JP2023130779A - Curable resin composition, cured product of the same, and semiconductor device - Google Patents

Abstract

To provide a curable resin composition which is curable by light such as ultraviolet light, as needed, by heat, and imparts its cured product with low dielectric characteristics.SOLUTION: A curable resin composition contains (A) a compound having at least two or more styrene structures in the molecule, and (B) a photopolymerization initiator.SELECTED DRAWING: Figure 3

Description

The present invention relates to a curable resin composition with excellent dielectric properties and a cured product thereof, and can be applied to a protective film for semiconductor elements, an interlayer insulating film, an insulating film for a rewiring layer, etc.

Conventionally, polyimide precursors and polybenzoxazole precursors, which have excellent heat resistance, electrical properties, and mechanical properties, have been used for protective films for semiconductor elements, interlayer insulating films formed on semiconductor surface layers, and insulating films for rewiring layers. A curable resin composition containing the following is used. As the curable resin composition containing the polyimide precursor, for example, JP-A-54-109828 (Patent Document 1) describes polyamic acid, a compound having a polymerizable unsaturated bond, and a photopolymerization initiator. A resin composition containing the same is described. Further, JP-A No. 2008-83468 (Patent Document 2) describes a resin composition containing a polyamic acid ester composition and a photopolymerization initiator. The curable polyimide precursor obtained in such a resin composition is a negative curable material whose unsaturated bonds are photocrosslinked with a photopolymerization initiator to form a pattern. Further, as the curable resin composition containing the polybenzoxazole precursor, for example, JP-A-56-27140 (Patent Document 3) and JP-A-11-237736 (Patent Document 4) disclose polybenzoxazole precursors. Resin compositions containing benzoxazole precursors and quinonediazide compounds are described. Such a resin composition is a positive curable material in which quinone diazide turns into indene carboxylic acid upon irradiation with light, and the irradiated area (exposed area) is dissolved in an alkaline developer to obtain a pattern.

Polyimide precursors and polybenzoxazole precursors such as those described in Patent Documents 1 to 4 require a dehydration ring closure reaction in the curing reaction, so in order to cure them, they must be heated to at least 230°C. It is necessary. However, when the heating temperature is as high as this, there is a possibility that the semiconductor element will be damaged. Furthermore, if the ring-closing reaction is insufficient, there is a concern that dielectric properties may deteriorate due to remaining polar groups such as carboxyl groups, phenolic hydroxyl groups, and amide bonds.

Japanese Patent Publication No. 54-109828 Japanese Patent Application Publication No. 2008-83468 Japanese Patent Publication No. 56-27140 Japanese Patent Application Publication No. 11-237736

The present invention has been made in view of the above points, and provides a curable resin composition that can be cured by light such as ultraviolet rays and, if necessary, heat, and whose cured product has low dielectric properties. The purpose is to

As a result of intensive research to solve the above problems, the present inventors found that a cured product of a curable resin composition containing a photopolymerization initiator and a compound having at least two styrene structures in the molecule has low dielectric properties. The present inventors have discovered that the present invention is excellent.

That is, the present invention relates to the following [1] to [8]. In the present invention, "(numerical value 1) to (numerical value 2)" indicates that the upper and lower limits are included.
[1]
A curable resin composition containing (A) a compound having at least two styrene structures in its molecule, and (B) a photopolymerization initiator.
[2]
The curable resin composition according to the above item [1], wherein the component (A) is a compound represented by the following formula (1),

(In formula (1), a plurality of R's each exist independently and represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p and r represent integers of 0 to 4, and q represents an integer from 0 to 3, and n is 1≦n≦20.)
[3]
The curable resin composition according to item [1] or [2], wherein the component (B) is a cationic photopolymerization initiator.
[4]
The curable resin composition according to item [1] or [2] above, wherein the component (B) is a radical photopolymerization initiator.
[5]
The curable resin composition according to item [1] or [2], wherein the component (B) is an oxime ester photoradical polymerization initiator.
[6]
Furthermore, the curable resin composition according to any one of the above items [1] to [5], which further contains an inorganic filler.
[7]
A cured product obtained by photocuring or photothermally curing the curable resin composition according to items [1] to [6] above.
[8]
A semiconductor device comprising the cured product according to item [7] above as at least one selected from the group consisting of a surface protective film, an interlayer insulating film, and a rewiring layer insulating film.

According to the present invention, it is possible to provide a resin composition having excellent low dielectric properties, a cured product thereof, and a semiconductor device including an interlayer insulating layer, a surface protection film, and an insulating film of a rewiring layer formed from the cured product. It is.

A GPC chart of Synthesis Example 1 is shown. A GPC chart of Synthesis Example 2 is shown. A ¹ H-NMR chart of Synthesis Example 2 is shown.

The curable resin composition of the present invention comprises (A) a compound having at least two styrene structures in the molecule (hereinafter also referred to as component (A)), (B) a photopolymerization initiator (hereinafter referred to as component (A)), and (B) a photoinitiator (hereinafter referred to as component (A)). Also referred to as B).

As component (A), any known compound having at least two or more styrene structures in the molecule may be used, such as OPE-2St (Mitsubishi Gas Chemical Co., Ltd.), ODV (Oligodivinyl copolymer, manufactured by Nippon Steel Chemical & Materials), 1,2-bis(vinylphenyl)ethane (BVPE: 4,4'-ethylenebisstyrene, 3,4'-ethylenebisstyrene, 3,3'-ethylenebis (compounds such as styrene), divinylfluorene, divinylbiphenyl, divinylnaphthalene, divinylbenzene, and a compound represented by the following formula (1). Component (A) may be used alone or in combination. Among these, from the viewpoints of heat resistance, dielectric properties, compatibility with other curable resins (epoxy resins, active ester resins, etc.), circuit embeddability, etc., the following formula (1) is used as component (A): Compounds represented by are preferred.

(In formula (1), each of the plurality of R's exists independently and represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p and r are integers of 0 to 4, and q is an integer of 0 to 4. Represents an integer of 3, n is the average value of the number of repetitions, and 1≦n≦20.)

