Curable resin composition and its cured product

Abstract

The present invention provides a curable resin composition and a cured product thereof that exhibit excellent heat resistance and low dielectric loss tangent. [Solution] A curable resin composition containing a maleimide resin having repeating units of the following formulas (a) and (b) and an acid value of 25 or less, and at least one selected from a specific resin other than the aforementioned resin and a photoradical polymerization initiator. The group X in formula (b) is represented by formula (Y). TIFF2026079731000022.tif48170 TIFF2026079731000023.tif21170

Description

Technical Field

[0001] The present invention relates to a curable resin composition and a cured product thereof, and is suitably used for electrical and electronic components such as semiconductor encapsulating materials, printed wiring boards, build-up laminated boards, resist films, optoelectronic substrates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.

Background Art

[0002] In recent years, due to the expansion of the fields of use, the required characteristics of laminated boards for mounting electrical and electronic components have become extensive and sophisticated. Conventionally, semiconductor chips have mainly been mounted on metal lead frames, but semiconductor chips with high processing capabilities such as central processing units (hereinafter referred to as CPUs) are increasingly being mounted on laminated boards made of polymer materials.

[0003] In the currently accelerating fifth-generation communication system "5G", further increases in capacity and high-speed communication are expected. In 5G, the frequency used will become higher, but for the realization of high-speed communication using high frequencies, reduction of transmission loss is important, and further low dielectric characteristics of the substrate material are required. The transmission loss occurring on a printed board is derived from conductor loss and dielectric loss. As described in Non-Patent Document 1, since conductor loss is proportional to the square root of the relative permittivity and the dielectric tangent of the dielectric, it can be said that improving the dielectric tangent with a higher contribution degree than the relative permittivity is effective for reducing transmission loss. Examples of low dielectric materials include thermoplastic materials typified by PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they are inferior in moldability compared to thermosetting resins. Based on this, the development of thermosetting resins with excellent low dielectric characteristics is desired.

[0004] In light of this situation, maleimide resins, which have excellent heat resistance and low dielectric properties, have recently been considered as printed circuit board materials for high-frequency applications. On the other hand, as pointed out in Patent Document 1 below, bismaleimide compounds, which have an imide structure in their molecules, are highly crystalline and have a high melting point of around 150°C, close to the 170-180°C that indicates the start of self-reaction. Therefore, they are difficult materials to prepare by impregnating them with a varnish and drying, or by melting and mixing them with epoxy resins, curing agents, fillers, etc., to produce molding materials. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-12671 [Overview of the project] [Problems that the invention aims to solve]

[0006] This invention has been made in view of the above circumstances, and aims to provide a curable resin composition and a cured product thereof that are excellent in heat resistance and low dielectric loss tangent. [Means for solving the problem]

[0007] The present invention relates to a maleimide resin having repeating units of the following formulas (a) and (b), with an acid value of 25 or less, At least one selected from the group consisting of maleimide resins other than the aforementioned maleimide resin, epoxy resin, activated ester resin, polyphenylene ether compound, polystyrene and modified thereof, polyethylene and modified thereof, thermoplastic elastomer, compound having an ethylenically unsaturated bond, cyanate ester resin, polybutadiene and modified thereof, and cyanate ester resin, This is a curable resin composition containing [a specific substance].

[0008] [ka]

[0009] (In the above formula, X is represented by the following formula (Y). Ra represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. m is the average value of the number of repetitions, and 1 ≦ m < 1000. n is the average value of the number of repetitions, and 1.1 ≦ n < 1000. (a) and (b) are each bonded by *, and the repeating positions may be random.)

[0010] [Chemical formula]

[0011] (In the above formula (Y), R1 exists independently and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R exists independently and represents a hydrocarbon group having 1 to 10 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocyclic ring. a is an integer of 0 to 4, and d is an integer of 0 to 2. * indicates the bonding position.)

[0012] In the present application, "(numerical value 1) to (numerical value 2)" indicates that the upper and lower limit values are included. [Advantages of the Invention]

[0013] According to the present invention, a curable resin composition excellent in heat resistance and low dielectric tangent can be provided. [Brief Description of the Drawings]

[0014] [Figure 1] The GPC chart of Synthesis Example 2 is shown. [Figure 2] The GPC chart of Synthesis Example 3 is shown. [Embodiments for Carrying Out the Invention]

[0015] Hereinafter, the embodiments according to the present invention (hereinafter, also referred to as "the present embodiment") will be described in more detail.

[0016] The curable resin composition of the present embodiment contains a maleimide resin having repeating units of the following formulas (a) and (b).

[0017]

Chemical formula

[0018] In the above formulas, X is represented by the following formula (Y). Ra represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. (a) and (b) are each bonded by a *, and the repeating positions may be random. m is the average value of the number of repetitions, 1 ≤ m < 1000, preferably 1 < m < 1000, more preferably 2 ≤ m ≤ 750, and particularly preferably 3 ≤ m ≤ 500. n is the average value of the number of repetitions, 1.1 ≤ n < 1000, preferably 1.1 < n < 1000, more preferably 1.1 < n ≤ 500, still more preferably 1.1 < n ≤ 100, and particularly preferably 1.1 < n ≤ 20. The values of m and n are derived from the styrene-based monomer maleic anhydride copolymer used as a raw material, and the values of m and n can be determined from the ratio of the styrene-based monomer and the acid anhydride and the molecular weight obtained from the acid value in the styrene-based monomer-maleic anhydride copolymer.

[0019]

Chemical formula

[0020] In the above formula (Y), R1 is present independently and is either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R is present independently and represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons with 10 or fewer carbon atoms in R are less prone to molecular vibration when exposed to high frequencies and therefore have excellent electrical properties. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle, and is more preferably substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene. a is an integer from 0 to 4. d is an integer from 0 to 2, and is preferably 0 or 1. * indicates the bond position.

[0021] The above formula (Y) is preferably one or more of the following formulas (A) to (F), and more preferably is formula (B) or (F).

[0022] [ka]

[0023] In the above formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons with 10 or fewer carbon atoms in R are less prone to molecular vibration when exposed to high frequencies, and therefore have excellent electrical properties. a is an integer from 0 to 4, and p is an integer from 1 to 20. * indicates the bond position.

[0024] The method for producing the above-mentioned maleimide resin is not particularly limited, but it can be obtained by reacting a styrene-based monomer malee anhydride copolymer with a compound containing two or more amino groups in its molecule and maleic anhydride.

[0025] The above-mentioned styrene-based monomer maleic acid copolymer is obtained by copolymerizing styrene and maleic anhydride. Any known polymerization method may be used, including radical polymerization, coordination polymerization, and various living polymerization methods. For example, it can be obtained by reacting styrene and maleic anhydride in toluene in the presence of a radical polymerization initiator. The resulting polymer may be a random polymer, a periodic copolymer, a block polymer, or an alternating copolymer. The stereoregularity of the polystyrene segments may be syndiotactic, atactic, isotactic, etc. The molecular weight is preferably 500 to 50000, more preferably 750 to 40000, even more preferably 1000 to 30000, and particularly preferably 1500 to 20000. If the molecular weight is less than 500, the resulting product becomes easily volatile, and the weight of the resin component decreases during heating, making it difficult to apply to the manufacturing process of substrate materials. Furthermore, if the molecular weight is greater than 30,000, stirring during manufacturing becomes difficult, and purification by washing with water becomes difficult.

[0026] Any known amine compound may be used as the compound having two or more amino groups as described above, but it is preferable to use an amine compound represented by the following formula (Y').

[0027] [ka]

[0028] In the above formula (Y'), R1 is an independent entity and is either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R is an independent entity and represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle, and is more preferably a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene. a is an integer from 0 to 4. d is an integer from 0 to 2, preferably 0 or 1. b is the average value of the number of repeats, and 1 ≤ b < 5.

[0029] The amine compound represented by the above formula (Y') is preferably one or more of the amine compounds represented by the following formulas (A') to (F'), and is more preferably (B') or (F').

[0030] [ka]

[0031] In the above formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons with 10 or fewer carbon atoms in R are less prone to molecular vibration when exposed to high frequencies, and therefore have excellent electrical properties. a is an integer from 0 to 4, and p is an integer from 1 to 20. b is the average value of the number of repetitions, and 1 ≤ b < 5.

