Curable resin composition and cured product thereof

Abstract

Provided is a curable resin composition that can obtain a cured product having superior low dielectric properties without hindering a curing reaction. A curable resin composition contains a compound represented by the following formula (1) and a compound having a phenolic hydroxyl group, and the content of the compound having a phenolic hydroxyl group is 0.0001 mass part or more and 0.13 mass part or less with respect to 100 mass parts of the compound represented by the following formula (1). (In the above formula (1), X is a hydrocarbon having 1 to 25 carbon atoms, and the multiple Rs each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; m each independently is an integer of 1 to 3; and n is an average value of the number of repetitions, which is a number of 1 to 20.)

Description

Technical Field

[0001] This invention relates to a curable resin composition and its cured form, suitable for use in semiconductor packaging materials, printed circuit boards, laminates and other electrical and electronic components, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, as well as 3D printing applications. Background Technology

[0002] In recent years, due to the expansion of their application fields, laminates carrying electrical and electronic components have required a wider range of highly sophisticated characteristics. Traditional semiconductor chips are mainly mounted on metal lead frames, but high-performance semiconductor chips, such as central processing units (CPUs), are increasingly being mounted on laminates made of polymer materials.

[0003] The 5G mobile communication system, currently under accelerated development, is expected to further achieve high capacity and high-speed communication. In 5G, the frequencies used will trend towards higher frequencies; however, to achieve high-speed communication utilizing high frequencies, reducing transmission losses is crucial, thus requiring further low dielectric properties of the substrate material. Transmission losses occurring on printed circuit boards originate from conductor losses and dielectric losses. As described in Non-Patent Document 1, since conductor losses are proportional to the square root of the relative permittivity of the dielectric and the dielectric loss tangent, improving the dielectric loss tangent, which contributes more significantly than the relative permittivity, is effective in reducing transmission losses. Examples of low dielectric materials include thermoplastics such as PTFE (Polytetrafluoroethylene) and LCP (Liquid Crystal Polymer), but their formability is inferior compared to thermosetting resins. Therefore, it is desirable to develop thermosetting resins and thermosetting resin compositions with excellent low dielectric properties.

[0004] Against this backdrop, thermosetting resin compositions exhibiting low dielectric loss tangent are currently being researched. For example, Patent Document 1 discloses a thermosetting resin composition containing bivinylphenyl ethane (BVPE) and thermosetting polyphenylene ether (Patent Document 1). This thermosetting resin composition improves the storage stability of the resin composition by using a polymerization inhibitor, of which 2,5-bis(1,1-dimethylbutyl)hydroquinone is used.

[0005] Generally speaking, when using polymerization inhibitors containing polar groups (substituents containing heteroatoms) in their structure, the more they are added, the better the storage stability becomes. However, on the other hand, the dielectric properties will deteriorate. This is a trade-off. Moreover, when the target compound for improving storage stability changes, the most suitable polymerization inhibitor will also change. Therefore, this selection is both difficult and an important issue.

[0006] Patent Document 2 discloses a composition containing a maleimide compound, an epoxy resin, and a phenolic resin, which improves storage stability by melting and mixing these components to form a solid state. From the viewpoint of long-distance transportation, such as sea freight, this approach is preferred, as it is ideal that the composition will not deteriorate even in summer shipboard temperatures that may exceed 60°C. However, because specific components are pre-mixed, they need to be dissolved again in an organic solvent after transportation to mix with other materials, and the range of components that can be selected for the composition is narrowed. Furthermore, from the viewpoint of improving dielectric properties, compounds containing compounds such as epoxy resins that generate polar groups such as hydroxyl groups upon curing are undesirable.

[0007] Existing technical documents

[0008] Non-patent literature

[0009] Non-Patent Document 1: "Signal Loss Factors in High-Speed ​​Signal Transmission on Printed Circuit Boards", 29th Spring Conference of the Electronic Packaging Society, Agenda No. (Identity, ID): 16P1-17, 2015

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 2008-115280

[0012] Patent Document 2: Japanese Patent Application Publication No. 2017-101152 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] The present invention was made in view of this situation, and its object is to provide a curable resin composition that does not hinder the curing reaction and can produce a cured product with excellent low dielectric properties.

[0015] Technical means to solve the problem

[0016] That is to say, the present invention relates to the following [1] to [5]. In addition, in the present invention, "(numerical value 1) to (numerical value 2)" indicates that it includes upper and lower limits. [1]

[0018] A curable resin composition comprising a compound represented by formula (1) below and a compound having phenolic hydroxyl groups, wherein the content of the compound having phenolic hydroxyl groups is 0.0001 parts by mass or more and 0.13 parts by mass or less relative to 100 parts by mass of the compound represented by formula (1) below.

[0019] [Chemistry 1]

[0020]

[0021] (In the above formula (1), X is a hydrocarbon with 1 to 25 carbon atoms, and the multiple existing Rs independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms; m is an integer from 1 to 3; n is the average of the number of repetitions, which is a number from 1 to 20) [2]

[0023] According to the curable resin composition described in the preceding paragraph [1], wherein X in the compound represented by the above formula (1) is any structure represented by the following formulas (A) to (H).

[0024] [Chemistry 2]

[0025]

[0026] (In the above formulas (A) to (H), the multiple Rs independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms; the multiple as are independent integers from 1 to 4; the multiple bs are independent integers from 1 to 3.) [3]

[0028] According to the curable resin composition described in the preceding paragraph [1] or [2], the compound having a phenolic hydroxyl group is selected from one or more compounds represented by the following formula (2-1) and compounds represented by the following formula (2-2).

[0029] [Chemistry 3]

[0030]

[0031] (In the above equations (2-1) and (2-2), the multiple existing R1 and R2 independently represent hydrocarbon groups with 1 to 10 carbon atoms; p is an integer from 1 to 5; q is an integer from 1 to 4.) [4]

[0033] The curing resin composition according to any one of the preceding items [1] to [3], wherein the curing resin composition further comprises: a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having ethylene unsaturated bonds, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, and a benzoxazine compound, or more than one of these. [5]

[0035] A hardened material obtained by hardening the hardening resin composition described in any one of the preceding items [1] to [4].