In the formula (1), p and r are 0 to 4, preferably 0 to 2, and more preferably 0. q is 0 to 3, preferably 0 to 2, and more preferably 0. n is 1≦n≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦10, particularly preferably 1.1≦n≦5 . The value of n can be calculated from the number average molecular weight (Mn) value of the compound of formula (1) determined by gel permeation chromatography (GPC). The number average molecular weight is preferably 200 or more and less than 5,000, more preferably 300 or more and less than 3,000, and particularly preferably 400 or more and less than 2,000. When the weight average molecular weight is less than 5,000, purification by washing with water becomes easy, and when it is 200 or more, the target compound does not volatilize in the solvent distillation step.

In the formula (1), R is a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group, preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms. It is a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms. Hydrocarbons in which R has 3 or less carbon atoms are less likely to undergo molecular vibration when exposed to high frequencies, and therefore have particularly excellent electrical properties.

The compound represented by the formula (1) is derived from the compound represented by the following formula (2).

(In formula (2), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p and r are integers of 0 to 4, and q is an integer of 0 to 4. represents an integer of 3, n is the average value of the number of repetitions, and 1≦n≦20.X represents a halogen atom.)

The preferred ranges of R, p, r, q, and n in formula (2) are the same as in formula (1). From the viewpoint of reactivity and stability of raw materials, X is preferably a bromine atom or a chlorine atom, and a bromine atom is particularly preferred.

The compound represented by the formula (1) can be obtained, for example, by subjecting the compound represented by the formula (2) to a dehydrohalogenation reaction in a solvent in the presence of a basic catalyst. Examples of solvents used include 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 methyl isobutyl. Examples include, but are not limited to, water-insoluble solvents such as ketone solvents such as ketones and cyclopentanone, and two or more types may be used in combination. Moreover, in addition to the water-insoluble solvent, an aprotic polar solvent can also be used in combination. Examples include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of them may be used in combination. When using an aprotic polar solvent, it is preferable to use one having a higher boiling point than the water-insoluble solvent used together. The catalyst is not particularly limited, but includes basic catalysts such as sodium hydroxide, potassium hydroxide, potassium carbonate, and the like. Since it is difficult to allow the dehydrohalogenation reaction to proceed completely, the aprotic polar solvent may be used in large excess relative to the substrate, or the dehydrohalogenation reaction may be carried out twice or three times or more. This may be repeated multiple times. For example, in the presence of a base catalyst in an organic solvent, the compound represented by formula (2) is subjected to a dehydrohalogenation reaction, and the resulting solution is washed with water, then returned to the reaction vessel, and a base catalyst is added thereto. You may react. By doing so, the degree of progress of the dehydrohalogenation reaction can be increased. That is, it is possible to reduce the amount of residual halogen contained in the target compound. The amount of residual halogen in the target product is preferably 1 to 10,000 ppm, more preferably 1 to 1,000 ppm, still more preferably 1 to 750 ppm. If the amount of residual halogen contained in the compound represented by the formula (1) is large, molecular vibration will occur when exposed to high frequency, which will have a particularly negative effect on electrical properties such as dielectric loss tangent. Further, if the amount of residual halogen is large, the risk of causing problems such as metal corrosion and ion migration increases in an environmental test such as a HAST test (High Accelerated Stress Test), so the above halogen content is preferable.

The method for producing the compound represented by formula (2) is not particularly limited, but for example, a compound having a 2-bromoethylbenzene structure and a bishalogenated methylaryl compound (or a bishydroxymethylaryl compound, etc.) are mixed with hydrochloric acid or sulfonic acid. The reaction may be carried out under an acid catalyst such as activated clay, or the compound having a 2-bromoethylbenzene structure and the bishydroxymethylaryl compound may be reacted under an acid catalyst such as hydrochloric acid, sulfonic acid or activated clay. When sulfonic acid or the like is used as a catalyst, the extraction step may be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon solvent such as cyclohexane or toluene may be used in combination. After extraction, the organic layer is washed with water until the waste water becomes neutral, and the solvent and excess compound having a 2-bromoethylbenzene structure are distilled off using an evaporator or the like, so that at least two or more compounds having a 2-bromoethylbenzene structure are present in the target molecule. - A compound having a bromoethylethylbenzene structure can be obtained.

Examples of compounds having a 2-bromoethylbenzene structure include 2-bromoethylbenzene, 1-(2-bromoethyl)-2-methylbenzene, 1-(2-bromoethyl)-3-methylbenzene, and 1-(2-bromoethyl). )-4-methylbenzene, 1-(2-bromoethyl)-2,3-dimethylbenzene, 1-(2-bromoethyl)-2,4-dimethylbenzene, 1-(2-bromoethyl)-2,5-dimethyl Examples include, but are not limited to, benzene, 1-(2-bromoethyl)-2,6-dimethylbenzene, and the like. These may be used alone or in combination of two or more. When the number of carbon atoms is large, solvent solubility improves, but heat resistance decreases, so it is preferable that the number of carbon atoms is unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms. It is more preferably substituted with a group, and most preferably unsubstituted or substituted with a methyl group.

Examples of the bishalogenated methylaryl compound include о-xylylene difluoride, m-xylylene difluoride, p-xylylene difluoride, о-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, Examples include, but are not limited to, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, о-xylylene diiodide, m-xylylene diiodide, p-xylylene diiodide, etc. isn't it. These may be used alone or in combination of two or more. From the viewpoint of reactivity of raw materials during synthesis, chloride compounds, bromide compounds, and iodide compounds are preferred, and chloride compounds and bromide compounds are more preferred.

Examples of the bishydroxymethylaryl compound include, but are not limited to, о-benzenedimethanol, m-benzenedimethanol, p-benzenedimethanol, and the like. These may be used alone or in combination of two or more. The amount of these used is preferably 0.05 to 0.8 parts by weight, more preferably 0.1 to 0.6 parts by weight per 1 part by weight of the compound having a 2-bromoethylbenzene structure.

When reacting a compound having a 2-bromoethylbenzene structure with a halogenated methylaryl compound, etc., hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, as well as aluminum chloride and zinc chloride may be used as catalysts, if necessary. Lewis acids such as activated clay, acid clay, white carbon, zeolite, solid acids such as silica alumina, acidic ion exchange resins, etc. can be used. These may be used alone or in combination of two or more. The amount of the catalyst used is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, per 1 mol of the compound having a 2-bromoethylbenzene structure. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult, while if it is too small, the progress of the reaction may be slowed down. The reaction may be carried out using an organic solvent such as hexane, cyclohexane, octane, toluene, xylene, etc., selected as necessary, or may be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of a compound having a 2-bromoethylbenzene structure, a halogenated methylaryl compound, and a solvent, if the catalyst contains water, water is removed from the system by azeotropy. Thereafter, the reaction is carried out at 40 to 180°C, preferably 50 to 170°C, for 0.5 to 20 hours. After the reaction is completed, the acidic catalyst may be neutralized with an aqueous alkali solution, but it is also possible to proceed to the water washing step without neutralization. In the water washing process, a water-insoluble organic solvent is added to the oil layer and water washing is repeated until the wastewater becomes neutral.