[0032] The acid value of the maleimide resin described above can be measured by titration. The acid value is preferably 25 or less, more preferably 20 or less, and particularly preferably 15 or less. The lower limit of the acid value may be 0, but it is preferably 3 or more. The acid components in the maleimide resin originate from unreacted styrene monomer malee anhydride copolymers, maleic anhydride, maleic acid as a by-product, and components containing the structure represented by the following formula (q) when the maleimide resin is synthesized. These components contribute to the deterioration of dielectric properties. Furthermore, components containing the structure represented by the following formula (q) have poor solvent solubility in organic solvents, causing crystal precipitation and contributing to the deterioration of storage stability.

[0033] [ka]

[0034] In the above formula, X, n, and * have the same meaning as in formula (b) above.

[0035] The above maleimide resin can also be made into a varnish by adding an organic solvent. Examples of organic solvents that can be used include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The varnish preferably contains 30 to 90% by weight of the above maleimide resin, and more preferably 40 to 80% by weight.

[0036] The method for producing the above maleimide resin is not particularly limited, but it can be obtained by reacting a styrene monomer maleic anhydride copolymer with a compound containing two or more amino groups in its molecule and maleic anhydride. Specifically, it can be obtained by a method in which a styrene monomer maleic anhydride copolymer and a compound containing two or more amino groups in its molecule are imidized in a solvent in the presence of a catalyst in the first step, and maleic anhydride is added in the second step to perform maleimidization. However, the order of the steps is not limited, and the order of the steps can be changed or performed simultaneously.

[0037] In the first imidation step, gelation due to three-dimensional crosslinking during the reaction can be prevented by adding an excess of amino groups from the amine compound to 1 mole of acid anhydride contained in the styrene monomer-maleic anhydride copolymer. In this case, the preferred range for the value (α / β) obtained by dividing the number of moles of amino groups (α) of the raw material amine by the number of moles of acid anhydride (β) of the styrene monomer-maleic anhydride copolymer is 1.1 to 20, preferably 1.1 to 15, and more preferably 1.1 to 10. If the amine is below the above range, gelation will occur, making production difficult. If it is above the above range, the amount of polystyrene introduced decreases, and sufficient improvement in electrical properties cannot be expected. Examples of solvents that can be used include non-water-soluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, but are not limited to these, and two or more may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent can also be used in combination. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more may be used in combination. When using an aprotic polar solvent, it is preferable to use one with a higher boiling point than the water-insoluble solvent used in combination. During the reaction, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, as well as Lewis acids such as aluminum chloride and zinc chloride, solid acids such as activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins may be used as catalysts as needed. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.1 to 0.8 moles per mole of amino groups of the amine compound used, preferably 0.2 to 0.7 moles. If too much catalyst is used, the viscosity of the reaction solution may become too high, making stirring difficult, and if too little is used, the reaction may proceed slowly.In the second step of imidation, the remaining amine can be completely maleimidized by adding maleic anhydride in an amount equal to or greater than the number of moles of amino groups of the amine added in excess in the first step, preferably 1.1 equivalents or more. A basic co-catalyst such as triethylamine can also be used alone or in combination as a co-catalyst for imidation. If a sulfonic acid is used as a catalyst, neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide may be performed before proceeding to the extraction step. The solid content concentration during the reaction is preferably 45-75%. If the solid content concentration is too low, the reaction rate will be poor, and unreacted acid anhydride groups will remain, resulting in a high acid value and deterioration of dielectric properties. On the other hand, if it is too high, the raw materials may not dissolve, or the viscosity will become too high, making stirring difficult.

[0038] For the extraction process, aromatic hydrocarbon solvents such as toluene or xylene may be used alone, or non-aromatic hydrocarbons such as cyclohexane or toluene may be used in combination. After extraction, it is preferable to wash the organic layer with water until the wastewater becomes neutral, and then wash it again with a mixed solution of water and a water-soluble organic solvent. This step improves the separation during water washing and further reduces impurities such as amicalcium, thereby lowering the acid value. Examples of water-soluble organic solvents that can be used include alcohols such as methanol, ethanol, 1-propanol, 2-methyl-2-propanol, 1-butanol, and isobutyl alcohol, as well as 1,2-dimethylethane, triethylamine, pyridine, and acetic acid. By distilling off the solvent from the organic layer after washing using an evaporator or the like, a maleimide resin having a polystyrene-like structure in its molecule can be obtained.

[0039] Styrene monomer-maleic anhydride copolymers are obtained by copolymerizing styrene monomers and maleic anhydride. Any known polymerization method may be used, including radical polymerization, coordination polymerization, and various living polymerization methods. For example, they can be obtained by reacting styrene monomers and maleic anhydride in toluene in the presence of a radical polymerization initiator. The resulting polymer may be a random polymer, a periodic copolymer, a block polymer, or an alternating copolymer. The stereoregularity of the polystyrene segments may be syndiotactic, atactic, isotactic, etc. It is particularly preferable that the styrene monomer-maleic anhydride copolymer is a styrene-maleic anhydride copolymer.

[0040] The weight-average molecular weight (Mw) of the styrene monomer maleic anhydride copolymer, as determined by gel permeation chromatography (GPC), is preferably 900 or more and less than 10,000, more preferably 1,500 or more and less than 9,000, and particularly preferably 2,000 or more and less than 8,000. The number-average molecular weight (Mn) is preferably 1,000 or more and less than 5,000, and more preferably 1,000 or more and less than 3,000. If the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are below the above upper limits, gelation can be prevented, and purification by washing with water becomes easier. If the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are above the above lower limits, the target compound will not volatilize during the solvent removal process.

[0041] The curable composition of this embodiment may contain a polymerization inhibitor in addition to the maleimide resin. Including a polymerization inhibitor improves storage stability and allows control of the reaction initiation temperature. Controlling the reaction initiation temperature makes it easier to ensure fluidity, prevents impregnation into glass cloth and the like, and facilitates B-stage processes such as prepreg formation. If the polymerization reaction proceeds too far during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur. Examples of polymerization inhibitors that can be used include phenolic, sulfuric, phosphorusic, hindered amine, nitroso, and nitroxyl radical type polymerization inhibitors. The polymerization inhibitor may be added when synthesizing the maleimide resin of this embodiment, or added after synthesis. Furthermore, the polymerization inhibitor can be used alone or in combination of two or more types. The amount of polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the resin component. These polymerization inhibitors can be used individually, but two or more types may be used in combination. In this embodiment, phenolic, hindered amine, nitroso, and nitroxyl radical type polymerization inhibitors are preferred.

[0042] Specific examples of phenolic polymerization inhibitors include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3, Monophenols such as 5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-o-cresol; 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl] Bisphenols such as )propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, and bis(3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl)calcium;Examples of high molecular weight phenols include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

[0043] Specific examples of sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearylul-3,3'-thiodipropionate.

[0044] Specific examples of phosphorus polymerization inhibitors include triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbi(2,4-di-t-butylphenyl) phosphite, and cyclic neopentanetetraylbi(2,4-di-t-butyl-4-methylphenyl) phosphite. Examples include phosphites such as bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite; and oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0045] Specific examples of hindered amine polymerization inhibitors include, but are not limited to, 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, Adekastab LA-63P, Adekastab LA-57, Adekastab LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, and Tinuvin791FB.

[0046] Specific examples of nitroso polymerization inhibitors include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, (cuperone), and preferably, ammonium salts of N-nitrosophenylhydroxyamine (cuperone).

[0047] Specific examples of nitroxyl radical polymerization inhibitors include, but are not limited to, di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

[0048] The curable composition of this embodiment contains, in addition to the maleimide resin described above, at least one selected from the group consisting of maleimide resins other than the maleimide resin described above, phenol resins, epoxy resins, amine resins, isocyanate resins, polyamide resins, polyimide resins, activated ester resins, polyphenylene ether compounds, polystyrene and its modified products, polyethylene and its modified products, thermoplastic elastomers, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and its modified products, cyanate ester resins, propenyl resins, metharyl resins, and benzoxazine compounds. These materials are described below. Of the above, it is preferable to include epoxy resins, compounds containing ethylenically unsaturated bonds, and cyanate ester resins in order to balance heat resistance, adhesion, and dielectric properties. By including these curable resins, the brittleness of the cured product can be improved and adhesion to metals can be enhanced, and cracks in the package can be suppressed during reliability tests such as solder reflow and thermal cycling. The amount of the curable resin used is preferably 10 times or less by weight, more preferably 5 times or less by weight, even more preferably 3 times or less by weight, and particularly preferably 1 time or less by weight, relative to the maleimide resin. A preferred lower limit is 0.5 times or more by weight, and even more preferably 1 time or more by weight. Using 10 times or less by weight allows the heat resistance and dielectric properties of the maleimide resin to be fully utilized.

