture was heated to 50°C to dissolve it. Then, while maintaining heat, 20.00 parts of 3-chlorophenylacetone were added, and the reaction was allowed to proceed for 2 hours. Afterward, the mixture was cooled to 30°C for crystallization. The solid was recovered by suction filtration and washed three times with excess acetone. The resulting wet filter cake was dried under reduced pressure at 80°C for 2 hours to obtain compound C7, represented by formula (7), as a white solid in 95% yield. The obtained C7 was then... 1 H-NMR spectral data are shown in Figure 7 .

[0287] [Chemistry 19]

[0288]

[0289] [Synthesis Example 7] Synthesis of Compound C8

[0290] Using compound C7 (10.58 parts) instead of compound C1 (10.00 parts), compound C8, represented by formula (8), was obtained as a white solid in 34% yield, otherwise identical to that in Synthesis Example 2. The obtained C8 was... 1 H-NMR spectral data are shown in Figure 8 .

[0291] [Chemistry 20]

[0292]

[0293] [Synthetic Example 8] Synthesis of Compound C9

[0294] 10.79 parts of phenyltrimethoxysilane and 5.99 parts of catechol were placed in a 300 ml separable flask. A solution prepared by dissolving 2.18 parts of sodium hydroxide in 35.0 parts of methanol was added and stirred for 30 minutes. A solution prepared by dissolving 15.96 parts of compound C1 in 16.0 parts of methanol was slowly added dropwise to the solution, and the reaction was allowed to proceed for 5 hours, resulting in crystallization. The solid was recovered by suction filtration and washed three times with excess methanol. The obtained wet filter cake was dried under reduced pressure at 80°C for 2 hours to obtain compound C9 represented by the following formula (9) as a white solid in 79% yield. The obtained C9 was... 1 H-NMR spectral data are shown in Figure 9 .

[0295] [Chemistry 21]

[0296]

[0297] [Examples 1-6, 14-16 and Comparative Examples 1-5]

[0298] Phenolic varnish hardener H-1 (hydroxyl equivalent of 107, manufactured by UBE Co., Ltd.), epoxy resin NC-3000 (hydroxyl equivalent of 276, manufactured by Nippon Kayaku Co., Ltd.), and various curing accelerators were added according to the amounts recorded in Tables 1 and 2. Then, 3.45 parts of acetone were added, stirred, mixed, and dried under reduced pressure at 80°C for 1 hour to obtain a solid curable resin composition (equivalence ratio of epoxy equivalent to hydroxyl equivalent of 1.0).

[0299] [Gel time determination at 150℃]

[0300] Appropriate amounts of the curable resin compositions obtained in Examples 1-6, 14, 15 and Comparative Examples 1-5 were placed on a hot plate at 150°C and stirred using a Teflon (registered trademark) spatula. The time to no adhesion on the sample, peeling from the hot plate, or loss of adhesion was measured using a gel time measuring device (Madoka MDK13G, manufactured by Cyber ​​Inc.). The results were set as the initial gel time and are shown in Tables 1-3.

[0301] In addition, after storing the curable resin composition at 50°C for 6 hours, the gel time was measured in the same manner as described above, and is set as the gel time after storage at 50°C for 6 hours and is shown in Tables 1 to 3.

[0302] The retention rate was determined by dividing the gelation time by the initial gelation time after storage at 50°C for 6 hours, and the results are shown in Tables 1 to 3.

[0303] [DSC measurement]

[0304] For the curable resin compositions obtained in Examples 1-6, 14-16 and Comparative Examples 1-5, the measurements were performed using a differential thermal thermogravimetric analyzer (TGA / DSC1 manufactured by Mettler Toledo) at a temperature range of 50°C to 350°C and a heating rate of 10°C / min. The peak temperatures are shown in Tables 1-3.

[0305] [Table 1]

[0306]

[0307] TPP-K: Tetraphenylphosphonium tetraphenylborate (manufactured by Beixing Chemical Industry Co., Ltd.)

[0308] TPP: Triphenylphosphine (manufactured by Fujifilm and Koichi Chemical Co., Ltd.)

[0309] 4-DMAP: 4-Dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0310] As shown in Table 1, it was confirmed that, compared with the curable resin compositions of the comparative examples, the curable resin compositions of the examples have a higher gel time retention rate and excellent storage stability.

[0311] [Table 2]

[0312]

[0313] [Table 3]

[0314]

[0315] As shown in Tables 2 and 3, it was confirmed that, compared with the curable resin compositions of the comparative examples, the curable resin compositions of the examples have a higher gel time retention rate and excellent storage stability.