The softening point of the compound represented by formula (2) is preferably 80°C or lower, more preferably 70°C or lower. When the softening point is 80° C. or less, the viscosity when induced into the compound represented by the formula (1) becomes low. This makes it easy to ensure fluidity, does not impair impregnating properties into glass cloth, carbon fiber, etc., and facilitates B-stage conversion such as prepreg formation. If the viscosity is lowered by increasing the amount of diluting solvent, there is a possibility that the resin will not adhere sufficiently to the fibrous material during the impregnation process.

The curable resin composition of the present invention contains a photopolymerization initiator as component (B). Component (B) is preferably a radical photopolymerization initiator or a cationic photopolymerization initiator. The content of component (B) is 0.001 to 20 parts by mass, more preferably 0.002 to 15 parts by mass, per 100 parts by mass of component (A). If it is less than 0.001 parts by mass, photocuring may be insufficient, and if it is more than 20 parts by mass, dielectric properties may be deteriorated. Preferred examples of component (B) are listed below, but the invention is not limited to these. One type of these may be used alone, or two or more types may be used in combination.

[Radical photopolymerization initiator]
The photo-radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals and initiates a chain polymerization reaction when irradiated with ultraviolet rays or visible light, but examples include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and diethyl. Thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2,4,6-trimethylbenzoyl Examples include diphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide and the like. 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 are manufactured by BASF) ), Sequal ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Kagaku Co., Ltd.), Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.), and the like. Among these, oxime ester initiators IRGACURER OXE01, OXE02, OXE03, and OXE04 are preferred.

[Photocationic polymerization initiator]
Radical polymerization initiators are not particularly limited as long as they are compounds that generate cationic species such as Brønsted acids and Lewis acids when irradiated with ultraviolet rays or visible light, but examples of photocationic polymerization initiators include aromatic iodonium complex salts and aromatic iodonium complexes. Examples include sulfonium complex salts. Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, tolylkumyliodonium tetrakis. Examples include (pentafluorophenyl)borate (manufactured by Rhodia, trade name: Rhodosil PI2074), di(4-tert-butyl)iodonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF, trade name: CGIBBI-C1), etc. . Specific examples of aromatic sulfonium complex salts include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San-Apro, trade name: CPI-101A), thiophenyldiphenylsulfonium tris(pentafluoroethyl) trifluorophosphate (manufactured by San-Apro, Inc.) , trade name: CPI-210S), 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name: SP-172), 4-thio A mixture of aromatic sulfonium hexafluoroantimonates containing phenyl diphenylsulfonium hexafluoroantimonate (manufactured by ACETO Corporate USA, trade name: CPI-6976) and triphenylsulfonium tris(trifluoromethanesulfonyl)methanide (manufactured by BASF, trade name: CGITPS) -C1), tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tris(trifluoromethylsulfonyl)methide (manufactured by BASF, product name: GSID26-1), tris[4-(4-acetylphenyl)sulfonyl Examples include phenyl]sulfonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate (manufactured by BASF, trade name: Irgacure PAG290). Among these, aromatic sulfonium complex salts are preferred in the present invention because they have high vertical rectangular processability and high thermal stability in the photosensitive image forming process. Among these, aromatic sulfonium hexafluoroantimonate containing 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluoroantimonate, 4-thiophenyldiphenylsulfonium hexafluoroantimonate Particularly preferred is a mixture of tris[4-(4-acetylphenyl)sulfonylphenyl]sulfonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate.

[Inorganic filler]
The curable resin composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, Examples include, but are not limited to, powders such as steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, and inorganic fillers made of these in spherical or crushed shapes. It's not a thing. Further, these may be used alone or in combination.

The amount of inorganic filler used when obtaining a curable resin composition for semiconductor encapsulation is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, based on 100 parts by mass of the curable resin composition. be. In addition, when obtaining a curable resin composition for an interlayer insulation layer forming material, a substrate material such as a copper-clad laminate, prepreg, or RCC, the amount of the above-mentioned inorganic filler used is based on 100 parts by mass of the curable resin composition. , preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight.

[Thermosetting accelerator]
The thermosetting properties of the curable resin composition of the present invention can also be improved by adding a thermosetting accelerator. The thermal curing accelerator is preferably a thermal anionic curing accelerator that generates anionic species by heating to promote thermal curing, or a thermal cationic curing accelerator that generates cationic species by heating to accelerate thermal curing.

Examples of thermal anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, Examples include benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine, 1,8-diazabicyclo( 5,4,0)-undecene is preferred. Other examples include phosphines such as triphenylphosphine, and quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide. It is not limited to. Further, these may be used alone or in combination.

Examples of thermal cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen). , organic acid ions, hydroxide ions, etc. (although not particularly specified, organic acid ions and hydroxide ions are particularly preferred), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, Examples include, but are not limited to, transition metal compounds (transition metal salts) such as zinc behenate, zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc. . Further, these may be used alone or in combination.

The blending amount of the thermosetting accelerator is 0.01 to 5.0 parts by mass, if necessary, when the nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. .

[Thermal radical polymerization initiator]
The thermosetting properties of the curable resin composition of the present invention can also be improved by adding a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals upon heating and initiates a chain polymerization reaction. Examples of thermal radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacols. It is preferable to use
Examples of the organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butyl peroxide). (oxyisopropyl)-dialkyl peroxides such as benzene, peroxyketals such as t-butylperoxybenzoate, 1,1-di-t-butylperoxycyclohexane, α-cumylperoxyneodecanoate, t- Butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t -Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate Alkyl peresters such as oxybenzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t-butyl) Examples include, but are not limited to, peroxycarbonates such as peroxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide. . Further, these may be used alone or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, and dialkyl peroxides is more preferable.
Examples of the azo compounds include azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. However, it is not limited to these. Further, these may be used alone or in combination.