[0036] [The effects of the invention]

[0037] According to the present invention, a curable resin composition can be provided, which can obtain a cured product with excellent low dielectric properties without hindering the curing reaction. Detailed Implementation

[0038] The following describes in more detail the embodiments of the present invention (hereinafter also referred to as "this embodiment").

[0039] The curable resin composition of this embodiment comprises a compound represented by the following formula (1) and a compound having phenolic hydroxyl groups.

[0040] [Chemistry 4]

[0041]

[0042] In formula (1) above, X is a hydrocarbon with 1 to 25 carbon atoms. Preferably, it contains a methylene chain, an alicyclic structure, or an aromatic ring; more preferably, it contains a methylene chain or an aromatic ring; and even more preferably, it contains at least one aromatic ring. The inclusion of an aromatic ring suppresses molecular vibrations, resulting in good dielectric properties and also contributing to improved heat resistance. Each of the multiple Rs independently represents a hydrogen atom or a hydrocarbon group with 1 to 5 carbon atoms, preferably a hydrogen atom or a carbon group with 1 to 3 carbon atoms. Hydrocarbons with 5 or fewer carbon atoms are less prone to molecular vibrations when exposed to high frequencies, thus exhibiting particularly excellent electrical properties. Furthermore, solvent solubility can be imparted without significantly impairing heat resistance. m is an integer from 1 to 3, more preferably 1 to 2. n is the average of the number of repetitions, which is a number from 1 to 20, preferably 1.1 to 20, particularly preferably 1.1 to 10, and most preferably 1.1 to 5. The value of n can be calculated from the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) measurement of the compound represented by formula (1) above. The number average molecular weight is preferably 200 or more and less than 5000, more preferably 300 or more and less than 3000, and particularly preferably 400 or more and less than 2000. When the weight average molecular weight is less than 5000, water washing purification becomes easier, and when it is 200 or more, the target compound will not volatilize during solvent distillation removal.

[0043] In the above formula (1), X is particularly preferred to be any structure represented by the following formulas (A) to (H).

[0044] [Chemistry 5]

[0045]

[0046] In formulas (A) to (H) above, each of the plurality of R's independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a carbon group having 1 to 3 carbon atoms. Hydrocarbons with 5 or fewer carbon atoms are less prone to molecular vibrations when exposed to high frequencies, and therefore possess particularly excellent electrical properties. Furthermore, solvent solubility can be imparted without significantly impairing heat resistance. Each of the plurality of a's independently represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably an integer from 1 to 2. Each of the plurality of b's independently represents an integer from 1 to 3, more preferably an integer from 1 to 2.

[0047] The curable resin composition of this embodiment further comprises a compound having phenolic hydroxyl groups. The amount of the compound having phenolic hydroxyl groups added is preferably 0.0001 parts by mass or more and 0.13 parts by mass or less, more preferably 0.001 parts by mass or more and 0.1 parts by mass or less, and even more preferably 0.003 parts by mass or more and 0.075 parts by mass or less, relative to 100 parts by mass of the compound represented by formula (1) above. Particularly preferred is 0.005 parts by mass or more and 0.05 parts by mass or less. If the amount is less than 0.0001 parts by mass, sufficient polymerization inhibition may not be obtained; if the amount exceeds 0.13 parts by mass, significant poor curing may occur.

[0048] The compounds having phenolic hydroxyl groups are preferably those represented by the following formula (2-1) or the following formula (2-2).

[0049] [Chemistry 6]

[0050]

[0051] In formula (2-1) above, R1 represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms. p is an integer from 1 to 5, preferably an integer from 2 to 4, and particularly preferably 3. In formula (2-2) above, R2 represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms. q is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 to 2. The hydrocarbon group regenerates the phenolic hydroxyl group by providing hydrogen to the phenoxy radical, thus improving the polymerization inhibition effect.

[0052] Compounds represented by formula (2-1) or formula (2-2) above are particularly preferred to be represented by any of the structures of formulas (2-a) to (2-b) below. Compounds represented by formula (2-a) achieve a reduction in polarity by introducing a large alkyl group near the hydroxyl group. Furthermore, due to the high symmetry of the molecule, the degradation of dielectric properties caused by addition is minimized. Compounds represented by formula (2-b) minimize the presence of highly polar hydroxyl groups in the system after free radical scavenging by adopting a quinone structure. In formula (2-b), for one hydroxyl group, the phenolic hydroxyl group introduced at the para-position increases the electron density of the compound represented by formula (2-b), thus improving free radical scavenging performance.

[0053] [Chemistry 7]

[0054]

[0055] In addition to the compounds represented by formula (1) and formula (2) above, various materials may be added to the curable resin composition of this embodiment to improve performance.

[0056] [Polymerization Inhibitor]

[0057] The curable resin composition of this embodiment may contain other polymerization inhibitors in addition to the compounds represented by formulas (2-1) and (2-2) above. However, when using polymerization inhibitors, the amount added is limited to a range that will not have a significant impact on the dielectric and curing properties of the curable resin composition of this embodiment.

[0058] Examples of polymerization inhibitors include phenolic, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitryl radical-based polymerization inhibitors.

[0059] Examples of monophenolic polymerization inhibitors 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-butylaniline)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; 2,2'-methylenebis(4-methyl) 4,4'-3-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-di Bisphenols such as ethylidene bis[3-(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.

[0060] Examples of sulfur-based polymerization inhibitors include, but are not limited to, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearate 3,3'-thiodipropionate.

[0061] 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[ Phosphites such as 2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite; oxaphosphazene oxides such as 9,10-dihydro-9-oxa-10-phosphazene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphazene-10-oxide, and 10-decoxy-9,10-dihydro-9-oxa-10-phosphazene-10-oxide, but not limited to these.

[0062] Examples of hindered amine polymerization inhibitors 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. LA-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.

[0063] Examples of nitroso polymerization inhibitors include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, and cupferron. Among these, ammonium salts of N-nitrosophenylhydroxyamine (cupferron) are preferred.

