Curable resin composition

Abstract

To provide a curable resin composition that has a low dielectric constant and low dielectric loss tangent, and that produces a cured product with minimal delamination from copper even after treatment with desmear solution. [Solution] (A) A cyclic imide resin with a specific structure, (B) A cyclic imide resin having a specific structure different from (A), and (C) Curing catalyst A curable resin composition containing [a specific ingredient]. (A) and (B) each have a maleimide group or a citraconimide group at both ends, and have a structure derived from a diamine with an aliphatic hydrocarbon group or a dimer acid skeleton, and / or a structure derived from a diamine with an arylene group.

Description

[Technical Field]

[0001] This invention relates to a curable resin composition. [Background technology]

[0002] In recent years, mobile communication devices such as mobile phones, their base station equipment, network infrastructure equipment such as servers and routers, and electronic devices such as large computers have seen a continuous increase in the speed and capacity of signals used. Consequently, high-frequency bands such as the 20GHz range are used in printed circuit boards mounted on these electronic devices, requiring insulating materials for printed circuit boards to have properties such as low dielectric constant and low dielectric loss tangent. Materials that may satisfy these properties include epoxy resins, modified polyphenylene ether resins, and maleimide resins (Patent Documents 1-4).

[0003] Furthermore, conventional methods for bonding insulating materials involved roughening the conductor circuit to increase adhesive strength through the anchoring effect. However, in the high-frequency range, the skin effect causes more electricity to flow through the surface of the conductor, resulting in longer signal paths and delays in roughened conductor circuits. Therefore, in high-frequency applications, the surface of the conductor circuit needs to be as smooth as possible, and the anchoring effect cannot be relied upon for adhesive strength. Aliphatic maleimide resins have low dielectric constant and low dielectric loss tangent, and exhibit high adhesive strength even to low-coarse copper (Patent Document 5). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-1965 [Patent Document 2] Japanese Patent Publication No. 2018-28044 [Patent Document 3] Japanese Patent Publication No. 2020-176190 [Patent Document 4] Japanese Patent Publication No. 2021-181531 [Patent Document 5] Japanese Patent Publication No. 2020-12026 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, resin compositions containing aliphatic maleimide resins have the disadvantage that their chemical resistance is low due to the alkyl group of the aliphatic maleimide, and that delamination from copper is likely to occur when treated with a desmear solution such as permanganate solution after via holes are formed by drilling or laser processing during the manufacturing process of printed circuit boards. Therefore, the present invention aims to provide a curable resin composition that exhibits a low dielectric constant and low dielectric loss tangent, while also producing a cured product with minimal delamination from copper even after treatment with a desmear solution. [Means for solving the problem]

[0006] As a result of diligent research to solve the above problems, the inventors of the present invention have found that the following curable resin composition can achieve the above objectives, and have completed the present invention. In other words, the present invention provides the following curable resin compositions, etc. <1> (A) A cyclic imide resin represented by the following formula (1), [ka] (In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms, which may contain heteroatoms, or a divalent hydrocarbon group derived from a dimer acid skeleton. B independently represents an arylene group having 6 or more carbon atoms, which may contain heteroatoms. X is a hydrogen atom or a methyl group, where n1 is between 0 and 200, m1 is between 0 and 200, and n1 and m1 are numbers such that n1 + m1 is between 21 and 400. The order of each repeating unit enclosed by n1 and m1 is not limited.) (B) Cyclic imide resin represented by the following formula (2): 1 to 40 parts by mass with respect to 100 parts by mass of component (A), [Chemical formula] (In formula (2), A, Q, B, and X are the same as above, n2 is 0 to 10, m2 is 0 to 10, and n2 and m2 are numbers such that n2 + m2 satisfies 0 to 20. Also, the order of each repeating unit enclosed by n2 and m2 is not limited.) and (C) Curing catalyst: 0.01 to 10 parts by mass with respect to 100 parts by mass of component (A) A curable resin composition containing the above. <2> The curable resin composition according to <1>, wherein the component (B) is a cyclic imide resin represented by the following formula (3). [Chemical formula] (In formula (3), A, Q, X, and n2 are the same as above.) [Advantages of the invention]

[0007] The curable resin composition of the present invention has a low relative permittivity and a low dielectric loss tangent, and forms a cured product with little peeling from copper even after being treated with a desmear solution. Therefore, the curable resin composition of the present invention is useful for applications such as copper-clad laminates, printed wiring boards, base films for flexible printed wiring boards, coverlay films, and semiconductor encapsulation materials. [Embodiments for carrying out the invention]

[0008] Hereinafter, the curable resin composition of the present invention will be described in detail.

