JP7418644B2 - Maleimide compounds, curable resin compositions and cured products thereof, and amine compounds - Google Patents

Description

The present invention relates to a maleimide compound, a curable resin composition, a cured product thereof, and an amine compound, and is applicable to semiconductor encapsulants, printed wiring boards, electrical/electronic parts such as build-up laminates, carbon fiber reinforced plastics, Lightweight, high-strength materials such as glass fiber reinforced plastics are suitable for use in 3D printing applications.

In recent years, the fields of use for laminates that carry electrical and electronic components have expanded, and the required characteristics have become broader and more sophisticated. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are mounted on laminated boards made of polymer materials. It is increasingly being installed.

In order to satisfy the heating characteristics that are the standard values for heat-resistant laminates, heat resistance (Tg) of at least 160° C. or higher is required (Non-Patent Document 1).

In addition, 5G, the fifth generation communication system whose development is currently accelerating, is expected to further increase capacity and speed. The need for materials with a low dielectric loss tangent is increasing, and a dielectric loss tangent of 0.005 or less is required at least at 10 GHz.

Furthermore, in the automotive field, computerization is progressing, and precision electronic equipment is sometimes placed near engine drive parts, so higher levels of heat and moisture resistance are required. SiC semiconductors are beginning to be used in trains, air conditioners, etc., and the encapsulating material for semiconductor elements is required to have extremely high heat resistance, so conventional epoxy resin encapsulating materials can no longer meet this demand.

Against this background, polymer materials that can have both heat resistance and low dielectric loss tangent characteristics are being investigated. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenol resin. However, on the other hand, since phenolic hydroxyl groups that do not participate in the curing reaction remain, the electrical properties cannot be said to be sufficient. Further, Patent Document 2 discloses an allyl ether resin in which the hydroxyl group is substituted with an allyl group. However, it has been shown that Claisen rearrangement occurs at 190°C, and at 200°C, which is the general molding temperature for substrates, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so electrical properties cannot be satisfied. do not have.

In addition, in recent years, 3D printing has been attracting attention as a three-dimensional modeling method, and this 3D printing method is being applied in fields that require reliability, such as aerospace, cars, and connectors for electronic components used in these. It's starting to happen. In particular, photocuring and thermosetting resins are being studied for applications typified by stereolithography (SLA) and digital light processing (DLP). Therefore, in the conventional method of transferring from a mold, stability and accuracy of shape are mainly required, but in 3D printing applications, heat resistance, mechanical properties, toughness, flame retardance, and even electrical properties are required. A variety of properties are required, and the development of materials for these properties is progressing. Furthermore, when used in structural members, changes in characteristics due to moisture absorption, etc. are a problem. Currently, acrylate resins and epoxy resins are used in such applications, but their cured products contain numerous ester bonds, ether bonds, and even hydroxyl groups, and do not have sufficient moisture absorption properties.

Japanese Patent Application Publication No. 04-359911 International Publication 2016/002704 Basic course “Substrate materials 5th” Heat-resistant glass epoxy substrate Vol. 8No. 6 (1993)

The present invention has been made in view of these circumstances, and provides a maleimide compound, a curable resin composition, a cured product thereof, and a raw material thereof, which has excellent heat resistance, low dielectric properties, and good curability. The purpose of this invention is to provide an amine compound.

That is, the present invention relates to the following [1] to [8]. In the present invention, "(numerical value 1) to (numerical value 2)" indicates that the upper and lower limits are included.
[1]
A maleimide compound represented by the following formula (1).

(In formula (1), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. X is represented by the following formula (2). m is An integer from 0 to 4, n is the average value of the number of repetitions, and 1≦m≦20.)

(In formula (2), 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 represents an integer of 0 to 4, and q represents an integer of 0 to 4. Represents an integer of 3. r is the average value of the number of repetitions, and is 1≦r≦20. * represents the bonding position with the aromatic ring in formula (1).)
[2]
A maleimide compound represented by the following formula (3).

(In formula (3), X is represented by the following formula (4). n is the average value of the number of repetitions, and is 1.1≦n≦20.)