The amount of the thermal radical polymerization initiator added is preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, per 100 parts by weight of the curable resin composition. If the amount of the thermal radical polymerization initiator used is less than 0.01 part by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, there is a risk of impairing dielectric properties such as dielectric constant and dielectric loss tangent. be.

[Polymerization inhibitor]
The curable resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, fluidity can be easily ensured, impregnating properties into glass cloth etc. are not impaired, and B-stage formation such as prepreg formation is facilitated. If the polymerization reaction progresses too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

The polymerization inhibitor may be added when synthesizing component (A), or may be added after synthesis. The amount of polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of component (A).

Examples of polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors. Furthermore, one kind of polymerization inhibitor may be used or a plurality of them may be used in combination. Among these, in the present invention, phenol type, hindered amine type, nitroso type, and nitroxyl radical type are preferable.

Examples of the phenolic polymerization inhibitor include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and 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) Monophenols such as -6-(4-hydroxy-3,5-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-hydroxy -hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy Benzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4, Bisphenols such as 8,10-tetraoxaspiro[5,5]undecane, bis(ethyl 3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium, 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 Examples include, but are not limited to, polymeric phenols such as -4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione and tocophenol. .

Examples of the sulfur-based polymerization inhibitor include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like. However, it is not limited to these.

Examples of the phosphorus polymerization inhibitor include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t -butylphenyl) phosphite, cyclic neopentanetetryrubis(octadecyl)phosphite, cyclic neopentanetetryruby(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetryruby(2, 4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, etc. 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, 10-desyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and other oxaphosphaphenanthrene oxides, etc. It is not limited.

Examples of the hindered amine polymerization inhibitor include Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Dekastab LA-82, Dekastab LA-81, Adekastab LA-77Y, and Adekastab LA-77Y. -77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, Tinuvi nPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB, etc. Examples include, but are not limited to.

Examples of the nitroso-based polymerization inhibitor include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine (cuperone), and the like. Among these, preferred is the ammonium salt of N-nitrosophenylhydroxyamine (cuperone).

Examples of the nitroxyl radical polymerization inhibitor include di-tert-butyl nitroxide, 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, 4-benzoyloxy-2,2,6,6 Examples include, but are not limited to, -tetramethylpiperidine-1-oxyl and the like.

[Flame retardants]
The curable resin composition of the present invention may contain a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), phosphorus-based flame retardants, etc., but halogen-free flame retardance has been achieved. From this viewpoint, phosphorus-based flame retardants are preferred.
The above-mentioned phosphorus-based flame retardant may be a reactive type flame retardant or an additive type flame retardant. Specific examples include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylenebis(dixylenyl phosphate), Phosphate esters such as 1,4-phenylenebis(dixylenyl phosphate) and 4,4'-biphenyl(dixylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- In addition to phosphanes such as oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, it is obtained by reacting an epoxy resin with the active hydrogen of the phosphanes. Examples include, but are not limited to, phosphorus-containing epoxy compounds, red phosphorus, and the like. Further, these may be used alone or in combination. Among the above-mentioned exemplified substances, phosphoric acid esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(dixylenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 4,4 '-Biphenyl (dixylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass, when the total mass of nonvolatile components excluding inorganic fillers in the curable resin composition is 100 parts by mass. . If it is less than 0.1 parts by mass, the flame retardance may be insufficient, and if it is more than 0.6 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[Light stabilizer]
A light stabilizer may be used in the curable resin composition of the present invention. As the light stabilizer, hindered amine light stabilizers, particularly HALS, etc. are suitable. Examples of HALS include 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 reaction product, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate reaction product , 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-piperidyl)imino}], 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-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4- Examples include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate (hydroxybenzyl)-2-n-butylmalonate. It may be used in combination with two or more.

The content of the light stabilizer is preferably in the range of 0.001 to 10 parts by mass, based on 100 parts by mass of nonvolatile components excluding inorganic fillers in the curable resin composition. If it is less than 0.001, it may be insufficient to exhibit a photostabilizing effect, and if it is more than 10, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[Binder resin]
The curable resin composition of the present invention may use a binder resin. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, silicone resin, etc., but are not limited to these. It's not something you can do. Further, these may be used alone or in combination.

The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, assuming that the nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. , preferably 0.05 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, if necessary.

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

The blending amount of the additive is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the curable resin composition.

[Organic solvent]
The curable resin composition of the present invention may contain an organic solvent. Examples of the organic solvent include aromatic solvents, ketone solvents, cyclic ether solvents, and ester solvents.
Examples of aromatic solvents include toluene, xylene, and tetralin. Examples of the ketone solvent include methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Examples of the cyclic ether solvent include tetrahydroxyfuran and dioxane. Examples of the ester solvent include ethyl lactate, ethyl acetate, butyl acetate, methyl benzoate, propylene glycol methyl ether acetate, and the like. In addition, high boiling point solvents such as DMF, NMP, and γ-butyrolactone may also be used.
These organic solvents may be used alone or in combination of two or more.

The curable resin composition of the present invention further includes an epoxy resin, an active ester compound, a phenol resin, a polyphenylene ether compound, an amine resin, a maleimide compound, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, Cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, etc. may be used, and these may be used alone or in combination. Among these compounds, polyphenylene ether compounds, compounds with ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof may be included in view of the balance of heat resistance, adhesion, and dielectric properties. is preferred. By containing these compounds, the brittleness of the cured product can be improved and the adhesion to metal can be improved, and cracks in the package can be suppressed during reliability tests such as during solder reflow and cooling/heating cycles.

Unless otherwise specified, the amount of the compound used is preferably 10 times or less, more preferably 5 times or less, particularly preferably 3 times or less by mass relative to the component (A). Further, a preferable lower limit is 0.1 times by mass or more, more preferably 0.25 times by mass or more, still more preferably 0.5 times by mass or more. By being within the above range, the effects of each compound added can be added while taking advantage of the effects of the heat resistance and dielectric properties of the component (A). Regarding these components, those illustrated below can be used.

[Epoxy resin]
Preferred examples of the epoxy resin are shown below, but the invention is not limited thereto. The epoxy resin may be liquid or solid, and may be used alone or in combination.

