JP2023130776A - Curable resin composition, resin sheet, and cured product of the same - Google Patents

Abstract

To provide a resin composition which has flexibility enough to be formed into films and excellent low dielectric characteristics.SOLUTION: A curable resin composition contains (A) a compound having at least two or more styrene structures in the molecule, (B) an epoxy resin, and (C) an active ester compound.SELECTED DRAWING: Figure 3

Description

The present invention relates to a curable resin composition, a resin sheet, and a cured product thereof, which have excellent dielectric properties, and are suitably used in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates. Ru.

Epoxy resin is used in a wide range of fields as an important component of film adhesives due to its versatility, curing properties, and excellent balance of properties.Epoxy resin is used in a wide range of fields as an important component of film adhesives, and is particularly used in the electrical and electronic fields as interlayer insulation layers of printed wiring boards and resin adhesives. Used for copper foil, etc.

In the fifth-generation communication system "5G", which is currently being developed at an accelerated pace, it is expected that further increases in capacity and high-speed communication will occur, and the need for low dielectric loss tangent materials will continue to increase. . However, when epoxy resin uses phenol or amine as a curing agent, due to its reaction mechanism, hydroxyl groups are generated during the curing reaction, which tends to deteriorate water absorption properties and electrical properties.

In Patent Document 1, an epoxy resin is cured using a compound in which the hydroxyl groups of a phenol novolac curing agent are partially acetylated. As a result, although the moldability as a film is excellent, the generation of hydroxyl groups generated by the reaction of epoxy groups cannot be suppressed, and it is difficult to satisfy the development needs of the next generation.

In view of this current situation, maleimide compounds having excellent low dielectric properties, heat resistance, and solvent solubility have been studied in recent years (Patent Document 2). Maleimide compounds themselves are characterized by high heat resistance due to their high crosslinking density, but there is a problem that the cured products tend to be brittle compared to epoxy resins (Non-Patent Document 1), so in order to make them into films, Additives that can impart flexibility must be used in combination in a certain amount or more, making it difficult to take advantage of the characteristics of maleimide compounds.

International Publication No. 2005/100435 JP2009-001783A

"Network Polymer" Vol. 38 No. 3 (2017) Material design of bismaleimide-based high heat-resistant resin

The present invention has been made in view of the above points, and aims to provide a curable resin composition that has sufficient flexibility to be formed into a film and has excellent low dielectric properties. be.

As a result of intensive research to solve the above problems, the present inventors found that a curable resin composition containing a compound having at least two styrene structures in the molecule, an epoxy resin, an active ester compound, and a curing accelerator. It was discovered that the cured product has excellent low dielectric properties, and the present invention was completed.

That is, the present invention relates to the following [1] to [13]. 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, (B) an epoxy resin, and (C) an active ester compound.
[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), 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.)
[3]
The curable resin composition according to item [1] or [2], wherein the component (C) is a compound having a vinyl group.
[4]
Furthermore, the curable resin composition according to any one of the above items [1] to [3], which further contains a maleimide compound.
[5]
The curable resin composition according to any one of items [1] to [4], further comprising an inorganic filler.
[6]
The curable resin composition according to any one of items [1] to [5] above, further comprising a curing accelerator.
[7]
The curable resin composition according to any one of items [1] to [6] above, further comprising a polymerization initiator.
[8]
The curable resin composition according to any one of items [1] to [7], which is used to form an insulating layer.
[9]
A resin sheet comprising the curable resin composition according to any one of [1] to [8] above and a support.
[10]
A cured product of the curable resin composition according to any one of [1] to [8] above or the resin sheet according to [9] above.
[11]
An insulating layer formed from the cured product according to item [10].
[12]
A printed wiring board comprising the insulating layer according to item [11].
[13]
A semiconductor device comprising the printed wiring board according to item [12].

According to the present invention, it is possible to provide a curable resin composition, a resin sheet, and a cured product thereof, an insulating layer, a printed wiring board, and a semiconductor device having excellent low dielectric properties and flexibility.

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) an epoxy resin (hereinafter referred to as component (B)). ) and (C) an active ester compound (hereinafter also referred to as component (C)).

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. It may be reacted. 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 an epoxy resin as component (B). Preferred examples of component (B) are shown below, but the invention is not limited thereto. In addition, component (B) may be used alone or in combination.

Among component (B), liquid epoxy resins include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, Examples include phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure. Among these, bisphenol A type epoxy resin is particularly preferred. 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.