[0064] Examples of nitryl radical polymerization inhibitors include, but are not limited to, di-tert-butyl nitroxide, 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.

[0065] The compound represented by formula (1) can be cured individually by heating or the like, but its performance can also be improved by adding various materials to make it a curable resin composition.

[0066] [Hardening Accelerator]

[0067] The curable resin composition of this embodiment can also have its curability improved by adding a curing accelerator. Preferably, the curing accelerator is an anionic curing accelerator that promotes the curing reaction by generating anions through ultraviolet or visible light irradiation or heating, or a cationic curing accelerator that promotes the curing reaction by generating cations through ultraviolet or visible light irradiation or heating.

[0068] 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, hexadecyltrimethylammonium salts, and hexadecyltrimethylammonium hydroxide, but these are not limited to these. Furthermore, one or more of these can be used together.

[0069] Examples of cationic hardening accelerators include: 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 carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc benzylate, zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), and transition metal compounds (transition metal salts), but are not limited to these. Furthermore, one or more of these can be used.

[0070] The amount of curing accelerator is 0.01 to 5.0 parts by weight relative to 100 parts by weight of the curing resin composition, as needed.

[0071] [Inorganic filler material]

[0072] The curable resin composition of this embodiment may 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 these can be formed into spherical or fragmented inorganic fillers, but are not limited to these. Furthermore, one or more of these fillers may be used.

[0073] The amount of inorganic filler used in obtaining a curable resin composition for semiconductor packaging 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 substrate materials such as interlayer insulating layer forming materials, copper foil laminates and prepregs, and resin-coated copper foil (RCC), the amount of the aforementioned 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.

[0074] [Polymerization initiator]

[0075] The curable resin composition of this embodiment can also have its curability improved by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylene unsaturated bonds; examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and free radical polymerization initiators. Among these, a free radical polymerization initiator with curability and moderate stability is preferred. A free radical polymerization initiator is a compound that generates free radicals and initiates a chain polymerization reaction through irradiation with ultraviolet or visible light or heating. Examples of usable free radical polymerization initiators include organic peroxides, azo compounds, and benzopinnatols. Organic peroxides are preferred because they have minimal impact on curing temperature control, exhaust gas suppression, and the electrical properties of decomposition products.

[0076] Examples of the aforementioned 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 peroxyneodecanate, tert-butyl peroxyneodecanate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amyl peroxy-2- Alkyl peroxide esters such as ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-pentylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, and tert-pentylperoxybenzoate; peroxide carbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctanoate, and lauroyl peroxide, but not limited to these. Furthermore, one or more of these may be used. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxide esters, and peroxide carbonates are preferred, and dialkyl peroxides are more preferred.

[0077] Examples of the azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanopentaic acid), and 2,2'-azobis(2,4-dimethylpentanonitrile). Furthermore, one or more of these compounds may be used.

[0078] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the curing resin composition, and particularly preferably 0.01 to 3 parts by mass. If the amount of polymerization initiator used is less than 0.01 parts by mass, there is a possibility that the molecular weight may not be sufficiently elongated during the polymerization reaction; if it is more than 5 parts by mass, there is a possibility that the dielectric constant, dielectric loss tangent, and other dielectric properties may be impaired.

[0079] [Flame retardant]

[0080] The curable resin composition of this embodiment may use 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.

[0081] The phosphorus-based flame retardant can be either a reactive or additive type. Specific examples include: trimethyl phosphate, triethyl phosphate, trimethylol phosphate, tri(xylyl) phosphate, tolyl diphenyl phosphate, tolyl-2,6-di(xylyl) phosphate, 1,3-phenylenebis(xylyl) phosphate, 1,4-phenylenebis(xylyl) phosphate, 4,4'-biphenyl(xylyl) phosphate, and other phosphate esters; phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the phosphanes, red phosphorus, etc., but are not limited to these. Furthermore, one or more of these substances may be used. Among the exemplary substances, phosphate esters, phosphines, or phosphorus-containing epoxy compounds are preferred, particularly 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4'-biphenyl(di(xylyl)phosphate), or phosphorus-containing epoxy compounds.

[0082] 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 be insufficient, and if it is more than 0.6 parts by weight, it may have an adverse effect on the hygroscopicity and dielectric properties of the cured material.

[0083] [Light stabilizer]

[0084] The curable resin composition of this embodiment can use 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 and 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-4-diyl)... Examples of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebaate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebaate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)sebaate, 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.

[0085] 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 curable resin composition. If it is less than 0.001 parts by weight, it may not be sufficient to exert a light stabilizing effect, and if it exceeds 0.1 parts by weight, it may have an adverse effect on the hygroscopicity and dielectric properties of the cured material.

[0086] [Adhesive Resin]

[0087] The curable resin composition of this embodiment can use an adhesive resin. Examples of adhesive resins include, butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy-NBR resins, silicone resins, etc., but are not limited to these. In addition, one or more of these can be used.

[0088] 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, and more preferably 0.05 to 20 parts by weight as needed, without impairing the flame retardancy and heat resistance of the cured material.

[0089] [additive]

[0090] The curable resin composition of this embodiment can use additives. Examples of additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, carbon black, phthalocyanine blue, phthalocyanine green, and other colorants.

[0091] The amount of additive 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.

[0092] The curable resin composition of this embodiment can also use epoxy resin, reactive ester compound, phenolic resin, polyphenylene ether compound, amine resin, compound having vinyl unsaturated bonds, isocyanate resin, polyamide resin, maleimide compound, cyanate ester resin, polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, etc., and one or more of these can be used. Among these compounds, from the perspective of balancing heat resistance, adhesion, and dielectric properties, compounds containing polyphenylene ether compound, compound having vinyl unsaturated bonds, cyanate ester resin, polybutadiene and its modified forms, and polystyrene and its modified forms are preferred. By containing these compounds, the brittleness of the cured product can be improved and the adhesion to metals can be enhanced, and cracks in the encapsulation during reflow soldering or reliability tests such as thermal cycling can be suppressed.