Examples of liquid epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, phenol novolac epoxy resin, and ester. Examples include alicyclic epoxy resins having a skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all made by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all made by Nippon Kayaku Co., Ltd.). manufactured by DIC Corporation, bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (manufactured by DIC Corporation, naphthalene type epoxy resin) , manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol novolac type epoxy resin) , "630", "630LSD" (manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), " "EX-721" (manufactured by Nagase ChemteX, glycidyl ester type epoxy resin), "Celoxide 2021P" (manufactured by Daicel, alicyclic epoxy resin with an ester skeleton), "PB-3600" (manufactured by Daicel, butadiene structure) ), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Examples of the solid epoxy resin include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, Biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin and biphenyl-type epoxy resins. Specific examples include "HP4032H" (manufactured by DIC, naphthalene type epoxy resin), "HP-4700", "HP-4710" (all of the above are naphthalene type tetrafunctional epoxy resins, manufactured by DIC), and "N-690". (manufactured by DIC Corporation, cresol novolak type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolak type epoxy resin), "HP-7200" (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin), "HP- 7200'', ``HP-7200HH'', ``HP-7200H'' (manufactured by DIC, dicyclopentadiene type epoxy resin), ``EXA-7311'', ``EXA-7311-G3'', ``EXA-7311-G4'' , "EXA-7311-G4S", "HP-6000" (manufactured by DIC, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC -7000L", "NC-7300" (manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (The above are manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (the above, Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (Nippon Steel & Sumikin Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-" 4000H", "YX-4000", "YL6121" (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin), "YX-8800" ( Mitsubishi Chemical Co., Ltd., anthracene type epoxy resin), "PG-100", "CG-500" (Osaka Gas Chemical Co., Ltd., fluorene type epoxy resin), "YL-7760" (Mitsubishi Chemical Co., Ltd., bisphenol AF type epoxy Resin), "YL-7800" (Mitsubishi Chemical Co., Ltd., fluorene type epoxy resin) "jER1010" (Mitsubishi Chemical Co., Ltd., solid bisphenol A type epoxy resin), "jER1031S" (Mitsubishi Chemical Co., Ltd., tetraphenylethane type) epoxy resin), etc. These may be used alone or in combination of two or more.

[Active ester compound]
The active ester compound refers to a compound that contains at least one ester bond in its structure and has an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond. Examples of active ester compounds include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. It can be obtained by a condensation reaction of at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable to use a carboxylic acid compound or an acid chloride and a hydroxy compound, and as the hydroxy compound, a phenol compound or a naphthol compound is preferable. The active ester compounds may be used alone or in combination of two or more.

Examples of the 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 the acid chloride include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecanedioyl dichloride, azeroyl chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dichloride Examples include carbonyl chloride and 4,4'-azodibenzoyl dichloride.

Examples of the phenol compound and naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, Examples include phloroglucin, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Examples include ester compounds, the compound described in Example 2 of International Publication No. 2020/095829, and the compound disclosed in International Publication No. 2020/059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. The dicyclopentadiene type diphenol structure represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, containing an acetylated product of phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester compound, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) is an acetylated product of phenol novolak as active ester compounds containing a benzoylated product of phenol novolac. Examples of the active ester curing agent include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the phosphorus atom-containing active ester curing agent include "EXB-9050L-62M" manufactured by DIC Corporation.

[Phenol resin]
A phenolic resin is a compound having two or more phenolic hydroxyl groups in its molecule. Examples of phenolic resins include reactants of phenols and aldehydes, reactants of phenols and diene compounds, reactants of phenols and ketones, reactants of phenols and substituted biphenyls, and phenols. Examples include, but are not limited to, reaction products of and substituted phenyls, and reaction products of bisphenols and aldehydes. Further, these may be used alone or in combination.
Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited thereto.
<Phenols>
Phenol, alkyl-substituted phenol, aromatic substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.
<Aldehydes>
Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.
<Diene compound>
Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.
<Ketones>
Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.
<Substituted biphenyls>
4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1' -Biphenyl etc.
<Substituted phenyls>
1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[Polyphenylene ether compound]
From the viewpoint of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, methacrylic group, or styrene structure. preferable. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure).
The number average molecular weight (Mn) of the polyphenylene ether compound is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, and even more preferably from 2,000 to 4,000. If the molecular weight is less than 500, the cured product tends to have insufficient heat resistance. Furthermore, if the molecular weight is greater than 5,000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, which tends to result in poor molding. In addition, the reactivity decreases, and the curing reaction takes a long time, and unreacted substances increase without being incorporated into the curing system, lowering the glass transition temperature of the cured product and reducing the heat resistance of the cured product. There is a tendency to
When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, excellent heat resistance, moldability, etc. can be exhibited while maintaining excellent dielectric properties. Note that the number average molecular weight here can be specifically measured using gel permeation chromatography or the like.

The polyphenylene ether compound may be obtained by a polymerization reaction, or may be obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. Moreover, radical polymerizability may be imparted to these raw materials by reacting them with a compound having an ethylenically unsaturated bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by this redistribution reaction has hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain, and therefore can maintain even higher heat resistance. This is preferable because functional groups can be introduced at both ends of the molecular chain even after modification with a compound having a sexually unsaturated bond. Further, polyphenylene ether compounds obtained by polymerization reactions are preferred because they exhibit excellent fluidity.

In the case of a polyphenylene ether compound obtained by a polymerization reaction, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions and the like. Further, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, it may be possible to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the larger the amount of the phenolic compound blended, the lower the molecular weight of the resulting polyphenylene ether compound. At this time, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but for example, a polyfunctional phenol having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolak, cresol novolak, etc. type compounds are preferably used. These may be used alone or in combination of two or more.

The content of the polyphenylene ether compound is not particularly limited, but it is preferably 5 to 1000 parts by mass, and 10 to 1000 parts by mass when the nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass More preferably, it is 750 parts by mass. When the content of the polyphenylene ether compound is within the above range, it is preferable that a cured product not only has excellent heat resistance but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[Amine resin]
An amine resin is a compound having two or more amino groups in its molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, naphthalene diamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), orthoethyl. Aniline novolac (reaction product of orthoethylaniline and formalin), reaction product of 2-methylaniline and formalin, reaction product of 2,6-diisopropylaniline and formalin, reaction product of 2,6-diethylaniline and formalin, 2-ethyl - Reaction product of 6-ethylaniline and formalin, reaction product of 2,6-dimethylaniline and formalin, aniline resin obtained by reaction of aniline and xylylene chloride, substituted with aniline described in Japanese Patent No. 6429862 Reaction products of biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), aniline and substituted phenyls (1 , 4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylenediisopropylene) Examples include, but are not limited to, 4,4'-(1,4-phenylene diisopropylidene) bisaniline, a reaction product of aniline and diisopropenylbenzene, and dimer diamine. Further, these may be used alone or in combination.