[0009] [(A) Cyclic imide resin represented by the following formula (1)] The cyclic imide resin of component (A) is the main component of the curable resin composition of the present invention and is represented by the following formula (1). By containing component (A), the cured product of the curable resin composition has a low relative permittivity and a low dielectric loss tangent, and forms a cured product with little peeling from copper even after being treated with a desmear solution. [Chemical formula] In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain heteroatoms or a divalent hydrocarbon group derived from a dimer acid skeleton. B independently represents an arylene group having 6 or more carbon atoms which may contain heteroatoms. X is a hydrogen atom or a methyl group, n1 is from 0 to 200, m1 is from 0 to 200, and n1 and m1 are numbers such that n1 + m1 satisfies 21 to 400. Also, the order of each repeating unit enclosed by n1 and m1 is not limited.

[0010] Here, the organic group represented by A in formula (1) is independently a tetravalent organic group containing a cyclic structure, and in particular, it is preferably any of the tetravalent organic groups represented by the following formulas. [Chemical formula] [[ID=**17**]]The bond to which the substituent in the above formula is not attached is bonded to the carbonyl carbon forming the cyclic imide structure in formula (1).

[0011] The organic group represented by Q in formula (1) is independently a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain heteroatoms or a divalent hydrocarbon group derived from a dimer acid skeleton, and is preferably a divalent aliphatic hydrocarbon group or a divalent hydrocarbon group derived from a dimer acid skeleton represented by any of the following structural formulas. [Chemical formula]

[0012] The bond to which the substituent in the above structural formula is not attached is bonded to the nitrogen atom forming the cyclic imide structure in formula (1). In the above structural formula, R 1 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 1 Note: The text seems to be a chemical formula description in Japanese, and I've tried my best to translate it accurately while keeping the specific tags intact as per the requirements. Some of the chemical formula notations might need further clarification depending on the actual chemical context.Preferably, it is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms. In the above structural formula, p 1 and p 2 Each of these numbers is 5 or greater, preferably between 5 and 12, more preferably between 6 and 10, and may be the same or different. In the above structural formula, p 3 and p 4 Each of these is a number greater than or equal to 0, preferably a number between 0 and 4, more preferably a number between 0 and 3, and may be the same or different. In the above structural formula, p 5 and p 6 Each of these is a number greater than or equal to 0, preferably a number between 0 and 4, more preferably a number between 0 and 2, and may be the same or different.

[0013] The divalent hydrocarbon group derived from the dimer acid skeleton is derived from dimer acid, a liquid fatty acid mainly composed of a 36-carbon dicarboxylic acid, produced by the dimerization of 18-carbon unsaturated fatty acids derived from natural materials such as vegetable oils. Dimer acid does not have a single skeleton but has multiple structures and several isomers exist. The dimer acid skeleton refers to a group derived from dimer amine, which has a structure in which the carboxyl group of such dimer acid is replaced with a primary aminomethyl group. From the viewpoint of heat resistance and reliability of the cured product, it is more preferable for the divalent hydrocarbon group derived from the dimer acid skeleton to have a structure in which the carbon-carbon double bond in the hydrocarbon group derived from the dimer acid skeleton is reduced by hydrogenation reaction. Generally, dimer acids may contain trimers (trimer acids) due to their use of natural materials such as vegetable oils as raw materials. However, it is preferable that the proportion of hydrocarbon groups derived from dimer acid is high, for example, 95% by mass or more, among the hydrocarbon groups derived from dimer acid and trimer acid. This is because it tends to result in superior dielectric properties, lower viscosity at high temperatures, excellent moldability, and reduced susceptibility to moisture absorption. As described above, since the dimer acid skeleton has a plurality of structures, in this specification, the divalent hydrocarbon group derived from the dimer acid skeleton is represented by -C 36 H 70 - as its average structure in some cases.

[0014] The organic group represented by B in formula (1) is independently an arylene group having 6 or more carbon atoms which may contain a hetero atom, and is preferably an arylene group represented by any of the following structural formulas.

Chemical formula

[0015] The bond to which no substituent is bonded in the above structural formula is bonded to the nitrogen atom that forms the cyclic imide structure in formula (1). In the above formula, R 2 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and are preferably a hydrogen atom or a methyl group. In the above formula, R 3 are each independently a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, and are preferably a methyl group or a trifluoromethyl group. In the above formula, Z is an oxygen atom, a sulfur atom or a methylene group, and is preferably an oxygen atom.