[0093] Unless otherwise specified, the amount of the above-mentioned compound used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass, relative to the compound represented by formula (1). Furthermore, the lower limit is preferably 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass. Within the above range, the low dielectric properties of the compound of this embodiment can be achieved while simultaneously providing the additional effects of the added compounds. These components can be substances exemplified below.

[0094] [Epoxy Resin]

[0095] Preferred examples of epoxy resins are shown below, but are not limited thereto. Furthermore, epoxy resins can be in liquid or solid form, and can be used alone or in combination.

[0096] 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), “828US”, “jER828EL”, “825”, and “828EL”. (The above are bisphenol A type epoxy resins manufactured by Mitsubishi Chemical Corporation), "jE807", "1750" (the above are bisphenol F type epoxy resins manufactured by Mitsubishi Chemical Corporation), "jER152" (phenolic varnish type epoxy resin manufactured by Mitsubishi Chemical Corporation), "630", "630LSD" (the above are glycidylamine type epoxy resins manufactured by Mitsubishi Chemical Corporation), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.), "EX-721" (Nagase Chemicals Co., Ltd.) The epoxy resins used include those manufactured by ChemteX (a company specializing in glycidyl ester epoxy resins), Celloxide 2021P (manufactured by Daicel, a cycloaliphatic epoxy resin with an ester backbone), PB-3600 (manufactured by Daicel, an epoxy resin with a butadiene structure), ZX1658, and ZX1658GS (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane epoxy resins). These can be used individually or in combination of two or more.

[0097] 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, naphthylene 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", "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, naphthyl ether type epoxy resin), EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., triphenol type epoxy resin), NC-7000L, NC-7300 (manufactured by Nippon Kayaku Co., Ltd., cyclopentadiene type epoxy resin), NC-7000L, NC-7300 (manufactured by Nippon Kayaku Co., Ltd., cyclopentadiene type epoxy resin), NC-7200H (manufactured by DIC, dicyclopentadiene type epoxy resin), NC-73 ... The following epoxy resins are manufactured by Nippon Chemical Co., Ltd.: Naphthol-cresol phenolic resin (varnish type), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (manufactured by Nippon Chemical Co., Ltd., biphenyl aralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (manufactured by Nippon Chemical Co., Ltd., dicyclopentadiene type epoxy resin), and "ESN475V" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.). Naphthol-type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthol phenolic varnish type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Co., Ltd., biphenyl-type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Co., Ltd., bixylenol-type epoxy resin), "YX-8800" (manufactured by Mitsubishi Chemical Co., Ltd., anthracene-type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd.) 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), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type epoxy resin), etc. These can be used individually or in combination of two or more.

[0098] [Active ester compounds]

[0099] 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, acid 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 acid 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.

[0100] Examples of the aforementioned carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0101] Examples of such acid chlorides include: acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl chloride, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipicoyl dichloride, dodecanedioyl 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.

[0102] Examples of the phenolic compounds and naphthol compounds include, for example: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid 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.

[0103] Specific examples of preferred 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, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit containing a phenylene-dicyclopentadiene-phenylene group.

[0104] 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), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC), which is an active ester compound containing a naphthalene structure. "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound containing acetylated compounds of phenolic varnish; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoyl compounds of phenolic varnish; "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent for acetylated compounds of phenolic varnish; and "EXB-9050L-62M" (manufactured by DIC Corporation), an active ester curing agent containing phosphorus atoms.

[0105] 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 exceeds the above range, excess epoxy groups or reactive ester groups may remain in the system, and the properties may deteriorate in high-temperature placement tests (150°C, 1000 hours, etc.) or long-term reliability tests under high temperature and high humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[0106] [Phenolic resin]

[0107] Phenolic resins are compounds with two or more phenolic hydroxyl groups within their molecules. Examples of phenolic resins include: reaction products of phenols and aldehydes, 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 compounds, and reaction products of bisphenols and aldehydes, but are not limited to these. Furthermore, one or more of these can be used.

[0108] The following are specific examples of the raw materials, but are not limited to these.

[0109] <Phenolic compounds>

[0110] Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.

[0111] Aldehydes

[0112] Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthal, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.

[0113] <Diene Compounds>

[0114] Dicyclopentadiene, terpenes, vinylcyclohexene, norbornene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.

[0115] Ketones

[0116] Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.

[0117] <Substituted biphenyls>

[0118] 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc.

[0119] <Substituted Phenyl>

[0120] 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0121] [Polyphenylene ether compounds]

[0122] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds having vinyl unsaturated bonds are preferred, and those having acrylic, methacrylic, or styrene structures are more preferred. Examples of commercially available products include SA-9000 (a polyphenylene ether compound with methacrylic groups manufactured by Saudi Arabia's Basic Industries Corporation (SABIC)) and OPE-2St 1200 (a polyphenylene ether compound with a styrene structure manufactured by Mitsubishi Gas Chemical Corporation).

[0123] 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. When the molecular weight is less than 500, the heat resistance of the cured material 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, the amount of unreacted material that has not entered the curing system increases, the glass transition temperature of the cured material decreases, and the heat resistance of the cured material tends to decrease.

[0124] If the number-average molecular weight of the polyphenylene ether compound is 500–5000, 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.

[0125] Polyphenylene ether compounds can be obtained through polymerization or by redistributing 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 ethylene-unsaturated bonds such as methacryloyl chloride, acryloyl chloride, and chloromethylstyrene. For example, polyphenylene ether compounds obtained through redistribution reactions can be obtained 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 that contribute to curing at both ends of the molecular chain, thus maintaining higher heat resistance. Furthermore, functional groups can be introduced at both ends of the molecular chain after modification with compounds possessing ethylene-unsaturated bonds, which is preferable in this respect. Additionally, polyphenylene ether compounds obtained through polymerization reactions exhibit excellent flowability, which is also preferable in this respect.

[0126] 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, but it is preferable to use polyfunctional phenolic compounds with two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenolic varnish, cresol varnish, etc. These can be used alone or in combination of two or more.