[Maleimide compound]
A maleimide compound is a compound having one or more maleimide groups in its molecule. Examples of maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), Zyrock-type maleimide compound (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compound (special Solidified by distilling off the solvent under reduced pressure from the resin solution containing the maleimide compound (M2) described in Example 4 of Publication No. 2009-001783), bisaminocumylbenzene-type maleimide (International Publication No. 2020/ 054601), maleimide compounds having an indane structure described in 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 Memorandum 31st Bismaleimide (1)” and MATERIAL STAGE Vol. 19, No. 2 2019 Maleimide compounds described in "~Continued Epoxy Resin CAS Number Story~Curing Agent CAS Number Memorandum 32nd Bismaleimide (2)" can be mentioned, but are not limited to these. Further, these may be used alone or in combination.

The amount of the maleimide compound added is preferably 10 times or less, more preferably 5 times or less, particularly preferably 3 times or less by mass relative to the component (A). Further, a preferable lower limit is 0.01 times by mass or more, more preferably 0.1 times by mass or more. Within the above range, the effects of the heat resistance, dielectric properties, and low water absorption of the component (A) can be utilized.

[Compound containing an ethylenically unsaturated bond]
A compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in its molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.
Examples of compounds containing ethylenically unsaturated bonds include the above-mentioned phenolic resins and halogenated compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.) reactants, phenols containing ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (1,4-bis( (chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy Examples include, but are not limited to, reaction products of resins or alcohols and (meth)acrylic acids (acrylic acid, methacrylic acid, etc.) and acid-modified products thereof. Further, these may be used alone or in combination.

The polybasic acid anhydride used to produce the acid-modified product is not particularly limited, and any polybasic acid anhydride having one or more acid anhydride structure in the molecule can be used. Specifically, succinic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerin bis(anhydro trimellitate) monoacetate, 1,2,3,4,-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4, 4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 -bis(3,4-anhydrodicarboxyphenyl)propane, 2,2-bis(3,4-anhydrodicarboxyphenyl)hexafluoropropane, 5-(2,5-dioxotetrahydro-3-furanyl) -3-Methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan Particularly preferred are polybasic acid anhydrides selected from -1,3-diones.

[Isocyanate resin]
An isocyanate resin is a compound having two or more isocyanate groups in its molecule. Examples of the isocyanate resin include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate. , aromatic diisocyanates such as naphthalene diisocyanate, aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, isocyanate monomers Examples include, but are not limited to, polyisocyanates such as isocyanate bodies obtained by trimerizing one or more types of burettes or the above diisocyanate compounds, and polyisocyanates obtained by a urethanization reaction between the above isocyanate compounds and a polyol compound. It's not a thing. Further, these may be used alone or in combination.

[Polyamide resin]
Examples of the polyamide resin include a reaction product of dicarboxylic acid with one or more of diamine, diisocyanate, and oxazoline, a reaction product of diamine and acid chloride, and a ring-opening polymer of a lactam compound. Further, these may be used alone or in combination.
Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited thereto.
<Diamine>
Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecane Diamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimer diamine, cyclohexanediamine, bis-(4- aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis( 4-Amino-3,5-dimethylphenyl)methanebis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-о-toluidine, 4,4'-methylenebis-о-ethylaniline, 4 , 4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenylsulfone, diaminodiphenyl ether, 1,3-bis( 3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4 '-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene , aminobenzylamine, diaminobenzophenone, etc.
<Diisocyanate>
Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2 -isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc.
<Dicarboxylic acid>
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4 , 4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc.
<Acid chloride>
Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacyl dichloride, adipic acid dichloride, dodecanedioyl dichloride, azeloyl chloride, 2, 5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl)ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azo Dibenzoyl dichloride etc.
<Lactam>
ε-caprolactam, ω-undecanelactam, ω-laurolactam, etc.

[Polyimide resin]
Examples of polyimide resins include, but are not limited to, reaction products of the diamines described above and tetracarboxylic dianhydrides exemplified below. Further, these may be used alone or in combination.
<Tetracarboxylic dianhydride>
4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic acid dianhydride Anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride Acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3 '-Biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4 '-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4 , 4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride Anhydride, 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 dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6 -Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrene Tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), cyclopentane Tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4' -Bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) acid) dianhydride, 2,2-propylidene-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]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane- 2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl)ether, 4,4'-biphenylbis(trimellitic acid monoester acid anhydride), 9,9 '-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[Cyanate ester resin]
Cyanate ester resin is a cyanate ester compound obtained by reacting a phenolic resin with cyanogen halide, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2, 2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5- Dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl) Examples include, but are not limited to, sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and those obtained by converting the hydroxyl group of a phenol/dicyclopentadiene cocondensate into a cyanate group. Further, these may be used alone or in combination.
Furthermore, cyanate ester compounds whose synthesis method is described in JP-A No. 2005-264154 are particularly preferred as cyanate ester compounds because they have low moisture absorption, excellent flame retardancy, and excellent dielectric properties.
The cyanate ester resin can optionally trimerize cyanate groups to form a sym-triazine ring. Catalysts such as lead acetylacetonate and dibutyltin maleate can also be included.

The catalyst is preferably used in an amount 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 cyanate ester resin.