(In formula (4), each of the plurality of R's exists independently and represents a hydrocarbon group having 1 to 5 carbon atoms. p represents an integer of 0 to 4, and r is the average value of the number of repeats. , 1.1≦r≦20. * represents the bonding position with the aromatic ring of the compound of formula (3).)
[3]
The maleimide compound according to the above item [2], wherein in the formula (4), p is 2, and the substitution position of R is ortho to the maleimide group.
[4]
A curable resin composition containing the maleimide compound according to any one of [1] to [3] above.
[5]
The curable resin composition according to item [4] above, further containing a radical polymerization initiator.
[6]
A cured product obtained by curing the curable resin composition described in the preceding item [4] or [5].
[7]
An amine compound represented by the following formula (5).

(In formula (5), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer of 0 to 4, and q represents 0 to 4. It represents an integer of 3. r is the average value of the number of repetitions, and 1≦r≦20.
[8]
A reaction product of the compound described in the preceding item [7] and maleic anhydride.

The cured product of the maleimide compound of the present invention has excellent properties such as high heat resistance and low dielectric properties. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, etc.

1 shows a GPC chart of the amine compound of Example 1. 1 shows a GPC chart of the maleimide compound of Example 1. 1 shows a ¹ H-NMR chart of the maleimide compound of Example 1. A GPC chart of the amine compound of Example 2 is shown. 1 shows a GPC chart of the maleimide compound of Example 2. 1 shows a ¹ H-NMR chart of the maleimide compound of Example 2. A GPC chart of the amine compound of Synthesis Example 1 is shown. A GPC chart of the maleimide compound of Synthesis Example 2 is shown.

The maleimide compound of the present invention is represented by the following formula (1).

(In formula (1), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. X is represented by the following formula (2). m is An integer from 0 to 4, n is the average value of the number of repetitions, and 1≦n≦20.)

(In formula (2), 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 represents an integer of 0 to 4, and q represents an integer of 0 to 4. Represents an integer of 3. r is the average value of the number of repetitions, and is 1≦r≦20. * represents the bonding position with the aromatic ring in formula (1).)

In the formula (1) and the formula (2), 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 10 carbon atoms. A hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms. If R has a small number of carbon atoms, molecular vibration will be difficult to occur when exposed to high frequency, so when R is a hydrocarbon group having 1 to 3 carbon atoms among the above descriptions, the electrical properties are particularly excellent.

In the formula (1), m is usually an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. n is the average value of the number of repetitions, usually 1≦m≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦18, particularly preferably 1.1≦n≦ It is 15. The value of n can be calculated from the number average molecular weight (Mn) value of the compound represented by formula (1) determined by gel permeation chromatography (GPC). The number average molecular weight is preferably 200 or more and less than 10,000, more preferably 1,000 or more and less than 7,500, and particularly preferably 2,000 or more and less than 5,000. When the number average molecular weight is less than 10,000, purification by washing with water becomes easy, and when it is 200 or more, there is little fear that the target compound will volatilize in the solvent distillation step.

In the formula (2), p usually represents an integer of 0 to 4, preferably 0 to 3, and more preferably 0 to 2. q usually represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 to 1, particularly preferably 0. r is the average value of the number of repetitions, usually 1≦m≦20, preferably 1.1≦n≦20, more preferably 1.1≦n≦18, particularly preferably 1.1≦n≦ It is 15.

A preferred embodiment of the maleimide compound represented by the formula (1) is a maleimide compound represented by the following formula (3).

(In formula (3), X is represented by the following formula (4). n is the average value of the number of repetitions, and is 1.1≦n≦20.)

(In formula (4), each of the plurality of R's exists independently and represents a hydrocarbon group having 1 to 5 carbon atoms. p represents an integer of 0 to 4, and r is the average value of the number of repeats. , 1.1≦r≦20. * represents the bonding position with the aromatic ring of the compound of formula (3).)

In the above formula (4), from the viewpoints of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance, it is particularly preferable that R be substituted with two substituents at ortho positions with respect to the maleimide group.

The maleimide compound represented by the formula (1) can be obtained, for example, by reacting a polymer of an amine compound represented by the following formula (5) with maleic anhydride. Although the polymerization and maleimidation reaction of the amine compound represented by the following formula (5) may be performed separately, the polymerization reaction and the maleimidation reaction of the amine compound represented by the following formula (5) may be performed in the presence of an acid catalyst such as methanesulfonic acid. The reaction may be carried out all at once. The conditions for the maleimidation reaction are not particularly limited, but the solvents used include, for example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, and acetic acid. Examples include, but are not limited to, water-insoluble solvents such as ester solvents such as ethyl and butyl acetate, and ketone solvents such as methyl isobutyl ketone 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. During the reaction, if necessary, as a catalyst, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride, zinc chloride, 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 generally 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, per 1 mol of the amino group of the amine compound used. 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. Further, as a co-catalyst for imidization, a basic co-catalyst such as triethylamine can be used alone or in combination. When a 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 is distilled off using an evaporator or the like to obtain the desired maleimide compound.