[0016] In formula (1), X is a hydrogen atom or a methyl group. In formula (1), n1 is 0 to 200, m1 is 0 to 200, and n1 and m1 are numbers such that n1 + m1 satisfies 21 to 400. By containing the component (A) in which n1 + m1 satisfies 21 to 400 at a specific ratio, the curable resin composition of the present invention becomes a cured product with little peeling from copper even after being treated with a desmear solution. The value of n1 + m1 is preferably 21 to 300, more preferably 21 to 250, and still more preferably 21 to 200. Furthermore, n1 and m1 are each between 0 and 200, and are not particularly limited as long as n1 + m1 satisfies 21 to 400. For example, when m1 = 0, n1 is preferably between 21 and 200, and more preferably between 25 and 150. Also, when m1 ≠ 0, n1 and m1 are each preferably between 11 and 100, and more preferably between 15 and 50. Furthermore, the order of each repeating unit enclosed by n1 and m1 is not restricted.

[0017] The weight-average molecular weight (Mw) of the cyclic imide resin represented by formula (1) is not particularly limited as long as n1 + m1 satisfies 21 to 400, but is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and even more preferably 40,000 to 300,000. A weight-average molecular weight (Mw) within this range is preferable because it results in less peeling from copper after treatment with desmear solution, and the terminal cyclic imide groups react efficiently.

[0018] In this specification, the weight-average molecular weight (Mw) refers to the weight-average molecular weight measured by GPC with polystyrene as the standard substance under the following conditions. [GPC measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (Sample concentration: 0.5% by mass - tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0019] There are no particular restrictions on the method for producing the cyclic imide resin of component (A). For example, an amine-terminated compound may be synthesized by reacting an acid anhydride with a diamine, and then the amine-terminated compound may be reacted with an excess of maleic anhydride or citraconic anhydride. These acid anhydrides and diamines are reacted in a desired equivalence ratio to satisfy n1 and m1 of formula (1). The equivalence ratio of the acid anhydride and diamine is preferably diamine / acid anhydride = 1.001 to 1.35, more preferably 1.01 to 1.3, and even more preferably 1.03 to 1.2.

[0020] Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyl diphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyl diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride. These acid anhydrides may be used individually or in combination of two or more, depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide resin, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride are preferred as acid anhydrides.

[0021] Examples of diamines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminodiphenylmethane, and 1,3-bis(4-aminophenoxy)benzene. Aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane; dimeramines, etc. These diamines may be used individually or in combination of two or more, depending on the purpose and application. From the perspective of the electrical properties of cyclic imide compounds, diamines are 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, and 4,4'-diamino-3,3' Aromatic diamines such as ,5,5'-tetraethyldiphenylmethane; aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, and 2-methylpentane-1,5-diamine; dimeramines are preferred, with 1,12-diaminododecane, dimeramines, and isophoronediamines being particularly preferred.

[0022] The equivalent amount of the cyclic imide group in component (A) is preferably 0.0001 to 0.1 mol / 100g, more preferably 0.0003 to 0.05 mol / 100g, even more preferably 0.0005 to 0.03 mol / 100g, and even more preferably 0.02 to 0.2 mol / 100g. Within this range, there is little peeling from the copper after treatment with the desmear solution, and the terminal cyclic imide groups react efficiently, which is preferable.

[0023] (A) Component may be used alone or in combination of two or more components. The amount of component (A) is 10 to 95% by mass, preferably 15 to 90% by mass, and more preferably 20 to 80% by mass of the resin composition.

[0024] [(B) Cyclic imide resin represented by the following formula (2)] The cyclic imide resin of component (B) is represented by the following formula (2). The curable resin composition of the present invention contains component (B), which results in a curable resin composition with a low dielectric constant and low dielectric loss tangent, while also having a low melt viscosity when heated and improved adhesion to copper and other substrates. [ka] In equation (2), A, Q, B, and X are the same as above, n2 is between 0 and 10, m2 is between 0 and 10, and n2 and m2 are numbers such that n2 + m2 is between 0 and 20. Furthermore, the order of each repeating unit enclosed by n2 and m2 is not restricted.

[0025] In equation (2), n2 is between 0 and 10, preferably between 0 and 8, and more preferably between 0 and 5. In formula (2), m2 is between 0 and 10, preferably between 0 and 8, and more preferably between 0 and 5. In formula (2), n² + m² is between 0 and 20, preferably between 0 and 16, and more preferably between 0 and 2 and 10. Furthermore, when there are multiple repeating units enclosed by n2 and m2, the order of each repeating unit is not limited.