[Polybutadiene and its modified products]
Polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule. In the structure derived from polybutadiene, some or all of the unsaturated bonds may be converted into single bonds by hydrogenation.
Examples of polybutadiene and modified products thereof include, but are not limited to, polybutadiene, hydroxyl group-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, etc. . Further, these may be used alone or in combination. Among 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), and 1,2-SBS (manufactured by Nippon Soda), and examples of polybutadiene include: Examples 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 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000. Below the lower limit of the above range, the amount of volatilization is large, making it difficult to adjust the solid content during preparation of prepreg, and above the upper limit of the above range, compatibility with other curable resins deteriorates. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, due to their polarity, compounds consisting mainly of hydrocarbons or compounds consisting only of hydrocarbons have low polarity. It is difficult to ensure compatibility with other compounds. On the other hand, the component (A) of the present invention does not have a skeleton design that actively introduces heteroatoms such as oxygen or nitrogen, and is therefore made of materials with low polarity and low dielectric properties, or only hydrocarbons. It also has excellent compatibility with compounds composed of

[Polystyrene and its modified products]
Polystyrene and modified products thereof are polystyrene or compounds having a structure derived from polystyrene in the 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.), and SEP (styrene-ethylene/propylene copolymer). Polymer: 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 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), SEBS (styrene-ethylene/butylene-styrene block copolymer: SEPTON 8004) , SEPTON 8006, SEPTON 8007L (all manufactured by Kuraray), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylene/ethylene propylene-styrene block copolymer: SEPTON HG252 manufactured by Kuraray), 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 copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka), Septon V9827 (manufactured by Kuraray), etc., but are not limited to these. Further, these may be used alone or in combination. Polystyrene and its modified products have higher heat resistance and are less susceptible to oxidative deterioration, so polystyrenes that do not have unsaturated bonds are preferred. The weight average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more, but if it is too large, in addition to polyphenylene ether compounds, low molecular weight components with weight average molecular weights of about 50 to 1,000 and weight average molecular weights of 1,000 to 1,000 are used. The molecular weight is preferably about 10,000 to 300,000, since the compatibility with oligomer components of about 5,000 will deteriorate and it will be difficult to ensure mixing and solvent stability.

The curable resin composition of the present invention can be used by known methods. For example, the curable resin composition of the present invention, the viscosity of which has been adjusted with the organic solvent, is applied to a support, and then dried at 50 to 180°C, preferably 80 to 140°C for 5 to 30 minutes to form a film. It can be made into a synthetic resin composition. Examples of the support include a silicon wafer, a ceramic substrate, a rigid substrate, a flexible substrate, and a silicon wafer on which an inorganic surface protection film such as a SiN film or a SiO2 film is formed.

The coating method is not particularly limited, and examples thereof include coating using a spin coater, slit coater, roll coater, etc., and screen printing. Among these, for example, as a coating method for silicon wafers, it is preferable to employ a coating method using a spin coater. Further, 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. When used as a protective film 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. When the film thickness is less than 3 μm, it tends to be unable to sufficiently protect the elements and circuits under the film, and when it exceeds 50 μm, it tends to be difficult to form fine patterns. In the present invention, even with a film thickness of 10 μm or more (preferably 10 to 20 μm), fine pattern formation is possible, and the aspect ratio of the opening diameter (Via diameter) of the through hole formed by exposure and development described below. It becomes possible to form a pattern in which the value is 0.3 or more (more preferably 0.5 or more).

Next, a mask having a predetermined pattern shape is applied to the film-like curable resin composition thus obtained, and exposure is performed to photopolymerize the curable resin composition of the present invention. Examples of the exposure method include contact exposure and reduction projection exposure. The exposure wavelength is preferably ultraviolet to visible light of 200 to 500 nm, and a standard reduction projection exposure machine (stepper) can be used. Further, the exposure wavelength is more preferably 256 to 436 nm, and even more preferably 256 to 365 nm, from the viewpoint of being able to form a fine pattern. The exposure amount is not particularly limited, but is preferably 100 to 5000 mJ/cm ² , more preferably 300 to 3000 mJ/cm ² .

Next, a polymer film (polymer) having a predetermined pattern can be obtained by performing development in which the unexposed portion of the film-like curable resin composition after the exposure is dissolved and removed with a developer. That is, in the exposed area, radicals or cationic species generated from the photopolymerization initiator by light irradiation cause component (A) and other compounds to crosslink, thereby making them insoluble in the developer. On the other hand, since the unexposed area dissolves in the developer, a pattern such as a through hole with a predetermined opening diameter (Via diameter) is formed by utilizing the difference in solubility in the developer between the exposed area and the unexposed area. A polymer film can be obtained. In addition to the above-mentioned solvents, the developer may further contain an alcoholic solvent such as methanol, ethanol, propanol, etc., in order to adjust the solubility during development. Examples of the developing method include a spray method, a paddle method, and a dip method.

Moreover, it is preferable to further rinse the polymer 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 polymer film after the development preferably has a residual film ratio of 90% or more from the viewpoint of suppressing the occurrence of surface roughness and facilitating dimensional design. In the present invention, the residual film ratio refers to the ratio of the thickness of the polymeric film after development to the thickness of the film-like curable resin composition after drying (before exposure) (thickness of the polymeric film after development/ Refers to the thickness of the film-like curable resin composition after drying (before exposure).

Next, the polymer film having a predetermined pattern obtained by the development is cured by heating as necessary, thereby obtaining a cured film (cured product) having a predetermined pattern. The heating temperature (curing temperature) is preferably 60 to 230°C, more preferably 150 to 230°C. Further, the heating time is preferably 30 to 120 minutes. In the present invention, the curing temperature refers to the temperature necessary to thermally cure the functional groups remaining unreacted during the exposure through a thermal reaction. Such a thermosetting reaction crosslinks the unreacted functional groups in the photopolymerization described above, but when the curable resin composition of the present invention is used, conventional polyimide precursors and polybenzoxazole precursors can be crosslinked. There is no need to raise the curing temperature as in This is because the curable resin composition of the present invention does not require a dehydration ring closure reaction.

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

The cured product after photocuring or photothermal curing (curing using both photocuring and thermosetting) obtained using the curable resin composition of the present invention includes surface protective films of semiconductor elements, interlayers, etc. It can be suitably used for at least one film selected from the group consisting of an insulating film and an insulating film of a rewiring layer. In addition, the curable resin composition of the present invention requires a film thickness of 10 μm or more in such a film, and an aspect ratio of the opening diameter (Via diameter) of the through hole is 0.3 or more (more preferably This is particularly effective in cases where patterning is required such that 0.5 or more).

The cured product of the present invention is used, for example, as a resist film, an interlayer insulating material for a build-up method, or as an optical waveguide for electrical/electronic/optical substrates such as printed circuit boards, optoelectronic boards, and optical boards. Specific examples of these include, for example, articles such as computers, home appliances, and mobile devices. The thickness of this cured material layer is usually about 0.5 to 160 μm, preferably about 1 to 100 μm.

Next, the present invention will be explained in more detail with reference to Examples. Hereinafter, unless otherwise specified, parts are parts by mass. Note that the present invention is not limited to these examples.