Among component (B), solid epoxy resins include, for example, 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. 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 preferable, naphthol type epoxy resin, Examples include bisphenol AF type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. 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" (manufactured by Mitsubishi Chemical Corporation, fluorene type epoxy resin) "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A type epoxy resin), "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane type) epoxy resin), etc. These may be used alone or in combination of two or more.

The curable resin composition of the present invention contains an active ester compound as component (C). 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. Component (C) includes, for example, 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.
Furthermore, component (C) is preferably an active ester compound having a vinyl group. Examples of the active ester compound having a vinyl group include the compound described in Example 2 of International Publication No. 2020/095829 and the compound disclosed in International Publication No. 2020/059625. Component (C) 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 component (C) include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and benzoylated products of phenol novolak. Examples include active ester compounds. 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.

Commercial products of component (C) 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, and an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation) is an active ester compound containing "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolak, and an acetylated product of phenol novolak. Examples of an active ester curing agent include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of a phosphorus atom-containing active ester curing agent include "EXB-9050L-62M" manufactured by DIC Corporation.

In the curable resin composition of the present invention, the content of component (A) is preferably 1 to 1000 parts by mass, when the total of component (B) and component (C) is 100 parts by mass. The amount is more preferably 900 parts by weight, and particularly preferably 10 to 800 parts by weight. If the content of component (A) is less than 1 part by mass, there are concerns that the dielectric properties will deteriorate and water will be easily absorbed, and if it is more than 1000 parts by mass, it will be difficult to develop sufficient flexibility to form a film. becomes.

Regarding the blending ratio of component (B) and component (C), the ratio of active ester equivalent (α) to epoxy equivalent (β) (α/β) is preferably 0.5 to 1.5, more preferably is from 0.8 to 1.2, more preferably from 0.90 to 1.10. If it is out of the above range, there is a risk that excess epoxy groups or active ester groups may remain in the system. :85%, etc.), the characteristics may deteriorate in long-term reliability tests.

[Maleimide compound]
The curable resin composition of the present invention may contain a 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.

[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 interlayer insulation layer forming material, copper clad laminate, prepreg, RCC, etc., the amount of the above-mentioned inorganic filler used is preferably 5% in the curable resin composition. ~80 parts by weight, more preferably 10 to 60 parts by weight.

[Curing accelerator]
The curable resin composition of the present invention can also have improved curability by adding a curing accelerator. Curing accelerators include anionic curing accelerators that promote the curing reaction by generating anions by irradiation or heating with ultraviolet rays or visible light, or anionic curing accelerators that promote the curing reaction by generating cations by irradiating or heating ultraviolet rays or visible light. Cationic curing accelerators are preferred.

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, and benzyl Examples include dimethylamine, 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, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide, etc. It is not limited to these. Further, these may be used alone or in combination.

Examples of 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 there are no particular specifications, organic acid ions and hydroxide ions are particularly preferred.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen Examples include transition metal compounds (transition metal salts) such as zinc acid ester, zinc myristate), zinc phosphate ester (zinc octyl phosphate, zinc stearyl phosphate), but are not limited to these. Further, these may be used alone or in combination.

The amount of the curing accelerator used is 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

[Polymerization initiator]
The curable resin composition of the present invention can also have improved curability by adding a polymerization initiator. A polymerization initiator is a compound that can polymerize olefin functional groups such as ethylenically unsaturated bonds, and includes olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, radical polymerization initiators, etc. It will be done. 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 upon irradiation with ultraviolet rays or visible light or heating, and initiates a chain polymerization reaction. Examples of 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 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 polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, dielectric properties such as dielectric constant and dielectric loss tangent may be impaired.

[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 nonvolatile content 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, when the total nonvolatile content excluding the inorganic filler in the curable resin composition is 100 parts by mass. If it is less than 0.001 parts by mass, it may be insufficient to exhibit a photostabilizing effect, and if it is more than 10 parts by mass, 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 in a range that does not impair the flame retardancy and heat resistance of the cured product, and when the total of components (A) to (C) is 100 parts by mass, it is 0.05 to 50 parts by mass. The amount is preferably 0.05 to 20 parts by mass, and more preferably 0.05 to 20 parts by mass.

[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.

The curable resin composition of the present invention further includes a phenol resin, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, a cyanate ester resin, a polybutadiene and a modified product thereof, Polystyrene, 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.

[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 when the total mass of components (A) to (C) is 100 parts by mass, it is preferably 5 to 1000 parts by mass, and 10 to 750 parts by mass. is more preferable. 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.