(In formula (5), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer of 0 to 4, and q represents 0 to 4. It represents an integer of 3. r is the average value of the number of repetitions, and 1≦r≦20.

In the formula (5), the preferred ranges of R, p, q, and r are the same as in the formula (2).

In the above formula (5), from the viewpoint of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance, the substitution position of R on the benzene ring to which the amino group is bonded is 2 ortho to the amine group. It is particularly preferred that one substituent is substituted.

The softening point of the amine compound represented by formula (5) is preferably 120°C or lower, more preferably 110°C or lower. When the softening point is 120°C or less, the viscosity when induced into the maleimide 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. The viscosity can be lowered by increasing the amount of diluting solvent, but in this case, the resin may not adhere sufficiently to the fibrous material during the impregnation process, so it is preferable to set the softening point to 120° C. or lower.

The amine compound represented by the formula (5) can be prepared, for example, by using an excess amount of diisopropenylbenzene (or α, α, α', α'-tetramethylbenzenedimethanols) in the presence of an acid catalyst. It can be obtained by reacting In this case, the substituent of the aniline compound is preferably unsubstituted or has an alkyl group having 1 to 5 carbon atoms, from the viewpoint of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance. Therefore, it is more preferable that the benzene ring is unsubstituted or has two alkyl groups having 1 to 3 carbon atoms at the ortho position of the benzene ring to which the amino group is bonded.
During synthesis, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, etc. are used as acid catalysts. 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 0.01 to 50% based on the total weight of the reaction substrates diisopropenylbenzene (or α, α, α', α'-tetramethylbenzenedimethanols) and anilines. % by weight, preferably from 0.1 to 35% by weight. If the amount of catalyst used is too large, unnecessary waste may increase, and if it is too small, the progress of the reaction may be slowed down. 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 reaction temperature is preferably 80 to 250°C, more preferably 90 to 240°C, even more preferably 100 to 230°C. If the reaction temperature is too high, unnecessary thermal decomposition reactions may occur, and if the reaction temperature is too low, the reaction may not proceed sufficiently. When α, α, α', α'-tetramethylbenzenedimethanols are used as a raw material or when an acidic catalyst containing water is used, the produced water or water in the system is azeotropically distilled with the solvent when the temperature is raised. remove it from the system. After the reaction is completed, the acidic catalyst is neutralized with an aqueous alkaline solution, etc., a water-insoluble organic solvent is added to the oil layer, water washing is repeated until the waste water becomes neutral, and then the solvent is removed under heating and reduced pressure. When activated clay or ion exchange resin is used, the reaction solution is filtered to remove the catalyst after the reaction is completed.

Examples of the anilines include aniline, о-methylaniline, m-methylaniline, p-methylaniline, о-ethylaniline, m-ethylaniline, p-ethylaniline, о-propylaniline, m-propylaniline, p-propylaniline, o-isopropylaniline, m-isopropylaniline, p-isopropylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-dipropylaniline, 2,6-isopropylaniline, 2 -Ethyl-6-methylaniline, 2-propyl-6-methylaniline, 2-isopropyl-6-methylaniline, 2-ethyl-6-propylaniline, 2-ethyl-6-isopropylaniline, etc. It is not limited to. 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 diisopropenylbenzene include 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, and alkyl substituted products thereof.
Examples of the α, α, α', α'-tetramethylbenzenedimethanols include α, α, α', α'-tetramethyl-1,2-benzenedimethanol, α, α, α', Examples include α'-tetramethyl-1,3-benzenedimethanol, α,α,α',α'-tetramethyl-1,4-benzenedimethanol, and alkyl substituted products thereof.
The diisopropenylbenzene and the α,α,α',α'-tetramethylbenzenedimethanols may be used alone or in combination of two or more. The amount of these used is preferably 1.0 to 10 times, more preferably 1.0 to 7.5 times, still more preferably 1.0 to 5 times, per mole of the amino group of the aniline. .0 times the mole.