[0049] Examples of maleimide resins other than the maleimide resins mentioned above, such as phenolic resins, polyphenylene ether compounds, epoxy resins, amine resins, compounds containing ethylenically unsaturated bonds, isocyanate resins, polyamide resins, polyimide resins, amine resins, cyanate ester resins, activated ester resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products, thermoplastic elastomers, and benzoxazine compounds, can be used as shown below.

[0050] Maleimide resins other than those listed above: Maleimide resins are compounds that contain one or more maleimide groups in their molecule. Examples include: 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimoidphenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimoidphenoxy)benzene, 1,3-bis(4-maleimoidphenoxy)benzene, and Zylok-type maleimide compounds (anilix). Maleimide (manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl type maleimide compound (solidified by solvent distillation under reduced pressure of a resin solution containing the maleimide compound (M2) described in Example 4 of Japanese Patent Publication No. 2009-001783), bisaminocumylbenzene type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compound having an indan structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "~Continued Epoxy Resin CAS Number Story~ Curing Agent CAS Number Memo No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 2 2019 "~Continued Epoxy Resin CAS Number Story~ Curing Agent CAS Number Memo No. 32" Examples include, but are not limited to, the maleimide compounds listed in "Bismaleimide (2)".

[0051] Phenolic resins: Phenolic resins are compounds having two or more phenolic hydroxyl groups in their molecule. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, and reaction products of bisphenols and aldehydes. Furthermore, these can be used individually or in combination of multiple types. Specific examples of each of the above ingredients are given below, but this list is not exhaustive. Polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, Polymers of divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.; polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); phenol resins obtained by polycondensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.); polycondensates of bisphenols and various aldehydes; polyphenylene ether compounds.

[0052] Any known polyphenylene ether compound may be used, but from the viewpoint of heat resistance and electrical properties, it is preferable that it be a polyphenylene ether compound having an ethylenically unsaturated double bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure. Examples of commercially available products include SA-9000-111 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group), OPE-2St 1200, and OPE-2St 2200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound having a styrene structure). 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 not to be sufficient. If the molecular weight is greater than 5000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to lead to molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, the amount of unreacted material that is not incorporated into the curing system increases, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease. If the number-average molecular weight of the polyphenylene ether compound is between 500 and 5000, it is possible to achieve excellent heat resistance and moldability while maintaining excellent dielectric properties. Specifically, the number-average molecular weight can be measured using methods such as gel permeation chromatography.

[0053] The polyphenylene ether compound may be obtained by polymerization or by redistributing a high molecular weight polyphenylene ether compound with a number average molecular weight of approximately 10,000 to 30,000. Alternatively, these compounds may be used as raw materials and reacted with compounds having ethylenically unsaturated double bonds, such as methacrylic chloride, acrylic chloride, and chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by redistribution is, for example, obtained by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to redistribute it. Polyphenylene ether compounds obtained by this redistribution reaction are preferable because they have hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain, thus maintaining even higher heat resistance, and because functional groups can be introduced to both ends of the molecular chain even after modification with a compound having ethylenically unsaturated double bonds. Furthermore, polyphenylene ether compounds obtained by polymerization are preferable because they exhibit excellent fluidity.

[0054] The molecular weight of polyphenylene ether compounds can be adjusted by adjusting polymerization conditions, etc., in the case of polyphenylene ether compounds obtained by polymerization reactions. In the case of polyphenylene ether compounds obtained by redistribution reactions, the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, this can be done by adjusting the amount of phenolic compound used in the redistribution reaction. That is, the higher the amount of phenolic compound used, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. Furthermore, the phenolic compound used in the redistribution reaction is not particularly limited, but polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, and cresol novolac, are preferably used. These may be used individually or in combination of two or more.

[0055] Furthermore, while the content of the polyphenylene ether compound is not particularly limited, it is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight, relative to the total weight of the curable resin components. A polyphenylene ether compound content of 10 to 90% by weight is preferable not only because it provides excellent heat resistance, but also because it yields a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[0056] Epoxy resins: Epoxy resins are compounds having two or more epoxy groups in their molecule. Examples include, but are not limited to, the aforementioned phenolic resins, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester epoxy resins.

[0057] Amine resins: Amine resins are compounds having two or more amino groups in their molecule. Examples of amine resins include, but are not limited to, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resins obtained by the reaction of aniline with xylylene chloride, aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) as described in Japanese Patent Publication No. 6429862, or substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene).

[0058] Compounds containing ethylenically unsaturated bonds: Compounds containing ethylenically unsaturated bonds are compounds that have one or more ethylenically unsaturated bonds in their molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Polycondensates of the aforementioned phenolic resin and halogenated compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylate chloride, allyl chloride, etc.), phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogenated compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone) Polycondensates of cyanuric acid (e.g., cyanuric acid chloride), polycondensates of epoxy resins or alcohols with substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), styrene resins, allyl group-containing compounds, acenaphthyl group-containing compounds (acenaphthylene, etc.), isocyanuric acid derivatives (TAIC from Mitsubishi Chemical Corporation, MA-DGIC, DA-MGIC, MeDAIC, L-DAIC, DD-1, etc. from Shikoku Chemicals), poly(arylene ether) polymers (HC-G0037, HC-G0024, HC-G0030, HC-G0038, all manufactured by JSR Corporation). These may contain monomer units containing pyridazine, pyrimidine, or pyrazine groups.) Reaction products of fluorenes or indenes with halogen compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methyl chloride, acrylate chloride, methacrylate chloride, etc.), compounds described in Japanese Patent No. 6951829, copolymers containing divinylbenzene as a constituent unit (ODV-XET(X3), ODV-XET(X4), ODV-XET(X5), all manufactured by Nippon Steel Chemical & Material Co., Ltd.), styrene, vinyltoluene, ethyl vinylbenzene Examples include, but are not limited to, divinylbenzene, vinylnaphthalene, vinylbiphenyl, vinylfluorene, divinylbenzene, divinylnaphthalene, divinylbiphenyl, divinylfluorene, BVPM (bis(vinylphenyl)methane), BVPE (bis(vinylphenyl)ethane), BVPH (bis(vinylphenyl)hexane), trivinylcyclohexane, and thermosetting cycloolefin copolymers (Mitsui Chemicals: GigaFreak, Zeon Corporation: TU-01A). These can be used individually or in combination.

[0059] Isocyanate resin: An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of isocyanate resins include aromatic diisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate, 2,4-tollylenediisocyanate, 2,6-tollylenediisocyanate, 4,4'-diphenylmethanediisocyanate, and naphthalenediisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, hydrogenated xylenediisocyanate, norbornenediisocyanate, and lysinediisocyanate; polyisocyanates such as biuret compounds of one or more isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethane reaction between the above isocyanate compounds and polyol compounds.

[0060] Polyamide resins: Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, or oxazolines with dicarboxylic acids, reaction products of diamines and acid chlorides, and ring-opening polymers of lactam compounds. These may be used individually or in combination of multiple types. Specific examples are given below, but are not limited to these. Polymers primarily made from one or more amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.) and lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam); or polymers primarily made from one or more diamines and one or more dicarboxylic acids. Diamines: Aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane; alicyclic diamines such as cyclohexanediamine, bis-(4-aminocyclohexyl)methane, and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine, etc. Dicarboxylic acids: Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succicic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids.