[0127] While there is no particular limitation on the content of the polyphenylene ether compound, it is preferably 5 to 1000 parts by weight, and more preferably 10 to 750 parts by weight, relative to 100 parts by weight of the curable resin composition. A polyphenylene ether compound content within the above range is preferred not only because it provides excellent heat resistance, but also because it allows for the production of cured products that fully utilize the superior dielectric properties of the polyphenylene ether compound.

[0128] [Amine resin]

[0129] Amine resins are compounds with two or more amino groups within their molecules. Examples of amine resins include: diaminodiphenylmethane, diaminodiphenyl sulfone, isophorone diamine, naphthyldiamine, aniline phenolic varnish (the product of the reaction of aniline and formalin), N-methylaniline phenolic varnish (the product of the reaction of N-methylaniline and formalin), n-ethylaniline phenolic varnish (the product of the reaction of n-ethylaniline and formalin), 2-methylaniline reacting with formalin, 2,6-diisopropylaniline reacting with formalin, 2,6-diethylaniline reacting with formalin, 2-ethyl-6-ethylaniline reacting with formalin, 2,6-dimethylaniline reacting with formalin, and amine resins produced by the reaction of aniline with 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.

[0130] [Compounds containing vinyl unsaturated bonds]

[0131] Compounds containing ethylene unsaturated bonds are those with one or more ethylene unsaturated bonds in their molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used.

[0132] Examples of compounds containing vinyl unsaturated bonds include, for instance, the reaction products of the aforementioned phenolic resins with halogen compounds containing vinyl unsaturated bonds (chloromethylstyrene, allyl chloride, methylallyl chloride, acryloyl chloride, methacryloyl chloride, etc.); the reaction products of phenols containing vinyl unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.); the reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.); and acid-modified derivatives of these compounds, but are not limited to these examples. In addition, one of these can be used, or multiple can be used together.

[0133] [Isocyanate resin]

[0134] Isocyanate resins are compounds having two or more isocyanate groups within their molecules. Examples of isocyanate resins 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.

[0135] [Polyamide resin]

[0136] Examples of polyamide resins include reaction products of diamines, diisocyanates, oxazolines, and dicarboxylic acids; reaction products of diamines and acid chlorides; and ring-opening polymers of lactam compounds. Furthermore, one or more of these can be used.

[0137] The following are specific examples of the above-mentioned raw materials, but are not limited to these.

[0138] <Diamine>

[0139] Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecananediamine, octadecanediamine, nonadecananediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimers 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) [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.

[0140] <Diisocyanate>

[0141] 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.

[0142] <Dicarboxylic acid>

[0143] 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.

[0144] <Acid chloride>

[0145] Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl dichloride, diacetyl chloride, glutaryl dichloride, octanoyl dichloride, sebacyl dichloride, adipyl dichloride, dodecanedioyl 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.

[0146] <lactam>

[0147] ε-caprolactam, ω-undecanolactam, ω-laurolactam, etc.

[0148] [Polyimide resin]

[0149] Examples of polyimide resins include, but are not limited to, the reactions of the aforementioned diamines with the tetracarboxylic dianhydrides exemplified below. Furthermore, these can be used individually or in combination.

[0150] <Tetracarboxylic dianhydride>

[0151] 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-diphenyl... Ethyl-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]phthalic anhydride [-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-1,4'-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.

[0152] [Maleimide compounds]

[0153] The curable resin composition of this embodiment may contain a maleimide compound. A maleimide compound is a compound having one or more maleimide groups within its molecule. Examples of maleimide compounds include: 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 Xyloc type maleimide compounds. Anilix maleimide (manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.), biphenyl aralkyl maleimide compounds (compounds that were solidified by removing the resin solution containing maleimide compound (M2) described in Example 4 of Japanese Patent Application Publication No. 2009-001783 under reduced pressure), 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, and the Material Stage (MATERIAL) The maleimide compounds described in "Epoxy Resin CAS Number Story - Hardener CAS Number Memorandum No. 31 (1)" or "Material Stage" Vol. 19, No. 22019 "Epoxy Resin CAS Number Story - Hardener CAS Number Memorandum No. 32 (2) (2)" are not limited to these. Furthermore, one or more of these compounds may be used.

[0154] [Cyanate ester resin]

[0155] Cyanate ester resins are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: dicyanatobenzene, tricyanoxybenzene, dicyanoxynaphthalene, dicyanoxybiphenyl, 2,2'-bis(4-cyanoxyphenyl)propane, bis(4-cyanoxyphenyl)methane, bis(3,5-dimethyl-4-cyanoxyphenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanoxyphenyl)propane, 2,2'-bis(4-cyanoxyphenyl)ethane, 2,2'-bis(4-cyanoxyphenyl)hexafluoropropane, bis(4-cyanoxyphenyl)sulfone, bis(4-cyanoxyphenyl) sulfide, phenolic phenolic varnish cyanate, and those obtained by converting the hydroxyl groups of a phenol-dicyclopentadiene cocondensate to cyanate ester groups, etc., but are not limited to these. Furthermore, these can be used alone or in combination.

[0156] 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.

[0157] To facilitate the trimerization of cyanate groups to form a sym-triazine ring as needed, cyanate ester resins may also contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetylacetone, and dibutyltin maleate.

[0158] The catalyst is used in an amount of 0.0001 to 0.10 parts by weight relative to 100 parts by weight of the cyanate resin and the curing resin composition, preferably 0.00015 to 0.0015 parts by weight.

[0159] Polybutadiene and its modified forms

[0160] Polybutadiene and its modified forms refer to polybutadiene, or compounds with structures derived from polybutadiene within their molecules. These polybutadiene-derived structures can be converted into single bonds through hydrogenation, where some or all of the unsaturated bonds are converted.

[0161] 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, for example, 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, for example, B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Corporation). The molecular weight of 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. Below the lower limit of this range, the volatile content is high, making it difficult to adjust the solid composition during prepreg production; above the upper limit of this range, 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 ensure due to their polarity. On the other hand, the compounds of this embodiment, because they are not designed with an active introduction of heteroatoms such as oxygen or nitrogen, exhibit excellent compatibility with materials having low polarity and low dielectric properties, or compounds containing only hydrocarbons.