[Polymerization initiator]
The curable resin composition of the present invention can also have improved curability by adding a polymerization initiator. Polymerization initiators are compounds that can polymerize olefin functional groups such as ethylenically unsaturated bonds, and include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Can be mentioned. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. In the case of olefin metathesis polymerization initiators such as Schrоck catalysts with molybdenum as the central metal, anionic polymerization initiators such as BuLi, and cationic polymerization initiators such as triethylaluminum, they have poor stability such as reacting with moisture in the air. .
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 mass, and 0.01 to 5 parts by mass, when the total nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. 3 parts by mass is particularly preferred. 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 the compound represented by formula (1), or may be added after synthesis. The amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the compound represented by formula (1).

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, Adeka Stab LA-72, Adeka Stab LA-68, Adeka Stab LA-63P, Adeka Stab LA-57, Adeka Stab LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinP A144, 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.

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

The amount of inorganic filler used when obtaining a curable resin composition for semiconductor encapsulation is preferably 80 to 92 parts by mass, more preferably 83 to 90 parts by mass, based on 100 parts by mass of the curable resin composition. be. In addition, when obtaining a curable resin composition for an interlayer insulation layer forming material, a substrate material such as a copper clad laminate, prepreg, or RCC, the amount of the above-mentioned inorganic filler used is 100 parts by mass of the curable resin composition. The amount is preferably 5 to 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. Examples of 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 benzyldimethyl. amine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., 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, and hexadecyltrimethylammonium hydroxide.
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 not particularly specified, organic acid ions and hydroxide ions are particularly preferred), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behenic acid) Examples include, but are not limited to, transition metal compounds (transition metal salts) such as zinc, zinc myristate) and zinc phosphate esters (octyl zinc phosphate, zinc stearyl phosphate). Further, these may be used alone or in combination.

The curing accelerator is used in an amount of 0.01 to 5.0 parts by mass, if necessary, based on 100 parts by mass of the total nonvolatile components excluding inorganic fillers in the curable resin composition.

[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-di-2,6-xylenyl phosphate, 1,3-phenylenebis(dixylenyl phosphate). ), phosphoric acid esters such as 1,4-phenylenebis(dixylenyl phosphate), 4,4'-biphenyl(dixylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene- In addition to phosphanes such as 10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, epoxy resins are reacted with the active hydrogen of the phosphanes. The resulting phosphorus-containing epoxy compounds include, but are not limited to, 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 within a range that does not impair the flame retardancy and heat resistance of the cured product, and the total nonvolatile content excluding inorganic fillers in the curable resin composition is 100 parts by mass. If so, the amount is preferably 0.05 to 50 parts by weight, more preferably 0.05 to 20 parts by weight.

[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 an epoxy resin, an active ester compound, a phenol resin, an amine resin, a maleimide compound, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a polyimide resin, a cyanate ester resin, Polyphenylene ether compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, etc. may be used, and these may be used alone or in combination. Among these compounds, compounds with ethylenically unsaturated bonds, cyanate ester resins, polyphenylene ether compounds, 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 to be used is preferably 10 times or less, more preferably 5 times or less, particularly preferably 3 times or less by mass, relative to the compound represented by formula (1). mass range. 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 compound represented by the formula (1). Regarding these components, those illustrated below can be used.

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

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

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

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

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

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

Examples of the phenol compound and naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, Examples include phloroglucin, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac, and phenol resins described below. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

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

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

Regarding the blending ratio of the active ester compound and the epoxy resin, the ratio (α/β) of active ester equivalent (α) to epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0. 8 to 1.2, more preferably 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.

[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.

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

[Maleimide compound]
A maleimide compound is a compound having one or more maleimide groups in its molecule. The curable resin composition of the present invention may contain a maleimide compound. 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. Examples include, but are not limited to, maleimide compounds published in 2019 "~Continued Epoxy Resin CAS Number Story~Curing Agent CAS Number Memorandum 32nd Bismaleimide (2)". 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 compound represented by formula (1). 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 heat resistance, dielectric properties, and low water absorption effects of the compound represented by formula (1) can be utilized.

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

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

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

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

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

The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the cyanate ester resin.

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

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

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

The content of the polyphenylene ether compound is not particularly limited, but it is preferably 5 to 1000 parts by mass, more preferably 10 to 750 parts by mass, based on 100 parts by mass of the compound represented by formula (1). 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.

[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 compound represented by formula (1) itself does not have a skeleton design that actively introduces heteroatoms such as oxygen or nitrogen, so it is a material with low polarity and low dielectric properties, It also has excellent compatibility with compounds composed only of hydrocarbons.