[0316] [Examples 7-12 and Comparative Examples 6-10]

[0317] The anhydride-based curing agent Rikacid MH-T (anhydride equivalent of 168, manufactured by Shin Nippon Rika Co., Ltd.; the main component is 4-methylhexahydrophthalic anhydride), epoxy resin JER828 (epoxy equivalent of 190, manufactured by Mitsubishi Chemical Co., Ltd.), and various curing accelerators were added according to the amounts recorded in Tables 4 and 5, and stirred and mixed to obtain a liquid curable resin composition (epoxy equivalent to anhydride equivalent of 1.0).

[0318] [Gel time determination at 150℃]

[0319] Appropriate amounts of the curable resin compositions obtained in Examples 7-12 and Comparative Examples 6-10 were placed on a hot plate at 150°C and stirred using a Teflon (registered trademark) spatula. The time to no adhesion on the sample, peeling from the hot plate, or loss of adhesion was measured using a gel time measuring device (Madoka MDK13G, manufactured by Cyber ​​Inc.). The results are set as gel times and are shown in Tables 4 and 5.

[0320] [Viscosity Measurement and Storage Stability Test]

[0321] For the curable resin compositions obtained in Examples 7-12 and Comparative Examples 6-10, the viscosity was measured using an E-type viscometer (TVE-25H manufactured by Toki Industries, Ltd.) at a measurement temperature of 25.0°C. The measured viscosity was set as the initial viscosity and is shown in Tables 4 and 5.

[0322] In addition, after storing the curing resin composition at 25°C for 24 hours, the viscosity was measured in the same manner as described above, and the viscosity increase rate was obtained by dividing it by the initial viscosity. The results are shown in Tables 4 and 5.

[0323] [Table 4]

[0324]

[0325] [Table 5]

[0326]

[0327] As shown in Tables 4 and 5, it was confirmed that the curable resin compositions of the Examples exhibited superior storage stability compared to the Comparative Examples. On the other hand, Comparative Example 7 showed excellent storage stability, but its gel time exceeded 800 seconds, indicating a problem with curability.

[0328] [Example 13 and Comparative Examples 11-13]

[0329] Ten parts of epoxy resin JER828 (epoxy equivalent 190, manufactured by Mitsubishi Chemical Corporation) and 5.78 parts of phenolic varnish hardener H-1 (hydroxyl equivalent 107, manufactured by UBE Corporation) were heated and stirred until completely dissolved. Then, 0.05 parts of various curing accelerators were stirred and mixed to obtain a liquid curable resin composition.

[0330] [Conductivity Measurement]

[0331] 4.0 parts of the curable resin composition obtained in Examples 13 and Comparative Examples 11-13 were poured into an aluminum foil petri dish (No. 2001, manufactured by Nonaka Rikaki Co., Ltd.) and cured at 150°C for 3 hours to obtain a cured product of the curable resin composition. 4.0 g of the obtained cured product and 40 g of ultrapure water were placed in a PCT container made of Teflon (registered trademark), and the PCT container was sealed in a pressure vessel made of SUS. Ion extraction was then performed in a small constant temperature test chamber (120°C / 100 hours). After extraction, the conductivity of the extracted water was measured using a SevenMulti-A instrument manufactured by Mettler Toledo, and the results are shown in Table 6.

[0332] [Table 6]

[0333]

[0334] As shown in Table 6, compared with the curing resin composition of the comparative example, the curing resin composition of the examples has lower conductivity of the extracted water, so it can be said that the cured product contains fewer conductive impurities.

[0335] <Sclerosing Test>

[0336] [Reference Example 1]

[0337] The following proportions were used: 0.2 parts of compound (C2) obtained in Synthesis Example 2, 20 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., a biphenyl aralkyl type epoxy resin), 0.5 parts of KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., a biphenyl aralkyl type phenolic resin), 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., an amine resin), and 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., a biphenyl aralkyl type phenolic resin). 0.5 parts of the following compounds: Unifiner W-575 (manufactured by Unitika, an active ester resin), G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., a carboxylic acid compound), MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., a maleimide resin), MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., a maleimide resin), CYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd., a bisphenol A cyanate ester resin), and OPE-2St. 2200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., polyphenylene ether compound) 60 parts, STR-2000 (manufactured by Nippon Kayaku Co., Ltd., styrene resin) 3 parts, KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., acrylate resin) 1 part, LDFI089 (polyamide-imide resin obtained by the method described in WO2023013224A1) 1 part, Septon 2104 (manufactured by Kuraray Co., Ltd., hydrogenated styrene-based thermoplastic elastomer) 1 part, TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Co., Ltd., allyl compound) 1 part, acenaphthene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts, phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.5 parts, DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound) 1 part, DCP: dicumyl peroxide (chemical drug Norylon (Kayaku The following ingredients are mixed in the following proportions: 1 part of Nouryon (a curing accelerator), 0.5 parts of 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., a curing accelerator), 0.5 parts of TPP (triphenylphosphine, manufactured by Hokko Chemical Co., Ltd., a curing accelerator), 0.1 parts of octope zinc (manufactured by Hope Pharmaceutical Co., Ltd., a curing accelerator), 0.1 parts of Sun Aid SI-B5 (manufactured by Sanshin Chemical Co., Ltd., a curing accelerator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran. The mixture is heated at 110°C for 10 minutes under nitrogen atmosphere and then at 220°C for 1 hour to obtain the cured product.