[0061] Polyimide resin: Examples include, but are not limited to, polycondensates of the aforementioned diamine and the tetracarboxylic dianhydrides exemplified below. Furthermore, these can be used individually or in combination of multiple types. Tetracarboxylic acid dianhydrides: 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2'-propyridene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride , thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene 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 dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-Anthracenetetracarboxylic dianhydride, 1,2,7,8-Phenanthrenetetracarboxylic dianhydride, Ethylenetetracarboxylic dianhydride, 1,2,3,4-Butanetetracarboxylic dianhydride, 1,2,3,4-Cyclobutanetetracarboxylic dianhydride, Cyclopentanetetracarboxylic dianhydride, Cyclohexane-1,2,3,4-Tetracarboxylic dianhydride 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride Water, 2,2-propyridene-4,4'-bis(cyclohexane-1,2-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]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxabi Cyclo[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 acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenylbis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

[0062] Cyanate ester resins are cyanate ester compounds obtained by reacting phenol resins with cyanide halides. Specific examples include, but are not limited to, dicyanatebenzene, tricyanatebenzene, dicyanate naphthalene, dicyanate biphenyl, 2,2'-bis(4-cyanatephenyl)propane (BisA-OCN, manufactured by Mitsubishi Gas Chemical Company, Inc.), bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis(4-cyanatephenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene cocondensates in which the hydroxyl groups have been converted to cyanate groups. Furthermore, the cyanate ester compound whose synthesis method is described in Japanese Patent Publication No. 2005-264154 is particularly preferred as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties. The cyanate ester resin may contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate, or commercially available 18% Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd.) to trimerize the cyanate groups as needed and form a sym-triazine ring. The catalyst is typically used in amounts of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the total weight of the curable resin composition.

[0063] Active ester resin: As a curing agent for curable resins other than the maleimide resin of this embodiment, such as epoxy resins, compounds having one or more active ester groups per molecule can be used as needed. Preferred active ester resins are compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Preferably, the active ester resin is obtained by a condensation reaction between at least one compound of a carboxylic acid compound and a thiocarboxylic acid compound and at least one compound of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and at least one compound of a phenol compound and a naphthol compound is preferred. 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. Examples of phenol compounds or naphthol compounds 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-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two molecules of phenol with one molecule of dicyclopentadiene. Preferred examples of activated ester resins include activated ester resins containing a dicyclopentadiene-type diphenol structure, activated ester resins containing a naphthalene structure, activated ester resins containing an acetylated phenol novolac, and activated ester resins containing a benzoylated phenol novolac. Among these, activated ester resins containing a naphthalene structure and activated ester resins containing a dicyclopentadiene-type diphenol structure are more preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene. Commercially available activated ester resins include, for example, activated ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation); activated ester resins containing a bisphenol A-type structure such as the "Unifiner series" (manufactured by Unitika Corporation); and activated ester resins containing a naphthalene structure such as "EX Examples include "B9416-70BK" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing acetylated phenol novolac; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester resins containing benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin that is an acetylated phenol novolac; and "EXB-9050L-62M" (manufactured by DIC Corporation) as an active ester resin containing phosphorus atoms.

[0064] Polybutadiene and its modified products: Polybutadiene and its modified products are compounds that contain polybutadiene or a structure derived from polybutadiene within their molecule. The structure derived from polybutadiene may have some or all of its unsaturated bonds converted to single bonds by hydrogenation. Examples of polybutadiene and its modified products include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminally (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. These may be used individually or in combination. Of these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Clay Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), while examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The weight-average molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10000, more preferably 750 to 7500, and even more preferably 1000 to 5000. Below the lower limit of the above range, the volatilization rate is high, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, compatibility with other curable resins deteriorates. Generally, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds consisting only of hydrocarbons, due to their polarity. On the other hand, the mixture of the present invention, because its framework design does not actively incorporate heteroatoms such as oxygen and nitrogen, exhibits excellent compatibility with materials that have low polarity and low dielectric properties, as well as compounds composed only of hydrocarbons.

[0065] Polystyrene and its modified products: Polystyrene and its modified products are compounds that have polystyrene or a structure derived from polystyrene within their molecule. Examples of polystyrene and its modified products include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray Co., Ltd.), and SEBS (styrene-ethylene-butylene-styrene). Examples of block copolymers include Septon 8004, Septon 8006, Septon 8007L (all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having hydroxyl groups at the ends of styrene-ethylene / ethylene-propylene-styrene block copolymers: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymers: Septon 5125, Septon 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymers: Hybrar 7125F, Hybrar 7311F, both manufactured by Kuraray Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymers: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Co., Ltd.)), but are not limited to these. Furthermore, these can be used individually or in combination of multiple types. Polystyrene and its modified products are preferable to be those without unsaturated bonds, as they have higher heat resistance and are less susceptible to oxidative degradation. Furthermore, while there are no particular restrictions on the weight-average molecular weight of polystyrene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as 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 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the molecular weight be around 10,000 to 300,000.

[0066] [Polyethylene and its modified forms] Polyethylene and its modified products refer to polyethylene or compounds having a polyethylene-derived structure within their molecules. Examples of polyethylene and its modified products include, but are not limited to, ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene 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. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers that contain a crosslinkable structure. Furthermore, these may be used individually or in combination of multiple types. While there are no particular restrictions on the weight-average molecular weight of polyethylene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as 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 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the molecular weight be around 10,000 to 300,000.

[0067] [Benzoxazine compounds] As the benzoxazine compound, 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 may be used. The compound having a phenolic hydroxyl group is not particularly limited, but for example, the aforementioned phenolic resins, phenols (which may have substituents such as alkenyl groups or alkyl groups), and bisphenols can be used. The compound having an amino group is not particularly limited, but for example, the aforementioned amine resins, diamines, and anilines (which may have substituents such as alkenyl groups or alkyl groups) can be used. As the aldehyde compound, for example, the aforementioned aldehydes can be used, but formaldehyde is preferred. Commercially available benzoxazine compounds may be used, including benzoxazine Pd, Fa, ALP-d (all manufactured by Shikoku Chemicals Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Nippon Materials Technology Co., Ltd.).

[0068] Curing accelerator: The curable resin composition of this embodiment can also have its curability improved by adding a curing accelerator. Preferred curing accelerators are anionic curing accelerators that promote the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or by heating, or cationic curing accelerators that promote the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or by heating.

[0069] Examples of anionic curing 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 salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide, but are not limited to these. These can be used individually or in combination.

[0070] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counterions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., with no particular preference, but organic acid ions and hydroxide ions are particularly preferred), tin octoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0071] The amount of curing accelerator used is 0.01 to 5.0 parts by mass per 100 parts by mass of the curable resin composition, as needed.

[0072] Polymerization initiator: 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 ethylenically unsaturated bonds, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. A radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Suitable radical polymerization initiators 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-(t-butylperoxyisopropyl)benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, and t-amyl peroxy-3,5,5-trimethylhexanoate. Examples include, but are not limited to, alkyl peresters such as sanoates, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyoctoate, and lauroyl peroxide; azo compounds such as azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile); and benzopinacols.It is preferable to use organic peroxides because they allow for control of the curing temperature, suppression of outgassing, and have minimal impact on the electrical properties of decomposition products. The amount of radical polymerization initiator added is preferably 0.01 to 5 parts by weight, and particularly preferably 0.01 to 3 parts by weight, per 100 parts by weight of the curable resin composition. If the amount of radical polymerization initiator used is too large, the molecular weight will not elongate sufficiently during the polymerization reaction.

[0073] The curable resin composition of this embodiment may also contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be reactive or additive. Specific examples of phosphorus-containing compounds include phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixyllenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixyllenyl phosphate, 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), and 4,4'-biphenyl(dixyllenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5- Phosphanes such as dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the phosphanes, red phosphorus, etc. are examples, but phosphate esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), 4,4'-biphenyl(dixyllenyl phosphate), or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound) / (total epoxy resin) of 0.1 to 0.6 (by weight). Below 0.1, the flame retardancy is insufficient, and above 0.6, there is a concern that it will adversely affect the hygroscopicity and dielectric properties of the cured product.

[0074] Furthermore, a light stabilizer may be added to the curable resin composition of this embodiment as needed. Suitable light stabilizers include hindered amine light stabilizers (HALS) and the like. While not specifically limited to HALS, typical examples include the polycondensate of dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, the polycondensate of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperi Examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), etc. HALS may be used individually or in combination of two or more types.