The content of polybutadiene and its modified product is not particularly limited, but it is preferably 5 to 1000 parts by mass, and 10 to 750 parts by mass, based on 100 parts by mass of the compound represented by formula (1). is more preferable. It is preferable that the polybutadiene and its modified products are within the above range, since not only are they excellent in heat resistance, but also cured products can be obtained that fully exhibit the excellent dielectric properties of the polybutadiene and its modified products.

[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 content of polystyrene and its modified product is not particularly limited, but it is preferably 5 to 1000 parts by mass, and 10 to 750 parts by mass, based on 100 parts by mass of the compound represented by formula (1). is more preferable. When styrene and its modified products are 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 polystyrene and its modified products.

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, by heating a mixture of the compound represented by formula (1) and other compounds in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent. Convert into prepolymer. 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.

A specific method for manufacturing the resin sheet is to prepare a varnished resin composition by blending an organic solvent, and then apply the varnished resin composition to the surface of the support film (Y). Further, there is a method of drying the organic solvent by heating or blowing hot air to form the resin composition layer (X).

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.
・GPC (gel permeation chromatography) analysis Calculated by polystyrene conversion using a polystyrene standard solution.
GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)
Column: Shodex KF-603 x 1, KF-602.5 x 1, KF-602 x 1, KF-601 x 1 (all manufactured by Showa Denko)
Guard column: Shodex KF-G 4A (manufactured by Showa Denko)
Coupling eluent: Tetrahydrofuran Flow rate: 1.5ml/min.
Column temperature: 40℃
Detection: RI (differential refraction detector)

・^1H -NMR analysis device: JNM-ECS400 manufactured by JEOL Ltd.

[Example 1]
In a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, add 24.3 parts of 2,6-dimethylaniline and 136 parts of α,α,α',α'-tetramethyl-1,3-benzenedimethanol. , 100 parts of toluene, and 35 parts of activated clay were charged, and reaction was carried out for 1.5 hours at an internal temperature of 110 to 135° C. while removing produced water by azeotropic dehydration. Thereafter, the internal temperature was raised to 210° C. while the toluene was being extracted, and the reaction was allowed to occur for 4 hours. After cooling, the extracted toluene was returned to the system, and 200 parts of toluene was newly added. Activated clay was removed by filtration to obtain a toluene solution (T-1) containing an amine compound represented by the following formula (6). A GPC chart of the obtained amine compound is shown in FIG.
Next, 100 parts of toluene, 29.4 parts of maleic anhydride, and 5.4 parts of methanesulfonic acid were added to a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, and while maintaining the internal temperature at 110°C. T-1 was added dropwise over 4 hours. Furthermore, a polymerization reaction of the olefin moiety of the amine represented by the following formula (6) and a maleimidization reaction of the amino group were carried out at 110° C. for 9 hours. After cooling, 200 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 133 parts of a maleimide compound (M-1) represented by the following formula (7) was obtained as a brown solid resin. A GPC chart of the obtained maleimide compound is shown in FIG. The number average molecular weight (Mn) was 2,082, and the weight average molecular weight (Mw) was 3,169. Further, a ¹ H-NMR chart (deuterochloroform) of the obtained maleimide compound is shown in FIG. A signal derived from the maleimide group was observed at 6.85 ppm on the ¹ H-NMR chart.

[Example 2]
In a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, add 35.4 parts of 2,6-diisopropylaniline and 136 parts of α,α,α',α'-tetramethyl-1,3-benzenedimethanol. , 100 parts of toluene, and 35 parts of activated clay were charged, and reaction was carried out at an internal temperature of 110 to 135° C. for 2 hours while removing produced water by azeotropic dehydration. Thereafter, the internal temperature was raised to 210° C. while toluene was extracted, and the reaction was continued for 9 hours. After cooling, the extracted toluene was returned to the system, and 200 parts of toluene was added. The activated clay was removed by filtration to obtain a toluene solution (T-2) containing an amine compound represented by the following formula (8). A GPC chart of the obtained amine compound is shown in FIG.
Next, 100 parts of toluene, 29.4 parts of maleic anhydride, and 5.4 parts of methanesulfonic acid were added to a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, and while maintaining the internal temperature at 110°C. T-2 was added dropwise over 2 hours. Furthermore, a polymerization reaction of the olefin moiety of the amine compound represented by the following formula (8) and a maleimidation reaction of the amino group were carried out at 110° C. for 10 hours. After cooling, 200 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 125 parts of a maleimide compound (M-2) represented by the following formula (9) was obtained as a brown solid resin. A GPC chart of the obtained maleimide compound is shown in FIG. The number average molecular weight (Mn) was 2007, and the weight average molecular weight (Mw) was 3301. Further, a ¹ H-NMR chart (deuterochloroform) of the obtained maleimide compound is shown in FIG. A signal derived from the maleimide group was observed at 6.85 ppm on the ¹ H-NMR chart.