[0162] Polystyrene and its modified forms

[0163] Polystyrene and its modified products refer to polystyrene, or compounds that have a structure derived from polystyrene within their molecules.

[0164] Examples of polystyrene and its modified forms include: polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocros RPS-1005 and RP-61, both manufactured by Nippon Catalyst Co., Ltd.), SEP (Styrene-Ethylene-Propylene copolymer) (Styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), and SEPS (Styrene-Ethylene-Propylene-Styrene copolymer) (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 copolymer) (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-Butylene-Styrene block copolymer) (Styrene-ethylene-butene-styrene block copolymers: Septon 8004, Septon 8006, Septon...). 8007L (all manufactured by Kuraray), SEEPS-ОH (a compound with hydroxyl groups at the end of a styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252, manufactured by Kuraray), SIS (Styrene-Isoprene-Styrene block copolymer: Septon 5125, Septon 5127, both manufactured by Kuraray), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F, both manufactured by Kuraray), SIBS (Styrene-Isobutylene-Styrene(styrene-isobutylene-styrene block copolymers: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Corporation)), etc., but not limited to these. 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, it is preferable to have no unsaturated bonds. Furthermore, there is no particular limitation on the weight average molecular weight of polystyrene and its modified forms being 10,000 or higher. However, if it is too high, the compatibility with low molecular weight components of about 50 to 1,000 and oligomer components of about 1,000 to 5,000, except for polyphenylene ether compounds, deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, a molecular weight of about 10,000 to 300,000 is preferred.

[0165] Polyethylene and its modified forms

[0166] Polyethylene and its modified forms refer to polyethylene or compounds with a molecular structure derived from polyethylene. Examples of polyethylene and its modified forms include: ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylene norbornene copolymers (Mitsui Chemicals EBT: K-8370EM, K-9330M, etc.), ethylene-propylene-vinyl norbornene copolymers (Mitsui Chemicals VNB-EPT: PX-006M, PX-008M, PX-009M, etc.), 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 crosslinkable structures are preferred. Furthermore, one or more of these can be used. There are no particular restrictions on the weight average molecular weight of polyethylene and its modified products as long as it is above 10,000. However, if it is too large, the compatibility with polyphenylene ether compounds, 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 deteriorate, and it will be difficult to ensure the stability of mixing and solvents. Therefore, it is preferred to be about 10,000 to 300,000.

[0167] [benzoxazine compound]

[0168] As benzoxazine compounds, any compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group can be used. While there are no particular limitations on compounds having a phenolic hydroxyl group, examples such as the aforementioned phenolic resins, phenols (which may have alkenyl, alkyl, or other substituents), and bisphenols can be used. While there are no particular limitations on compounds having an amino group, examples such as the aforementioned amine resins, diamines, and anilines (which may have alkenyl, alkyl, or other substituents) can be used. As aldehyde compounds, examples such as the aforementioned aldehydes can be used, but formaldehyde is preferred. Commercially available benzoxazine compounds can also be used, such as benzoxazine Pd, Fa, ALP-d (all manufactured by Shikoku Chemical Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, JBZ-OP100I (all manufactured by JFE Chemical Co., Ltd.), and BTBz (manufactured by Nippon Materials Technology Co., Ltd.).

[0169] The curable resin composition of this embodiment is obtained by mixing the above-mentioned components in a prescribed ratio, pre-curing at 130°C to 180°C for 30 to 500 seconds, and then post-curing at 150°C to 200°C for 2 to 15 hours to fully carry out the curing reaction, thereby obtaining the cured product of this embodiment. Alternatively, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and then post-curing may be performed after removing the solvent.

[0170] While there are no particular limitations on the method for preparing the curable resin composition of this embodiment, it is possible to simply mix the components uniformly, or to prepolymerize them. For example, a mixture containing the compounds of this embodiment can be prepolymerized by heating, either in the presence or absence of a curing accelerator or polymerization initiator, or in the presence or absence of a solvent. Similarly, prepolymerization can be performed by adding compounds such as amine compounds, compounds having ethylene unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and its modified forms, polystyrene and its modified forms, inorganic fillers, and other additives. The mixing or prepolymerization of the components can be performed using, for example, an extruder, a kneading machine, or rollers in the absence of a solvent, or in the presence of a solvent using a reaction vessel equipped with a stirring device.

[0171] As a method for uniform mixing, the resin composition is prepared by kneading and mixing using equipment such as a kneading machine, rollers, or planetary mixer within a temperature range of 50℃ to 100℃, resulting in a homogeneous resin composition. The obtained resin composition is then pulverized and molded into cylindrical tablets, granular powder, or powder molded bodies using a molding machine such as a tablet machine. Alternatively, these compositions can be melt-molded onto a surface support to form sheets with a thickness of 0.05 mm to 10 mm, thus creating a curable resin composition molded body. The obtained molded body becomes non-sticky at 0℃ to 20℃, and its fluidity and curability remain almost unchanged even after storage at -25℃ to 0℃ for more than a week.

[0172] The obtained molded body can be molded into a hardened material using a transfer molding machine or a compression molding machine.

[0173] The curable resin composition of this embodiment can be prepared into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of this embodiment can be dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone to prepare a varnish. This varnish is then impregnated in a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a prepreg. This prepreg is then hot-pressed to produce a cured product of the curable resin composition of this embodiment. The amount of solvent used is 10% to 70% by weight, preferably 15% to 70% by weight, in the mixture of the curable resin composition of this embodiment and the solvent. Furthermore, if it is a liquid composition, a cured product containing carbon fibers can be obtained directly, for example, by resin transfer molding (RTM).

[0174] Furthermore, the curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve the flexibility of the B-stage, etc. This film-type resin composition is obtained by applying the curable resin composition of this embodiment as a varnish onto a release film, removing the solvent under heat, and then performing B-stage curing to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.