Various analytical methods used in the examples are described below.
<Weight average molecular weight (Mw), number average molecular weight (Mn)>
Calculated by polystyrene conversion using a polystyrene standard solution.
GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
Column: Shodex KF-603, KF-602x2, KF-601x2)
Coupling eluent: Tetrahydrofuran Flow rate: 0.5ml/min.
Column temperature: 40℃
Detection: RI (differential refraction detector)

[Synthesis example 1]
The flask was equipped with a thermometer, condenser, and stirrer, as well as an aspirator and base trap. Into this flask were 370.1 parts of 2-bromoethylbenzene (manufactured by Tokyo Kasei Co., Ltd.), 175.1 parts of α,α'-dichloro-p-xylene (manufactured by Tokyo Kasei Co., Ltd.), and 27.1 parts of methanesulfonic acid (manufactured by Tokyo Kasei Co., Ltd.). 3 parts were charged, and the reaction was carried out at 130° C. for 6 hours while the generated hydrogen chloride was collected with a base trap. 100 parts of toluene and 600 parts of cyclohexane were added for extraction, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent and excess 2-bromoethylbenzene under heating and reduced pressure, 380 parts of a compound (BEB-1) having a 2-bromoethylbenzene structure represented by the following formula (3) was obtained as a liquid resin (Mn :938, Mw:1290). A GPC chart of the obtained compound is shown in FIG. The average value n of repeating units calculated from the area % of the GPC chart was 2.2.

[Synthesis example 2]
300 parts of BEB-1 obtained in Synthesis Example 1, 245 parts of toluene, 735 parts of dimethyl sulfoxide, and 4-hydroxy-2,2,6,6-tetramethylpiperidine were placed in a flask equipped with a thermometer, a cooling tube, and a stirrer. 0.15 parts of -1-oxyl free radicals and 146.4 parts of a 50 wt% aqueous sodium hydroxide solution were added, and the reaction was continued at 40°C for 6 hours. After washing the organic layer by adding 100 parts of water, the organic layer was returned to the reaction vessel. 735 parts of dimethyl sulfoxide and 9.8 parts of a 50 wt % sodium hydroxide aqueous solution were added, and the mixture was reacted again at 40°C for 1 hour, 300 parts of toluene was added, and the organic layer was repeatedly washed with 100 parts of water until the waste water became neutral. . The mixture was concentrated under reduced pressure using an evaporator to obtain 180 parts of a compound (O-1) having two or more styrene structures in the molecule represented by the following formula (4). A GPC chart of the obtained compound is shown in FIG. 2. Furthermore, ¹ H-NMR data (deuterochloroform) of the obtained compound is shown in FIG. Signals derived from vinyl groups were observed at 5.10-5.30 ppm, 5.50-5.85 ppm, and 6.60-6.80 ppm in the ¹ H-NMR chart. The average value n of the repeating unit calculated from the area % of the GPC chart was 2.2 (the molecular weight of the resin component was Mn: 797, Mw: 1187).

[Examples 1-3, Comparative Examples 1-2]
Blend each material in the proportions shown in Table 1, coat it on a PET film so that the film thickness is 100 μm, paste the PET film on the side that is not in contact with the film, and use a high-pressure mercury lamp (365 nm) at 3000 mJ/cm ² irradiated with ultraviolet rays. Dielectric properties were measured using the thus obtained photocured film.
Further, a photocured film was obtained in the same manner as above, and then thermally cured at 180° C. for 1 hour using an oven. Dielectric properties were measured using the photothermally cured film thus obtained.
In addition, in the evaluation, test pieces were cut into desired sizes using a laser cutter as needed, and the evaluation was performed.

<Dielectric constant test/dielectric loss tangent test>
A test was conducted using a cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by ATE Corporation. The sample size was 1.7 mm wide x 100 mm long, and the test was conducted with a thickness of 0.1 mm.

・Ｒ－６８４：トリシクロデカンジメタノールとアクリル酸の反応物（日本化薬社製）
・ＲＥ－３１０Ｓ：液状ビスフェノールＡ型エポキシ樹脂（日本化薬社製）
・ОＸＥ－０４：オキシムエステル系光ラジカル重合開始剤（ＢＡＳＦ社製）
・Ｉｒｇａｃｕｒｅ２９０：スルホニウム塩系光カチオン重合開始剤（ＢＡＳＦ社製）

・R-684: Reaction product of tricyclodecane dimethanol and acrylic acid (manufactured by Nippon Kayaku Co., Ltd.)
・RE-310S: Liquid bisphenol A type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
・OXE-04: Oxime ester photoradical polymerization initiator (manufactured by BASF)
・Irgacure290: Sulfonium salt-based photocationic polymerization initiator (manufactured by BASF)

From the results in Table 1, it was confirmed that Examples 1 and 2 were superior in low dielectric properties after photocuring and photothermal curing compared to the conventionally used acrylate resin composition (Comparative Example 1).

From the results in Table 1, it was confirmed that Example 3 was superior in low dielectric properties after photocuring and photothermal curing compared to the conventionally used epoxy resin composition (Comparative Example 2).

The curable resin composition, resin sheet, and cured product thereof of the present invention can be used as resist films, interlayer insulation materials for build-up methods, and optical waveguides for electrical, electronic, and optical substrates such as printed circuit boards, optoelectronic boards, and optical boards. Used for base materials such as

Claims (8)

A curable resin composition containing (A) a compound having at least two styrene structures in its molecule, and (B) a photopolymerization initiator. The curable resin composition according to claim 1, wherein the component (A) is a compound represented by the following formula (1),

(In formula (1), a plurality of R's each exist independently and represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated alkyl group. p and r represent integers of 0 to 4, and q represents an integer from 0 to 3, and n is 1≦n≦20.) The curable resin composition according to claim 1 or 2, wherein the component (B) is a cationic photopolymerization initiator. The curable resin composition according to claim 1 or 2, wherein the component (B) is a radical photopolymerization initiator. The curable resin composition according to claim 1 or 2, wherein the component (B) is an oxime ester photoradical polymerization initiator. The curable resin composition according to any one of claims 1 to 5, further comprising an inorganic filler. A cured product obtained by photocuring or photothermally curing the curable resin composition according to claim 1. A semiconductor device comprising the cured product according to claim 7 as at least one selected from the group consisting of a surface protection film, an interlayer insulation film, and a rewiring layer insulation film.

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