[0075] Furthermore, a binder resin may be added to the curable resin composition of this embodiment as needed. Examples of binder resins include, but are not limited to, but but include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenolic resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. The amount of binder resin added is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, preferably 0.05 to 50 parts by weight per 100 parts by weight of the resin component, and more preferably 0.05 to 20 parts by weight as needed.

[0076] Furthermore, the curable resin composition of this embodiment may optionally contain powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, or inorganic fillers made from these in spherical or crushed form. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the above-mentioned inorganic filler used is usually in the range of 80 to 92% by weight, preferably 83 to 90% by weight, of the curable resin composition.

[0077] The curable resin composition of this embodiment may contain known additives as needed. Specific examples of additives that can be used include polybutadiene and its modified counterparts, modified acrylonitrile copolymers, polyphenylene ether, polystyrene and its modified counterparts, polyethylene and its modified counterparts, polyimide, fluororesin, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, per 100 parts by weight of the curable resin composition. From the viewpoint of low water absorption and electrical properties, polybutadiene and its modified counterparts, polyphenylene ether, polystyrene and its modified counterparts, polyethylene and its modified counterparts, and fluororesin are preferred. From the viewpoint of electrical properties, adhesion, and low water absorption, polystyrene and its modified counterparts, polyethylene and its modified counterparts, and polybutadiene and its modified counterparts are preferred. Specifically, examples include butadiene-based thermoplastic elastomers such as styrene-butadiene copolymers (SBR: RICON-100, RICON-181, RICON-184, all manufactured by Clay Valley, etc.) and acrylonitrile-butadiene copolymers; and styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene / isoprene)-styrene copolymer, and styrene-ethylene-propylene-styrene copolymer. These styrene-based thermoplastic elastomers may be used individually or in combination of two or more types.Among these high molecular weight materials, styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymer, hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, hydrogenated styrene-isoprene-styrene copolymer, and hydrogenated styrene(butadiene / isoprene)-styrene copolymer are preferred, and styrene-isoprene-styrene copolymer, hydrogenated styrene-butadiene-styrene copolymer, hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene(butadiene / isoprene)-styrene copolymer, and styrene-ethylene-propylene-styrene copolymer are even more preferred because they have higher heat resistance and are less susceptible to oxidative degradation. Specifically, Septon 1020, Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, Septon 8004, Septon 8006, Septon 8007L, Septon HG252, Septon V9827, Hybrar 7125 (hydrogenated), Hybrar 7215F, Hybrar 7311F, Septon 2104 (both manufactured by Kuraray Co., Ltd.) Furthermore, there are no particular restrictions on the weight-average molecular weight of the styrene-based thermoplastic elastomer as long as it is 10,000 or more, but if it is too large, the compatibility with polyphenylene ether compounds, as well as 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 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferable that it be around 10,000 to 300,000. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, due to their polarity, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons, among the above-mentioned additives and curable resin components. On the other hand, the maleimide resin mixture of this embodiment does not have a skeleton design that actively introduces heteroatoms such as oxygen and nitrogen (it has few polar groups), and therefore has excellent compatibility with materials that have low polarity and low dielectric properties, as well as compounds composed only of hydrocarbons.

[0078] The curable resin composition of this embodiment is obtained by uniformly mixing the above components in predetermined proportions. Pre-curing is typically performed at 130-180°C for 30-500 seconds, followed by post-curing at 150-250°C for 2-15 hours to ensure a sufficient curing reaction and obtain the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, and then cured after removing the solvent.

[0079] The curable resin composition obtained in this embodiment has moisture resistance, heat resistance, and high adhesion. Therefore, the curable resin composition of this embodiment can be used in a wide range of fields where moisture resistance, heat resistance, and high adhesion are required. Specifically, it is useful as a material for all kinds of electrical and electronic components such as insulating materials, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), encapsulating materials, and resists. In addition to molding materials and composite materials, it can also be used in fields such as paint materials, adhesives, and 3D printing. In particular, its solder reflow resistance is beneficial in semiconductor encapsulation.

[0080] The semiconductor device is sealed with the curable resin composition of this embodiment. Examples of semiconductor devices include DIP (Dual In-Line Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and the like.

[0081] The method for preparing the curable resin composition of this embodiment is not particularly limited, but may be done by simply uniformly mixing each component or by prepolymerization. For example, the maleimide resin of this embodiment may be prepolymerized by heating in the presence or absence of a catalyst, and in the presence or absence of a solvent. Similarly, in addition to the maleimide resin of this embodiment, prepolymerization may be performed by adding curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate ester compounds, phenolic resins, and acid anhydride compounds, and other additives. Mixing or prepolymerizing each component may be done using, for example, an extruder, kneader, or roll in the absence of a solvent, and a reaction vessel with a stirring device may be used in the presence of a solvent.

[0082] For uniform mixing, the resin composition is kneaded using equipment such as a kneader, roll, or planetary mixer at a temperature in the range of 50 to 100°C. After pulverization, the resulting resin composition can be molded into cylindrical tablets using a molding machine such as a tablet machine, or into granular powder or powdery molded bodies. Alternatively, these compositions can be melted on a surface support and molded into sheets with a thickness of 0.05 mm to 10 mm to produce curable resin composition molded bodies. The resulting molded bodies are non-sticky at 0 to 20°C and maintain almost no decrease in fluidity or curability even after storage at -25 to 0°C for more than a week. The resulting molded body can be molded into a hardened product using a transfer molding machine or a compression molding machine.

[0083] The curable resin composition of this embodiment can also be modified by adding an organic solvent to form a varnish-like composition (hereinafter simply referred to as varnish). The curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as needed to form a varnish. This varnish can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and the resulting prepreg can be heat-dried. The resulting prepreg can then be hot-press-molded to obtain a cured product of the curable resin composition of this embodiment. In this case, the solvent used is typically in an amount that accounts for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of this embodiment and the solvent. If the composition is in liquid form, a cured product of the curable resin containing carbon fibers can also be obtained directly, for example, by the RTM (Resin Transfer Molding) method.

[0084] Furthermore, the curable composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and other properties in the B-stage. Such a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of this embodiment as a curable resin composition varnish onto a release film, removing the solvent under heating, and then performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

[0085] The curable resin composition of this embodiment can be heated and melted to reduce viscosity and impregnate reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples include, but are not limited to, 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; inorganic fibers other than glass; poly(p-phenylene terephthalamide) (Kevlar®, manufactured by DuPont); fully aromatic polyamides; polyesters; and organic fibers such as poly(p-phenylene benzoxazole), polyimide, and carbon fibers. The shape of the substrate is not particularly limited, but examples include woven fabrics, nonwoven fabrics, rovings, and chopped strand mats. As for the weaving method of the woven fabric, plain weave, twill weave, etc., are known, and these can be appropriately selected and used depending on the intended application and performance. Furthermore, glass woven fabrics that have been opened or surface-treated with silane coupling agents are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Alternatively, a prepreg can be obtained by impregnating the reinforcing fibers with the varnish and then heating and drying them.

[0086] The laminate of this embodiment comprises one or more of the above-mentioned prepregs. The laminate is not particularly limited as long as it comprises one or more of the above-mentioned prepregs, and may have any other layers. The method for manufacturing the laminate is not particularly limited and can be any generally known method as appropriate. For example, when forming a metal foil laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., can be used, and the laminate can be obtained by laminating the above-mentioned prepregs together and heating and pressing them. At this time, the heating temperature is not particularly limited, but 65 to 300°C is preferred, and 120 to 270°C is more preferred. The pressurizing pressure is not particularly limited, but if the pressurizing pressure is too high it is difficult to adjust the solid content of the resin in the laminate and the quality is not stable, and if the pressurizing pressure is too low it becomes difficult to form air bubbles and the adhesion between the layers is poor, so 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred. The laminate of this embodiment can be suitably used as a metal foil laminate described later by comprising a layer made of metal foil. By cutting the above prepreg into the desired shape, laminating it with copper foil or other materials as needed, and then applying pressure to the laminate using methods such as press molding, autoclave molding, or sheet winding molding while heating and curing a curable resin composition, electrical and electronic laminates (printed wiring boards) and carbon fiber reinforced materials can be obtained.