[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.

[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 compound obtained by reacting a phenol 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)sulfone, Examples include, but are not limited to, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and a phenol/dicyclopentadiene cocondensate with the hydroxyl group converted to 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, based on 100 parts by weight of the total weight of the cyanate ester resin and components (A) to (C). .

[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 is obtained by preparing the above-mentioned components in predetermined proportions, precured at 130 to 180°C for 30 to 500 seconds, and further cured at 150 to 200°C for 2 to 500 seconds. By post-curing for 15 hours, a sufficient curing reaction proceeds and the cured product of the present invention is obtained. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the composition can be cured after removing the solvent.

The method for preparing the curable resin composition of the present invention is not particularly limited, but the components may be simply mixed uniformly or may be prepolymerized. For example, a mixture of components (A) to (C) is heated to form a prepolymer in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent. Similarly, compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, inorganic fillers, and other additives are added to preform. It may also be made into a polymer. For mixing or prepolymerization of each component, for example, an extruder, kneader, roll, etc. are used in the absence of a solvent, and a reaction vessel equipped with a stirring device, etc., is used in the presence of a solvent.

The method for uniformly mixing is to knead the resin composition using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100° C. to obtain a uniform resin composition. After the obtained resin composition is crushed, it is molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or it is made into a granular powder or powder-like molded product, or the composition is molded onto a surface support. It is also possible to make a curable resin composition molded product by melting it and molding it into a sheet with a thickness of 0.05 mm to 10 mm. The obtained molded product becomes a non-sticky molded product at 0 to 20°C, and its fluidity and hardenability hardly decrease even if it is stored at -25 to 0°C for one week or more.
The obtained molded product can be molded into a cured product using a transfer molding machine or a compression molding machine.

The curable resin composition of the present invention can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent. The curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, etc. as necessary to form a varnish, which can be applied to glass fibers or carbon fibers. A cured product of the curable resin composition of the present invention can be obtained by hot press molding a prepreg obtained by impregnating a base material such as polyester fiber, polyamide fiber, alumina fiber, or paper and drying it by heating. . The solvent used in this case is used in an amount that accounts for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Further, if the composition is a liquid composition, a cured resin containing carbon fibers can be obtained as it is, for example, by the RTM method.

Furthermore, the curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition can be obtained by applying the curable resin composition of the present invention as the curable resin composition varnish onto a release film, removing the solvent under heating, and then B-staging it. It is obtained as a sheet adhesive. This sheet adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

A prepreg can also be obtained by heating and melting the curable resin composition of the present invention, reducing the viscosity, and impregnating it into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Specific examples include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, as well as inorganic fibers other than glass and polyester fibers. Examples include, but are not limited to, paraphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), fully aromatic polyamide, polyester, polyparaphenylenebenzoxazole, polyimide, and organic fibers such as carbon fiber. The shape of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. In addition, plain weaving, Nanako weaving, twill weaving, etc. are known as weaving methods of the woven fabric, and the weaving method can be appropriately selected from these known methods depending on the intended use and performance. In addition, woven fabrics subjected to opening treatment or glass woven fabrics whose surface is treated with a silane coupling agent or the like are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Further, a prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying the impregnated fibers by heating.

Moreover, a laminate can also be manufactured using the above prepreg. The laminate is not particularly limited as long as it includes one or more prepregs, and may include any other layers. The method for manufacturing the laminate is not particularly limited, and any generally known method can be appropriately applied. For example, when molding a metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. Obtainable. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. The pressure to be applied is not particularly limited, but if the pressure is too high, it will be difficult to adjust the solids content of the resin in the laminate, and the quality will not be stable.If the pressure is too low, air bubbles and adhesion between the laminates may occur. 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminate of this embodiment can be suitably used as a metal foil-clad laminate, which will be described later, by including a layer made of metal foil.
After cutting the above prepreg into a desired shape and laminating it with copper foil etc. if necessary, the curable resin composition is heated and cured while applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, etc. Electrical and electronic laminates (printed wiring boards) and carbon fiber reinforced materials can be obtained.