[0338] [Reference Example 2]

[0339] The following proportions were used: 0.5 parts of compound (C2) obtained in Synthesis Example 2, 50 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., a biphenyl aralkyl epoxy resin), 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., a maleimide resin), 5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., a styrene resin), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., an acrylate resin), 1 part of Irgacure OXE-04 (manufactured by BASF, a photopolymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, a photopolymerization initiator). The mixture was coated onto a PET film with a thickness of 100 μm. A PET film was also attached to the surfaces not in contact with the film. The film was then irradiated with a high-pressure mercury lamp (365 nm) at 3000 mJ / cm². 2 Ultraviolet light can be used to obtain a hardened substance.

[0340] Industrial availability

[0341] The alkali-generating agent of the present invention can be used, for example, as a potential curing accelerator for epoxy compounds. Due to its excellent storage stability, refrigerated storage of the composition is not required; furthermore, due to its excellent curing properties, it can be cured at low temperatures. Because the cured product contains few conductive impurities, it is useful for resin sealing of various electrical / electronic or semiconductor components.

Claims

1. A base generating agent comprising a pyridinium cation and an anionic residue of an organic or inorganic acid, and represented by the following formula (a). [Chemistry 1] (In formula (a), A represents a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain heteroatoms; R1 to R5 represent hydrogen atoms or electron-donating groups, respectively; R1 and R2, R2 and R3, R3 and R4, and R4 and R5 can be bonded to form a ring structure; R6 to R 10 Each of the following groups independently represents a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfinic acid group, sulfonyl group, sulfonic acid group, phosphono group, oxophosphono group, phosphonyl group, phosphonate group, amino group, or ammonium group, R6 and R7, R7 and R8, R8 and R9, R9 and R 10 They can be bonded separately to form a ring structure.

2. The alkali generating agent according to claim 1, wherein R1, R2, R4, and R5 in formula (a) are hydrogen atoms, and R3 is a hydrogen atom or a dimethylamino group.

3. The alkali generating agent according to claim 1 or 2, wherein A in formula (a) is an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, or a divalent hydrocarbon group having 1 to 8 carbon atoms comprising a carbonyl group, an ether group, an ester group, an amide group, or a sulfide group.

4. The base-generating agent according to claim 1 or 2, wherein the anionic residue X in formula (a) - It contains halogen atoms, boron atoms, or silicon atoms.

5. The base-generating agent according to claim 1 or 2, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-1). [Chemistry 2] (In equation (b-1), R) 11 ~R 14 Each of these can be independently represented as a straight-chain or branched alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted aromatic ring.

6. The alkali-generating agent according to claim 5, wherein R of formula (b-1) 11 ~R 14 All are phenyl.

7. The base-generating agent according to claim 1 or 2, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-2). [Chemistry 3] (In formula (b-2), Y1 and Y2 are organic groups, which may be the same or different from each other; Z1 represents a substituted or unsubstituted aromatic ring or an organic group with a heterocyclic ring or a substituted or unsubstituted aliphatic group).

8. The base-generating agent according to claim 1 or 2, wherein the anionic residue X in formula (a) - It is represented by the following formula (b-3) or the following formula (b-4). [Chemistry 4] [Chemistry 5] 。 9. A curable resin composition comprising the alkali-generating agent as described in claim 1 or 2.

10. The curable resin composition according to claim 9, further comprising an epoxy resin.

11. The curable resin composition according to claim 10, further comprising a curing agent.

12. The curable resin composition according to claim 9, further comprising at least one selected from the group consisting of maleimide compounds, polyphenylene ether compounds, compounds having vinyl unsaturated bonds, cyanate ester compounds, polybutadiene and its modifications, polystyrene and its modifications, and polyethylene and its modifications.

13. The curable resin composition according to claim 9 further comprises at least one selected from thermal polymerization initiators, photopolymerization initiators, anionic curing accelerators, and cationic curing accelerators.

14. The curable resin composition according to claim 9, used in any one of semiconductor sealants, adhesives, adhesive films, prepregs, interlayer insulating materials, and thermally conductive and heat-dissipating materials.

15. A cured product, which is a cured product of the curable resin composition as described in claim 9.

16. A printed wiring board having the hardened material as described in claim 15.

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