[0087] The cured product of this embodiment can be used in various applications such as molding materials, adhesives, composite materials, and paints. Because the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is suitably used in electrical and electronic components such as encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, printed circuit boards, and build-up laminates, as well as in composite materials for lightweight, high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

[0088] (Another embodiment) The cured product of this embodiment can be further used as a resist film, an interlayer insulating material for build-up methods, or an optical waveguide on substrates such as printed circuit boards, optoelectronic substrates, and optical substrates, which are electrical, electronic, and optical materials. Specific examples of these applications include, for example, computers, home appliances, and portable devices. The thickness of this cured product layer is typically around 0.5 to 160 μm, with 1 to 100 μm being preferred.

[0089] The curable resin composition of this embodiment preferably contains a photopolymerization initiator. A photoradical polymerization initiator or a photocationic polymerization initiator is preferred as the photopolymerization initiator. The content of the photopolymerization initiator is 0.001 to 20 parts by mass, more preferably 0.002 to 15 parts by mass, per 100 parts by mass of the resin component. A content of less than 0.001 parts by mass may result in insufficient photocuring, while a content of more than 20 parts by mass may worsen the dielectric properties. Examples of preferred photopolymerization initiators are given below, but the invention is not limited to these; they may be used individually or in combination of two or more.

[0090] Photoradical polymerization initiators: While not particularly limited, any compound that generates radicals and initiates a chain polymerization reaction upon irradiation with ultraviolet or visible light can be used as a photoradical polymerization initiator. Examples include benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphate, camphorquinone, 9-fluorenone, and diphenyl disulfide. Specifically, IRGACURE... RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, OXE03, OXE04, DAROCURE RTM 1173, LUCIRIN RTM TPO (both manufactured by BASF), Sequall RTMExamples include Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Chemical Co., Ltd.), and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.). Among these, the oxime ester initiators IRGACURER OXE01, OXE02, OXE03, and OXE04 are preferred.

[0091] Photocationic polymerization initiators: Photocationic polymerization initiators are not particularly limited to radical polymerization initiators, as long as they are compounds that generate cation species such as Brønsted acids and Lewis acids upon irradiation with ultraviolet or visible light, but aromatic iodonium complex salts and aromatic sulfonium complex salts can be given as examples. Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, tolylcmyliodonium tetrakis(pentafluorophenyl) borate (manufactured by Rhodia, trade name: Rhodesil PI2074), and di(4-tert-butyl)iodonium tris(trifluoromethanesulfonyl) methanide (manufactured by BASF, trade name: CGIBBI-C1). Specific examples of aromatic sulfonium complex salts include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by Sunapro, trade name: CPI-101A), thiophenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate (manufactured by Sunapro, trade name: CPI-210S), 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name: SP-172), and aromatic sulfonium hexafluoroantimonate containing 4-thiophenyldiphenylsulfonium hexafluoroantimonate. Examples include a mixture of thymonates (manufactured by ACETOCorporateUSA, trade name: CPI-6976), triphenylsulfonium tris(trifluoromethanesulfonyl)methandide (manufactured by BASF, trade name: CGITPS-C1), tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tris(trifluoromethylsulfonyl)methide (manufactured by BASF, trade name: GSID26-1), and tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate (manufactured by BASF, trade name: Irgacure PAG290).Of these, in the present invention, aromatic sulfonium complex salts that have high vertical rectangular processability and high thermal stability are preferred in the photosensitive image forming process. Among these, a mixture of aromatic sulfonium hexafluoroantimonates containing 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate and 4-thiophenyldiphenylsulfonium hexafluoroantimonate, and tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate are particularly preferred.

[0092] The curable resin composition of this embodiment can be used by known methods. For example, the curable resin composition of the present invention, whose viscosity has been adjusted with an organic solvent, can be applied to a support and then dried at 50 to 180°C, preferably 80 to 140°C, for 5 to 30 minutes to obtain a film-like curable resin composition. Examples of the support include silicon wafers, ceramic substrates, rigid substrates, flexible substrates, and silicon wafers on which an inorganic surface protective film such as a SiN film or an SiO2 film has been formed.

[0093] The coating method is not particularly limited, but examples include coating using a spin coater, slit coater, roll coater, etc., and screen printing. Among these, for example, when coating a silicon wafer, it is preferable to use a coating method using a spin coater. The film thickness of the film-like curable resin composition can be arbitrarily adjusted by adjusting the concentration of the curable resin composition and the coating thickness, and is not particularly limited, but for example, when it is used as a protective film for semiconductor devices or an interlayer insulating film, the film thickness after drying is preferably 3 to 50 μm, more preferably 5 to 30 μm, and even more preferably 5 to 20 μm. If the film thickness is less than 3 μm, it tends not to adequately protect the devices and circuits beneath the film, and if it exceeds 50 μm, it tends not to be possible to form fine patterns. In the present invention, even with a film thickness of 10 μm or more (preferably 10 to 20 μm), it is possible to form fine patterns, and it is possible to form patterns in which the aspect ratio of the aperture diameter (Via diameter) of the through holes formed by exposure and development described later is 0.3 or more (more preferably 0.5 or more).

[0094] Next, the film-like curable resin composition obtained in this manner is exposed to light by applying a mask having a predetermined pattern shape to photopolymerize the curable resin composition of the present invention. The exposure method can be contact exposure or reduction projection exposure. The exposure wavelength is preferably ultraviolet to visible light in the range of 200 to 500 nm, and a standard reduction projection exposure machine (stepper) can be used. Furthermore, from the viewpoint of forming fine patterns, the exposure wavelength is more preferably 256 to 436 nm, and even more preferably 256 to 365 nm. The exposure amount is not particularly limited, but is preferably 100 to 5000 mJ / cm². 2 Preferably, the concentration is 300-3000 mJ / cm². 2 It is preferable that it be so.

[0095] Next, by developing the film-like curable resin composition after exposure, dissolving and removing the unexposed portion with a developer, a polymerized film (polymer) having a predetermined pattern can be obtained. That is, in the exposed portion, radicals or cation species generated from the photopolymerization initiator by light irradiation cause crosslinking of component (A) and other compounds, making them insoluble in the developer. In contrast, the unexposed portion dissolves in the developer, so by utilizing the difference in solubility in the developer between the exposed portion and the unexposed portion, a polymerized film having a pattern such as through-holes of a predetermined aperture diameter (Via diameter) can be obtained. As the developer, the aforementioned solvent can be used, and it may further contain alcohol-based solvents such as methanol, ethanol, or propanol to adjust the solubility during development. Examples of the development method include the spray method, the paddle method, and the dip method.

[0096] Furthermore, it is preferable to further rinse the polymerized film having a predetermined pattern obtained by the development with an organic solvent such as cyclopentanone or a mixed solvent of cyclopentanone and ethanol. The polymerized film after development preferably has a residual film rate of 90% or more, from the viewpoint of suppressing surface roughness and facilitating dimensional design. In the present invention, the residual film rate refers to the ratio of the thickness of the polymerized film after development to the thickness of the film-like curable resin composition after drying (before exposure) (thickness of the polymerized film after development / thickness of the film-like curable resin composition after drying (before exposure)).

[0097] Next, the polymerized film having a predetermined pattern obtained by the development process can be heated and cured as needed to obtain a cured film (cured product) having a predetermined pattern. The heating temperature (curing temperature) is preferably 60 to 230°C, and more preferably 150 to 230°C. The heating time is preferably 30 to 120 minutes. In this invention, the curing temperature refers to the temperature required to thermally cure the functional groups that remain unreacted during exposure through a thermal reaction.

[0098] As described above, by using the curable resin composition of the present invention, a cured film having a fine pattern can be obtained. Preferably, the aspect ratio of the aperture diameter (Via diameter) of the formed through-holes is 0.3 or greater, and more preferably 0.5 or greater. In this invention, the aperture diameter can be determined by measuring it using an optical microscope or a scanning electron microscope (SEM).

[0099] The cured product obtained using such a curable resin composition of the present invention after photocuring or photothermal curing (curing by combining photocuring and thermal curing) can be suitably used for at least one type of film selected from the group consisting of surface protective films for semiconductor devices, interlayer insulating films, and insulating films for redistribution layers. Furthermore, the curable resin composition of the present invention is particularly effective when such a film requires a film thickness of 10 μm or more, and when patterning is required such that the aspect ratio of the through-hole opening diameter (Via diameter) is 0.3 or more (more preferably 0.5 or more). [Examples]

[0100] Next, the present invention will be described in more detail with reference to examples. Hereinafter, unless otherwise specified, parts refer to parts by weight. However, the present invention is not limited to these examples.