The curable resin composition of the present invention can also be made into a resin sheet. As a method for obtaining a resin sheet from the curable resin composition of the present invention, for example, the curable resin composition is coated on a support film (support), and then dried to form a resin composition layer on the support film. For example, a method of forming a . When the curable resin composition of the present invention is used for a resin sheet, the film softens under the laminating temperature conditions (70°C to 140°C) in the vacuum lamination method, and is present on the circuit board at the same time as the circuit board is laminated. It is important that the resin exhibits fluidity (resin flow) that allows the resin to be filled in via holes or through holes, and it is preferable to mix the above-mentioned components so as to exhibit such characteristics. Note that the resulting resin sheets and circuit boards (copper-clad laminates, etc.) do not exhibit locally different characteristic values due to phase separation, and can maintain a constant level of performance at any location. In order to achieve this, uniformity in appearance is required.

Here, the diameter of the through hole of the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, and it is preferable that resin filling is possible within this range. Note that when laminating both sides of the circuit board, it is desirable that about 1/2 of the through holes be filled.

As a specific method for manufacturing the resin sheet, after preparing a varnished resin composition by blending an organic solvent, applying the varnished resin composition to the surface of the support film (Y), Further, a method of forming the resin composition layer (X) by drying the organic solvent by heating or blowing hot air may be mentioned.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. It is preferable to use carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is also preferable to use them in a proportion such that the nonvolatile content is 30 to 60% by mass. preferable.

Note that the thickness of the resin composition layer (X) to be formed needs to be greater than or equal to the thickness of the conductor layer. Since the conductor layer of the circuit board has a thickness in the range of 5 to 70 μm, the resin composition layer (X) preferably has a thickness of 10 to 100 μm. In addition, the said resin composition layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and from scratching it.

The supporting film and protective film may be made of polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, polyester such as polyethylene terephthalate (PET) or polyethylene naphthalate, polycarbonate, polyimide, or release paper or metal foil such as copper foil or aluminum foil. etc. can be mentioned. Note that the support film and the protective film may be subjected to a release treatment in addition to mud treatment and corona treatment. The thickness of the support film is not particularly limited, but is 10 to 150 μm, preferably 25 to 50 μm. Further, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer by heating and curing. If the support film (Y) is peeled off after the resin composition layer constituting the resin sheet is cured by heating, it is possible to prevent dust and the like from adhering during the curing process. If the support film is to be peeled off after curing, a release treatment is applied to the support film in advance.

Note that a multilayer printed circuit board can be manufactured from the resin sheet obtained as described above. For example, if the resin composition layer (X) is protected with a protective film, after peeling off the protective film, apply the resin composition layer (X) to one or both sides of the circuit board so as to be in direct contact with the circuit board. , for example, by a vacuum lamination method. The lamination method may be a batch method or a continuous method using rolls. Furthermore, if necessary, the resin sheet and the circuit board may be heated (preheated) before lamination. As for the laminating conditions, it is preferable that the pressure bonding temperature (laminate temperature) is 70 to 140°C, and the pressure bonding pressure is 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable that the lamination is carried out under a reduced air pressure of 20 mmHg (26.7 hPa) or less.

Further, a semiconductor device can be manufactured using the curable resin composition of the present invention. 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), and TQFP. (Think Quad Flat Package), etc.

The curable resin composition and cured product thereof of the present invention can be used in a wide range of fields. Specifically, it can be used for various purposes such as molding materials, adhesives, composite materials, and paints. Since the cured product of the curable resin composition according to the present invention exhibits excellent heat resistance and dielectric properties, it can be used as an encapsulant for semiconductor devices, an encapsulant for liquid crystal display devices, an encapsulant for organic EL devices, a laminate ( It is suitably used for electrical/electronic parts such as printed wiring boards, BGA substrates, build-up boards, etc., composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

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).

[Synthesis example 3]
With reference to International Publication No. 2020/059434, an active ester compound (E-1) represented by the following formula (5) was synthesized.

[Synthesis example 4]
Following Example 2 of International Publication No. 2020/095829, a reaction product of polyphenylene ether (SA-90: manufactured by SABIC), hydroxyl-terminated polybutadiene (G-3000: manufactured by Nippon Soda), terephthalic acid dichloride, and methacrylic acid chloride was used. It was obtained as a toluene solution containing 30 wt% solid content (ES-1). Ester equivalent is 1127.6g/eq. The total aromatic ester equivalent derived from the reaction of aromatic acid chloride and phenolic hydroxyl group is 1526.6 g/eq. Met. Regarding this compound, the total aromatic ester equivalent is treated as the active ester equivalent.