[Synthesis example 1]
In a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, 48.5 parts of 2,6-dimethylaniline and 155 parts of α,α,α',α'-tetramethyl-1,3-benzenedimethanol were added. 4 parts of toluene, 100 parts of toluene, and 30.6 parts of activated clay were charged, and the internal temperature was raised to 210°C over 2 hours while removing toluene and generated water by azeotropic dehydration, and the reaction was allowed to proceed for 3 hours (GPC chart) (shown in Figure 7). After cooling the internal temperature to 120°C, 145.4 parts of 2,6-dimethylaniline was added and reacted at 220°C for 3 hours. After cooling, the extracted toluene was returned to the system, and 200 parts of toluene was added. The activated clay was removed by filtration, and the solvent and excess 2,6-dimethylaniline were distilled off to obtain 207 parts of an amine compound (A-1) represented by the following formula (10) as a brown solid resin ( Amine equivalent: 272.7 g/eq.). A GPC chart of the obtained amine compound is shown in FIG. The number average molecular weight (Mn) was 1048, and the weight average molecular weight (Mw) was 1252.

[Synthesis example 2]
Add 50 parts of toluene, 53.9 parts of maleic anhydride, and 2 parts of methanesulfonic acid to a flask equipped with a thermometer, condenser, stirrer, and Dean Stark, and add the toluene and NMP solution of A-1 while maintaining the reflux state. (A-1: 100 parts, toluene: 75 parts, NMP 25 parts) was added dropwise over 1 hour. The maleimidation reaction of the amino group was carried out under reflux conditions for 2 hours. After cooling, 100 parts of toluene was added, and the organic layer was washed five times with 100 parts of water. By distilling off the solvent under heating and reduced pressure, 117 parts of a maleimide compound (M-3) represented by the following formula (11) was obtained as a brown solid resin. A GPC chart of the obtained maleimide compound is shown in FIG. The number average molecular weight (Mn) was 1,353, and the weight average molecular weight (Mw) was 1,562.

[Examples 3 to 6, Comparative Example 1]
After mixing each compound obtained in Examples 1 to 2 and Synthesis Example 2 and a thermal radical initiator DCP (dicumyl peroxide, manufactured by Tokyo Kasei Co., Ltd.) in the proportions shown in Tables 1 and 2, mirror-finished copper foil ( T4X (manufactured by Fukuda Metal Copper Foil Co., Ltd.) was vacuum press-molded and cured at 220° C. for 2 hours. At this time, a cushion paper having a thickness of 250 .mu.m was hollowed out in the center to have a length and width of 150 mm as a spacer. In the evaluation, test pieces were cut out to a desired size using a laser cutter as needed, and the evaluation was performed. The evaluation results are shown in Tables 1 and 2.

<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 0.3 mm.

<Heat resistance (DSC)>
Differential scanning calorimeter: DSC6220 (manufactured by SII Nanotechnology)
Measurement temperature range: 30-330℃
Temperature increase rate: 10°C/min Atmosphere: Nitrogen (30mL/min)
Sample amount: 5mg
Tg: The inflection point of the DSC chart was defined as Tg.

From the results in Tables 1 and 2, it was confirmed that the curable resin composition of the present invention has excellent dielectric properties and heat resistance.

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

Claims (1)

A maleimide compound with a number average molecular weight of 1,000 or more and less than 10,000, which is obtained by reacting an amine compound represented by the following formula (5) with maleic anhydride in the presence of an acid catalyst and has a reacted double bond in the α-methylstyrene structure. and a maleimide compound represented by the following formula (12) .

(In formula (5), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer of 0 to 4, and q represents 0 to 4. Represents an integer of 3. r is the average value of the number of repetitions, and 1≦r≦20.)

(In formula (12), multiple R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer of 0 to 4, and q represents an integer of 0 to 4. Represents an integer of 3. r is the average value of the number of repetitions, and 1≦r≦20.)

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