[0175] The curable resin composition of this embodiment can be heated and melted, and its viscosity reduced to impregnate reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers, thereby obtaining a prepreg. Specific examples include glass fibers such as E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, spherical glass cloth, NE-glass cloth, and T-glass cloth. Further examples include inorganic fibers other than glass, or organic fibers such as polyparaphenylene terephthalamide (Kevlar, a registered trademark, manufactured by DuPont), fully aromatic polyamides, polyesters, polyparaphenylene benzoxazole, polyimide, and carbon fibers, but these are not particularly limited. The shape of the substrate is not particularly limited; examples include woven fabrics, non-woven fabrics, roving, and chopped strand mat. In addition, known weaving methods include plain weave, basket weave, and twill weave, and these methods can be appropriately selected based on the target application or performance. Furthermore, glass fabrics that have undergone fiber opening treatment or surface treatment using silane coupling agents are preferably used. The thickness of the substrate is not particularly limited, but is preferably around 0.01 mm to 0.4 mm. Alternatively, a prepreg can be obtained by impregnating the varnish into reinforcing fibers and then heating and drying it.

[0176] In addition, the aforementioned prepregs can also be used to manufacture laminates. A laminate only needs to include one or more prepregs and is not particularly limited; it can have any other layers. As a method for manufacturing the laminate, generally known methods can be appropriately applied and are not particularly limited. For example, in forming a laminate with metal foil, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc., can be used. The laminate can be obtained by stacking the prepregs together and heating and pressurizing them. The heating temperature is not particularly limited, but is preferably 65°C to 300°C, more preferably 120°C to 270°C. Furthermore, the pressure applied is not particularly limited. If the pressure is too high, it is difficult to adjust the solid composition of the resin in the laminate, resulting in unstable quality. Conversely, if the pressure is too low, air bubbles or poor adhesion between layers will occur. Therefore, 2.0 MPa to 5.0 MPa is preferred, more preferably 2.5 MPa to 4.0 MPa. The laminate of this embodiment, by including a layer made of metal foil, can be suitable for use as a metal foil-coated laminate as described later.

[0177] The prepreg is cut into the desired shape and, as needed, laminated with copper foil, etc., while applying pressure to the laminate using pressing, autoclave forming, sheet winding, etc., and heating and curing the curable resin composition, thereby obtaining an electrical and electronic laminate (printed wiring board) or carbon fiber reinforced material.

[0178] The curable resin composition of this embodiment can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of this embodiment, for example, a method can be described by coating the curable resin composition onto a support film (support body), drying it, and forming a resin composition layer on the support film. When using the curable resin composition of this embodiment in a resin sheet, it is crucial that the film softens under the lamination temperature conditions (70°C to 140°C) of a vacuum lamination method and exhibits the fluidity (resin flow) to fill the vias or through holes present in the circuit board while being laminated with the circuit board. It is preferable to formulate the above-mentioned components to exhibit such characteristics. Furthermore, in order to prevent the occurrence of localized differences in characteristic values ​​due to phase separation or the like in the obtained resin sheet and circuit board (copper-clad laminate, etc.), uniform appearance is required to ensure consistent performance in any location.

[0179] Here, the diameter of the through-holes in the circuit board is 0.1 mm to 0.5 mm, and the depth is 0.1 mm to 1.2 mm, preferably within this range for resin filling. Furthermore, when the circuit board is laminated on both sides, it is desirable that approximately half of the through-holes are filled.

[0180] As a specific method for manufacturing the above-mentioned resin sheet, one can include preparing an organic solvent to clear the resin composition, coating the cleared resin composition on the surface of a support film (Y), and further drying the organic solvent by heating or hot air blowing to form a resin composition layer (X).

[0181] As for the organic solvent used herein, ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferred; acetates such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, and carbitol acetate are preferred; carbitols such as cellosol and butyl carbitol are preferred; aromatic hydrocarbons such as toluene and xylene are preferred; and dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred. The proportion of organic solvent used is preferably such that the non-volatile matter accounts for 30% to 60% of the total mass.

[0182] Furthermore, the thickness of the resin composition layer (X) formed thereon needs to be greater than or equal to the thickness of the conductor layer of the circuit board on which the resin composition layer (X) is laminated. The conductor layer thickness of the circuit board is in the range of 5 μm to 70 μm, therefore, the thickness of the resin composition layer (X) is preferably 10 μm to 100 μm. In addition, the resin composition layer (X) in this embodiment can be protected by the protective film described later. Protective film protection prevents dust and the like from adhering to the surface of the resin composition layer (X) and prevents scratches.

[0183] The aforementioned support film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; polyimide; and even release paper and metal foils such as copper foil and aluminum foil. Furthermore, the support film and protective film can be subjected to matte treatment, corona treatment, and release treatment. The thickness of the support film is not particularly limited, but it is typically between 10 μm and 150 μm, preferably in the range of 25 μm to 50 μm. The thickness of the protective film is preferably between 1 μm and 40 μm.

[0184] The aforementioned support film (Y) is peeled off after the resin composition layer (X) is laminated onto the circuit board, or after the resin composition layer (X) is heat-cured to form an insulating layer. Peeling off the support film (Y) after the resin composition layer (X) constituting the resin sheet has been heat-cured prevents the adhesion of dust and other contaminants during the curing process. When peeling off the support film (Y) after the resin composition layer (X) has cured, a release treatment is applied beforehand.

[0185] Furthermore, the resin sheet obtained from the above method can be used to manufacture multilayer printed circuit boards. For example, when the resin composition layer (X) is protected by a protective film, after peeling off the protective film, the resin composition layer (X) is directly contacted with the circuit board and laminated onto one or both sides of the circuit board using, for example, a vacuum lamination method. The lamination method can be batch or continuous roller lamination. Additionally, if necessary, the resin sheet and the circuit board can be heated (preheated) before lamination. The lamination conditions are as follows: the pressing temperature (lamination temperature) is preferably 70°C to 140°C, and the pressing pressure is preferably 1 kgf / cm². 2 ~11 kgf / cm 2 (9.8×10) 4 N / m 2 ~107.9×10 4 N / m 2 The lamination is preferably carried out under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0186] Furthermore, the curable resin composition of this embodiment can be used to manufacture semiconductor devices. Examples of semiconductor devices include DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package).