[Examples 1 and 2, Comparative Example 1]
In Example 1, each material was blended in the proportions shown in Table 1, and acetone was added to make an acetone solution with a solid content of 66 wt%. The solution was coated on mirror-finished copper foil to a wet film thickness of 200 μm, and vacuum coated. After pre-drying in an oven at 60°C for 30 minutes, it was cured at 220°C for 1 hour. Thereafter, a cured film was obtained by etching the copper foil using ferric chloride.
In Example 2, each material including ES-1 with a solid content of 30 wt% was mixed in the proportions shown in Table 1 to make a toluene solution with a solid content of 39 wt%, and the solution was coated on mirror-finished copper foil so that the wet film thickness was 200 μm. After pre-drying in a vacuum oven at 60°C for 30 minutes, it was cured at 220°C for 1 hour. Thereafter, a cured film was obtained by etching the copper foil using ferric chloride.
In Comparative Example 1, each material was blended in the proportions shown in Table 1, and acetone was added to make an acetone solution with a solid content of 66 wt%. The solution was coated on mirror-finished copper foil to a wet film thickness of 200 μm, and vacuum-treated. After pre-drying in an oven at 60°C for 30 minutes, it was cured at 175°C for 2 hours. Thereafter, a cured film was obtained by etching the copper foil using ferric chloride.
Each of the cured films of Examples 1 and 2 and Comparative Example 1 was evaluated by cutting test pieces into desired sizes using a laser cutter.

<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.

・ＮＣ－３０００－Ｈ：ビフェニルアラルキル型エポキシ樹脂（日本化薬社製）
・ＤＭＡＰ：ジメチルアミノピリジン（硬化促進剤、東京化成社製）
・２Ｅ４ＭＺ：２－エチル－４－メチルイミダゾール（硬化促進剤、四国化成社製）

・NC-3000-H: Biphenylaralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
・DMAP: Dimethylaminopyridine (curing accelerator, manufactured by Tokyo Kasei Co., Ltd.)
・2E4MZ: 2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Co., Ltd.)

From the results in Table 1, it was confirmed that Examples 1 and 2 had excellent low dielectric properties.

[Example 3, Comparative Example 2]
Each material was blended in the proportions shown in Table 2, and coated on mirror-finished copper foil to a wet film thickness of 200 μm, pre-dried in a vacuum oven at 60° C. for 30 minutes, and then cured at 220° C. for 1 hour. After curing, the copper foil was etched using ferric chloride to obtain a cured film.

<Compatibility test>
After blending each material in the ratio shown in Table 2 in a polybottle (I-BOY: manufactured by AS ONE Corporation), after stirring for 1 hour at 25 ° C. at a rotation speed of 100 rpm using a roller mixer (MIX-ROTAR VMR-5: manufactured by AS ONE Corporation), Evaluation was performed using the following criteria. The results are shown in Table 2.
・If a uniform solution is obtained when each material except the inorganic filler is made into a resin solution: ○ ・If a uniform solution is not obtained when each material except the inorganic filler is made into a resin solution: ×

<Film forming property test>
Evaluation was performed using the following criteria. The results are shown in Table 2.
・If there are no cracks or breaks in the cured film after etching treatment: ○・If cracks or breaks occur in the cured film after etching treatment: ×

・ＤＭＡＰ：ジメチルアミノピリジン（硬化促進剤、東京化成社製）
・ＭＳＲ－２２１２：シリカフィラー（龍森社製）

・DMAP: Dimethylaminopyridine (curing accelerator, manufactured by Tokyo Kasei Co., Ltd.)
・MSR-2212: Silica filler (manufactured by Ryumorisha)

From the results in Table 2, it was confirmed that Example 3 had excellent compatibility and sufficient flexibility to form a film.

The curable resin composition, resin sheet, and cured product thereof of the present invention are suitably used for electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

Claims (13)

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

(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.) The curable resin composition according to claim 1 or 2, wherein the component (C) is a compound having a vinyl group. The curable resin composition according to any one of claims 1 to 3, further comprising a maleimide compound. The curable resin composition according to any one of claims 1 to 4, further comprising an inorganic filler. The curable resin composition according to any one of claims 1 to 5, further comprising a curing accelerator. The curable resin composition according to any one of claims 1 to 6, further comprising a polymerization initiator. The curable resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer. A resin sheet comprising the curable resin composition according to any one of claims 1 to 8 and a support. A cured product of the curable resin composition according to any one of claims 1 to 8 or the resin sheet according to claim 9. An insulating layer formed from the cured product according to claim 10. A printed wiring board comprising the insulating layer according to claim 11. A semiconductor device comprising the printed wiring board according to claim 12.

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