[0101] The various analytical methods used in the examples are described below. <Gel Permeation Chromatography (GPC)> Manufacturer: Shimadzu Corporation Columns: Guard columns SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603 Flow rate: 0.3ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: RI (Differential Refraction Detector)

[0102] <Acid Value Measurement> Equipment: Hiranuma Automatic Titrator COM-1600 Equipment conditions: Reference electrode RE-201 Platinum indicator electrode PT-301 Measurement method: The acid value was measured in accordance with JIS K 2501 "Petroleum products and lubricating oils - Neutralization value test method". The titration solvent was a mixed solvent of THF / IPA (v / v=7 / 3). 50 ml of titration solvent was measured into a beaker, and 5 ml of buffer storage solution B for petroleum product neutralization value measurement was added to the sample. The pH was then measured to determine the endpoint pH. Subsequently, 50 ml of titration solvent was measured into a beaker and titrated with 0.1 mol / L 2-propanol potassium hydroxide solution (for petroleum product neutralization value measurement) using a potentiometric titrator to obtain a blank value. 0.4 g of the maleimide resin mixture obtained in the synthesis example was accurately weighed into a beaker, 50 ml of titration solvent was added, and the solution was dissolved with a stirrer. The solution was then titrated to the endpoint.

[0103] [Synthesis Example 1] A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was purged with nitrogen. 559 parts of aniline, 291 parts of α,α,α',α'-tetramethylbenzenedimethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 360 parts of toluene were added, followed by 63 parts of 35% hydrochloric acid aqueous solution. Stirring was then started. The internal temperature was raised to 160°C while the water produced by dehydration was removed along with the toluene, and the reaction was allowed to proceed for 15 hours. After cooling to room temperature, the removed toluene and water were returned to the system, and 88 parts of 30% sodium hydroxide aqueous solution were added for neutralization. Subsequently, the organic layer was washed with water until the waste liquid was neutral, and then concentrated to obtain 458 parts of an aromatic amine resin represented by the following formula (A1). The amine equivalent of the aromatic amine resin (A1) was 185 g / eq.

[0104] [ka]

[0105] [Synthesis Example 2] A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 31.0 parts toluene, 10.3 parts n-methylpyrrolidone, 22.3 parts amine resin (A1) obtained in Synthesis Example 1, 0.9 parts methanesulfonic acid, and 39.6 parts styrene-maleic anhydride copolymer (acid value: 89, Mn: 3,774, Mw: 6,938), and reacted at 120°C for 15 hours. After cooling, 15.5 parts toluene, 5.2 parts n-methylpyrrolidone, and 13.2 parts maleic anhydride were added, and the reaction was continued under reflux for 6 hours. After cooling, the reaction solution was diluted with 379.0 parts toluene, and the organic layer was washed with 143.0 parts 10% saline solution until the waste liquid was neutral. The target compound (M1) was obtained as toluene varnish by distilling off the solvent under heating and reduced pressure. The GPC chart of the obtained compound is shown in Figure 1. The acid value was 13. Based on the acid value and molecular weight of the raw material, styrene-maleic anhydride copolymer, m was calculated to be 61.4 and n to be 5.5.

[0106] [Synthesis Example 3] A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 16.5 parts toluene, 5.5 parts n-methylpyrrolidone, 10.6 parts 4,4-methylenebis(2-ethyl-6-methylaniline), 0.4 parts methanesulfonic acid, and 22.4 parts styrene-maleic anhydride copolymer (acid value: 151, Mn: 2,454, Mw: 4,997), and reacted at 120°C for 15 hours. After cooling, 8.3 parts toluene, 2.8 parts n-methylpyrrolidone, and 6.6 parts maleic anhydride were added, and the reaction was continued under reflux for 6 hours. After cooling, the reaction solution was diluted with 202.6 parts toluene, and the organic layer was washed with 76.5 parts 10% saline solution until the waste liquid was neutral. The target compound (M2) was obtained as toluene varnish by distilling off the solvent under heating and reduced pressure. The GPC chart of the obtained compound is shown in Figure 2. The acid value was 6.6. Based on the acid value and molecular weight of the raw material, styrene-maleic anhydride copolymer, m was calculated to be 41.6 and n to be 6.7.

[0107] [Examples 1-6] A 250 μm cushion paper with a 100 mm x 50 mm cutout in the center was placed on a copper foil. 5.0 g of the sample, formulated according to the ratios shown in Table 1, was placed in the center of the cutout. With another piece of copper foil on either side, the mixture was molded using a vacuum heating press and cured at 220°C for 2 hours. Subsequently, the copper foil was etched using ferric chloride to obtain a cured film. The dielectric loss tangent and glass transition temperature (Tg) of the cured film were measured using the method described below and are shown in Table 1.

[0108] <Dielectric Loss Tangent Test> Tests were conducted using a 10GHz cavity resonator manufactured by AET Co., Ltd. at 25°C using the cavity resonator perturbation method. The sample size was 1.7 mm wide x 100 mm long with a thickness of 1.7 mm. <Heat resistance test (DMA)> Equipment: DMA Q800 (TA instruments) Measurement temperature range: 30~350℃ Heating rate: 2°C / min Sample size: 5mm wide x 40mm long x 0.5mm thick Criteria for judgment: The peak point of tanδ is defined as Tg.

[0109] [Table 1]

[0110] • M3: (Maleimide resin obtained by the method described in Synthesis Example 3 of International Publication No. 2022 / 210433) • NC-3000 (epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) • Unifiner W-575 (active ester, manufactured by Unitika Ltd.) • SA-9000-111 (a polyphenylene ether compound with a methacrylate structure, manufactured by Sabic) • OPE-2St 1200 (a polyphenylene ether compound having a styrene structure, manufactured by Mitsubishi Gas Chemical Company, Inc.) • OPE-2St 2200 (a polyphenylene ether compound with a styrene structure, manufactured by Mitsubishi Gas Chemical Company, Inc.) • Ricon100 (styrene-butadiene copolymer, manufactured by Clay Valley Corporation) • Septon 2104 (styrene-ethylene-propylene-styrene-rubber, manufactured by Kuraray Co., Ltd.) • TAIC (Triallyl Isocyanurate, manufactured by Mitsubishi Chemical Corporation) • Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.) • BisA-OCN (2,2'-bis(4-cyanatephenyl)propane, manufactured by Mitsubishi Gas Chemical Company, Inc.) • DCP (Dicumyl Peroxide, manufactured by Kayaku Nurion Co., Ltd.) • 18% Octope Zn (manufactured by Hope Pharmaceutical Co., Ltd.)

[0111] The results in Table 1 confirm that Examples 1-6 possess excellent heat resistance and low dielectric loss tangent. The attenuation rate of signals flowing through the dielectric material that makes up a printed circuit board is proportional to the dielectric loss tangent. Since signal attenuation directly translates into heat generation and causes a temperature rise, a low dielectric loss tangent is important for printed circuit board materials.

[0112] [Example 7] The photosensitive resin composition, formulated in the proportions shown in Table 2, was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) to a thickness of 20 μm using an applicator. The coating was dried in a hot air dryer at 80°C for 30 minutes, and then exposed to ultraviolet light at 3000 mJ / cm² using a UV irradiator (GS YUASA: CS 30L-1). 2 The copper foil was irradiated with ultraviolet light. Afterward, it was confirmed whether a hardened film could be obtained by etching the copper foil with ferric chloride.

[0113] [Table 2]

[0114] • OXE-04 (Photoradical polymerization initiator, manufactured by BASF Japan Ltd.) • MIZ-001 (maleimide resin, manufactured by Nippon Kayaku Co., Ltd.)

[0115] <Hardening Test> [Reference Example 1] 10 parts of the compound described in Synthesis Example 2, 20 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, active ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), 60 parts of OPE-2st 2200 (manufactured by Mitsubishi Gas Chemical Company, polyphenylene ether compound), 3 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (compound having an ethylenically unsaturated bond), KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 1 part Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 0.5 parts 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as solvent, and 49 parts of tetrahydrofuran.By mixing the ingredients in a 6:1 ratio and heating them under a nitrogen atmosphere at 110°C for 10 minutes, then at 220°C for 1 hour, a cured product was obtained.