[0187] The curable resin composition and its cured product of this embodiment can be used in a wide range of fields. Specifically, it can be used for various applications such as molding materials, adhesives, composite materials, and coatings. The cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, and is therefore suitable for use in packaging materials for semiconductor components, packaging materials for liquid crystal display components, packaging materials for organic electroluminescence (EL) components, electrical and electronic components such as laminates (printed circuit boards, BGA substrates, stacked substrates, etc.), composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

[0188] Example

[0189] The present invention will now be described in more detail through embodiments. Hereinafter, unless otherwise specified, "part" refers to a portion by weight. Furthermore, this embodiment is not limited to these embodiments.

[0190] The various analytical methods used in the examples are described below.

[0191] <GPC (Gel Permeation Chromatography) Analysis>

[0192] Tubing: SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603

[0193] Flow rate: 1.5 ml / min.

[0194] Column temperature: 40℃

[0195] Solvent used: THF (tetrahydrofuran)

[0196] Detector: RI (Differential Refractive Index Detector)

[0197] [Examples 1-7, Comparative Examples 1-3]

[0198] Using the amounts of biphenyl aralkyl maleimide resin M-1 (cured by solvent distillation of the resin solution containing maleimide resin (M2) described in Synthesis Example 4 of Japanese Patent Application Publication No. 2009-001783 after solvent removal under reduced pressure), polymerization inhibitor, and polymerization initiator shown in Table 1, mirror copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) was sandwiched between the resin and vacuum-pressed, and then cured at 220°C for 2 hours. At this time, a 250 μm thick cushioning paper was used as a gasket, with a 150 mm diameter cutout in the center. For evaluation, the test piece was cut to the required size using a laser cutter as needed, and then evaluated.

[0199] <Reactivity Evaluation>

[0200] Differential scanning calorimetry (DSC) measurements were performed under the following conditions. Observations of only one peak were rated as ○, and observations of two peaks were rated as ×, indicating the presence of unhardened components. Furthermore, in cases where two peaks were observed, the heat release from the high-temperature side peak was recorded as residual heat release.

[0201] Differential scanning calorimeter: DSC6220 (manufactured by SII Nanotechnology)

[0202] Measurement temperature range: 30℃~350℃

[0203] Heating rate: 10℃ / minute

[0204] Atmosphere: Nitrogen (30 mL / min)

[0205] Sample size: 5 mg

[0206] <Dielectric constant test / Dielectric loss tangent test>

[0207] A 10 GHz cavity resonator manufactured by AET Corporation was used for testing at 25°C using the cavity resonator perturbation method. The sample dimensions were 1.7 mm wide × 100 mm long and 0.2 mm thick. The evaluation results are shown in Table 1. Note that "-" in Table 1 indicates no measurement was performed. Although DSC measurements could be performed on Comparative Example 4, the low hardening degree resulted in a brittle hardened material, making it impossible to obtain a sample for dielectric property measurement.

[0208] [Table 1]

[0209]

[0210] MHQ: 2-Methylhydroquinone

[0211] BHT: 2,6-di-tert-butyl-4-methylphenol

[0212] Benzothiazine: Thiodiphenylamine

[0213] HTEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical

[0214] DCP: dicumyl peroxide

[0215] [Examples 8-9, Comparative Example 7]

[0216] <Evaluation of Preservation Stability>

[0217] Diphenylaryl maleimide resin M-1 and polymerization inhibitor were prepared according to the proportions shown in Table 2 and melted at 120°C while nitrogen was blown in at a rate of 25 mL / min in a 500 mL four-necked flask. The mixture was stirred at 120°C, and samples were taken at 6 and 12 hours to measure the gas permeable polymer (GPC). The area percentage of GPC at residence times of 14 to 17 minutes was compared. The area change was calculated by dividing the GPC area percentage at 12 hours (14 to 17 minutes) by the GPC area percentage at 6 hours (14 to 17 minutes). The results are shown in Table 2.

[0218] [Table 2]

[0219]

[0220] The results in Table 1 confirm that the curable resin composition of the present invention can produce a cured product with excellent low dielectric properties without hindering the curing reaction. Furthermore, the results in Table 2 confirm that it exhibits excellent high-temperature storage stability.

[0221] Industrial utilization potential

[0222] The curable resin composition of the present invention is suitable for use in electrical and electronic components such as semiconductor packaging materials, printed circuit boards, and multilayer boards.

Claims

1. A curable resin composition comprising a compound represented by the following formula (1) and a compound having phenolic hydroxyl groups, wherein the content of the compound having phenolic hydroxyl groups is 0.0001 parts by mass and 0.13 parts by mass or less relative to 100 parts by mass of the compound represented by the following formula (1). [Chemistry 1] (In the above formula (1), X is a hydrocarbon with 1 to 25 carbon atoms, and the multiple existing Rs independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms. m is an integer from 1 to 3. n is the average of the number of repetitions, which is a number from 1 to 20).

2. The curable resin composition according to claim 1, wherein, X in the compound represented by formula (1) is any structure represented by formulas (A) to (H) below. [Chemistry 2] (In the above formulas (A) to (H), the multiple Rs independently represent hydrogen atoms or hydrocarbon groups with 1 to 5 carbon atoms. The multiple as are independent integers from 1 to 4. The multiple bs are independent integers from 1 to 3.) 3. The curable resin composition according to claim 1, wherein, The compound having a phenolic hydroxyl group is selected from one or more of the compounds represented by formula (2-1) and formula (2-2). [Chemistry 3] (In the above equations (2-1) and (2-2), the multiple existing R1 and R2 independently represent hydrocarbon groups with 1 to 10 carbon atoms. p is an integer from 1 to 5. q is an integer from 1 to 4).

4. The curable resin composition according to claim 1, wherein, The curable resin composition further comprises one or more of the following: a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, an amine resin, a compound having vinyl unsaturated bonds, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and its modified forms, polystyrene and its modified forms, polyethylene and its modified forms, and a benzoxazine compound.

5. A hardened compound obtained by hardening the hardening resin composition as described in any one of claims 1 to 4.

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