[0116] [Reference example 2] A mixture of 10 parts of the compound described in Synthesis Example 2, 50 parts of NC-3000 (manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of the compound described in Example 10 of Japanese Patent No. 6951829 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, polymerization initiator) was applied to a PET film to a thickness of 100 μm. Another PET film was attached to the side not in contact with the film, and the mixture was subjected to a high-pressure mercury lamp (365 nm) at a pressure of 3000 mJ / cm². 2 By irradiating it with ultraviolet light, a cured product could be obtained. [Industrial applicability]

[0117] The curable resin composition and its cured product of the present invention are useful for applications such as insulating materials for electrical and electronic components (high-reliability semiconductor encapsulating materials, etc.), laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), resist films, substrates such as printed circuit boards as optical waveguides, optoelectronic substrates and optical substrates, adhesives (conductive adhesives, etc.), various composite materials including CFRP, paints, and 3D printing.

[0118] [Note] As described above, this embodiment includes the following disclosures. [1] A maleimide resin having repeating units of the following formulas (a) and (b), with an acid value of 25 or less, At least one selected from the group consisting of maleimide resins other than the aforementioned maleimide resin, epoxy resin, activated ester resin, polyphenylene ether compound, polystyrene and modified thereof, polyethylene and modified thereof, thermoplastic elastomer, compound having an ethylenically unsaturated bond, cyanate ester resin, polybutadiene and modified thereof, and cyanate ester resin, A curable resin composition containing [a specific ingredient].

[0119] [ka]

[0120] (In the above formula, X is represented by the following formula (Y). Ra represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. m is the average number of repeats, where 1 ≤ m < 1000. n is the average number of repeats, where 1.1 ≤ n < 1000. (a) and (b) are linked by *, and the repeat positions may be random.)

[0121] [ka]

[0122] (In the above formula (Y), each R1 exists independently and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each R exists independently and represents a hydrocarbon group having 1 to 10 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocycle. a is an integer from 0 to 4, and d is an integer from 0 to 2. * indicates a bond position.) [2] The curable resin composition according to the preceding paragraph [1], wherein the Ar is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene. [3] The curable resin composition according to the preceding paragraph [1], wherein formula (Y) is one or more of the following formulas (A) to (F).

[0123] [ka]

[0124] (In the above formula, R represents a hydrocarbon group with 1 to 10 carbon atoms, a is an integer from 0 to 4, and p is an integer from 1 to 20. * indicates the bond position.) [4] A maleimide resin obtained by reacting a styrene-based monomer maleic anhydride copolymer with a compound containing two or more amino groups in its molecule and maleic anhydride, wherein the compound containing two or more amino groups in its molecule is one or more of the amine compounds represented by the following formula (Y'), and the acid value of the maleimide resin is 25 or less. A curable resin composition containing at least one selected from the group consisting of maleimide resins other than the aforementioned maleimide resin, epoxy resins, activated ester resins, polyphenylene ether compounds, polystyrene and modified products thereof, polyethylene and modified products thereof, thermoplastic elastomers, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, cyanate ester resins, epoxy resins, activated ester compounds, phenol resins, amine resins, isocyanate resins, polyamide resins, polyimide resins, and benzoxazine compounds.

[0125] [ka]

[0126] (In the above formula (Y'), each R1 exists independently and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each R exists independently and represents a hydrocarbon group having 1 to 10 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocycle. a is an integer from 0 to 4, and d is an integer from 0 to 2. b is the average value of the number of repeats, where 1 ≤ b < 5.) [5] The curable resin composition according to the preceding paragraph [4], wherein the Ar is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene. [6] The curable resin composition according to item [4] above, wherein the amine compound represented by formula (Y') is one or more of the amine compounds represented by the following formulas (A') to (F').

[0127] [ka]

[0128] (In the above formula, R represents a hydrocarbon group with 1 to 10 carbon atoms, a is an integer from 0 to 4, and p is an integer from 1 to 20. b is the average value of the number of repetitions, where 1 ≤ n < 5.) [7] Furthermore, a curable resin composition according to any one of the preceding paragraphs [1] to [6], comprising a curing accelerator. [8] Furthermore, a curable resin composition according to any one of the preceding paragraphs [1] to [7], comprising a photoradical polymerization initiator. [9] A curable resin composition for use as a resist, as described in any one of the preceding paragraphs [1] to [8].

[10] A curable resin composition for printed circuit boards, as described in any one of the preceding paragraphs [1] to [8].

[11] A varnish comprising a curable resin composition and an organic solvent as described in any one of the preceding paragraphs [1] to

[10] .

[12] A cured product obtained by curing a curable resin composition described in any one of the preceding paragraphs [1] to

[10] .

Claims

1. A maleimide resin having repeating units of the following formulas (a) and (b), with an acid value of 25 or less, At least one selected from the group consisting of maleimide resins other than the aforementioned maleimide resin, epoxy resin, activated ester resin, polyphenylene ether compound, polystyrene and modified thereof, polyethylene and modified thereof, thermoplastic elastomer, compound having an ethylenically unsaturated bond, cyanate ester resin, polybutadiene and modified thereof, and cyanate ester resin, A curable resin composition containing [a specific ingredient]. 【Chemistry 1】 (In the above formula, X is represented by the following formula (Y). Ra represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. m is the average number of repetitions, where 1 ≤ m < 1000. n is the average number of repetitions, where 1.1 ≤ n < 1000. (a) and (b) are linked by *, and the repetition positions may be random.) 【Chemistry 2】 (In the above formula (Y), R １ Each of the following exists independently and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the following exists independently and represents a hydrocarbon group having 1 to 10 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocycle. a is an integer from 0 to 4, and d is an integer from 0 to 2. * indicates a bond position.

2. The curable resin composition according to claim 1, wherein Ar is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene.

3. The curable resin composition according to claim 1, wherein formula (Y) is one or more of the following formulas (A) to (F). 【Transformation 3】 (In the above formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, a is an integer from 0 to 4, and p is an integer from 1 to 20. * indicates the bond position.)

4. A maleimide resin obtained by reacting a styrene-based monomer maleic anhydride copolymer with a compound containing two or more amino groups in its molecule and maleic anhydride, wherein the compound containing two or more amino groups in its molecule is one or more of the amine compounds represented by the following formula (Y'), and the acid value of the maleimide resin is 25 or less. A curable resin composition containing at least one selected from the group consisting of maleimide resins other than the aforementioned maleimide resin, epoxy resin, activated ester resin, polyphenylene ether compound, polystyrene and modified thereof, polyethylene and modified thereof, thermoplastic elastomer, compound having an ethylenically unsaturated bond, cyanate ester resin, polybutadiene and modified thereof, phenol resin, amine resin, isocyanate resin, polyamide resin, polyimide resin, and benzoxazine compound. 【Chemistry 4】 (In the above formula (Y'), R １ Each of the following elements exists independently and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Each of the following elements exists independently and represents a hydrocarbon group having 1 to 10 carbon atoms. Ar represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocycle. a is an integer from 0 to 4, and d is an integer from 0 to 2. b is the average number of repeats, where 1 ≤ b < 5.

5. The curable resin composition according to claim 4, wherein Ar is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene.

6. The curable resin composition according to claim 4, wherein the amine compound represented by formula (Y') is one or more amine compounds represented by the following formulas (A') to (F'). 【Transformation 5】 (In the above formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, a is an integer from 0 to 4, and p is an integer from 1 to 20. b is the average value of the number of repetitions, where 1 ≤ n < 5.)

7. Furthermore, the curable resin composition according to any one of claims 1 to 6, further containing a curing accelerator.

8. Furthermore, the curable resin composition according to any one of claims 1 to 6, further containing a photoradical polymerization initiator.

9. A curable resin composition according to any one of claims 1 to 6, for use as a resist.

10. A curable resin composition according to any one of claims 1 to 6, for use in printed circuit boards.

11. A varnish comprising the curable resin composition and an organic solvent according to any one of claims 1 to 6.

12. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 6.

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