[0026] The weight-average molecular weight (Mw) of the cyclic imide resin represented by formula (2) is not particularly limited as long as n² + m² satisfies the range of 0 to 20, but is preferably 300 to 30,000, more preferably 500 to 20,000, and even more preferably 1,000 to 10,000. A weight-average molecular weight (Mw) within this range is preferable because it results in a low melt viscosity when heated and improved adhesion to copper and other substrates.

[0027] Furthermore, component (B) is preferably a cyclic imide resin represented by the following formula (3). [ka] Equation (3) above is the form of equation (2) where m2 = 0. Therefore, in equation (3), A, Q, X, and n2 are the same as above, and the preferred form is also the same as above.

[0028] There are no particular restrictions on the method for producing the cyclic imide resin of component (B). For example, one method involves reacting a diamine with an excess of maleic anhydride or citraconic anhydride. Another method involves reacting an acid anhydride with a diamine to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with an excess of maleic anhydride or citraconic anhydride. These diamines and acid anhydrides are reacted in a desired equivalence ratio to satisfy n1 and m1 of formula (1). There are no particular restrictions on the charging ratio of the diamine and acid anhydride, but diamine / acid anhydride = 1.35 to 3.0 is preferred, 1.4 to 2.5 is more preferred, and 1.5 to 2.0 is even more preferred.

[0029] Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyl diphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyl diphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride. These acid anhydrides may be used individually or in combination of two or more, depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide resin, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride are preferred as acid anhydrides.

[0030] Examples of diamines include 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminodiphenylmethane, and 1,3-bis(4-aminophenoxy)benzene. Aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane; dimeramines, etc. These diamines may be used individually or in combination of two or more, depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide compound, the diamine is preferably an aromatic diamine such as 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane; aliphatic diamines such as 1,12-diaminododecane, 1,10-diaminodecane, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine; and dimeramine is preferred, with 1,12-diaminododecane, dimeramine, and isophoronediamine being particularly preferred.

[0031] The equivalent amount of the cyclic imide group in component (B) is preferably 0.01 to 0.5 mol / 100g, more preferably 0.03 to 0.3 mol / 100g, even more preferably 0.05 to 0.1 mol / 100g, and even more preferably 0.02 to 0.2 mol / 100g. This range is preferable because it allows for efficient reaction of the terminal cyclic imide groups.

[0032] The amount of component (B) is 1 to 40 parts by mass per 100 parts by mass of component (A), preferably 5 to 30 parts by mass, and more preferably 10 to 25 parts by mass. If the amount of component (B) is less than 1 part by mass per 100 parts by mass of component (A), the melt viscosity of the resin composition will not decrease sufficiently, resulting in poor adhesion to copper. If the amount of component (B) is more than 40 parts by mass per 100 parts by mass of component (A), delamination from copper may occur when the cured resin composition is treated with desmear solution.

[0033] Furthermore, the cyclic imide resin of component (B) may be a commercially available product. Examples of commercially available products include BMI-689, BMI-1400, BMI-1500 (all manufactured by Designer Molecules Inc.), SLK-6895, SLK-1500 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, the cyclic imide resin of component (B) may be used alone or in combination of two or more types.

[0034] [(C) Curing catalyst] Component (C) is a curing catalyst, intended to accelerate the curing of the resin composition. There are no particular restrictions on the curing catalyst for component (C), but examples include thermal radical polymerization initiators and thermal anionic polymerization initiators.

[0035] Examples of thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di-t -Butyl peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl Tyl-2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Pill peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-Tetramethylbutyl peroxyneodecanoate, 1-Cyclohexyl-1-methylethyl peroxyneodecanoate, t-Hexyl peroxyneodecanoate, t-Butyl peroxyneodecanoate, t-Hexyl peroxypivalate, t-Butyl peroxypivalate, 2,5-Dimethyl-2,5-Bis(2-ethylhexanoyl peroxy)hexane, 1,1,3,3-Tetramethylbutyl peroxy-2-ethylhexanoate, 1-Cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-Hexyl peroxy Xy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxymalic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy Organic peroxides such as -oxy-m-butyloylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide), 2,2'-azobis[N-(2-methylpropyl)-2-methylpropionamide], 2,2'-azobis[N-(2-methyl 2,2'-Azobis(N-Hexyl-2-methylpropionamide), 2,2'-Azobis(N-Propyl-2-methylpropionamide), 2,2'-Azobis(N-Ethyl-2-methylpropionamide), 2,2'-Azobis[2-Methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-Azobis{2-Methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,Examples of azo compounds include 2'-azobis[N-(2-propenyl)-2-methylpropionamide] and dimethyl-1,1'-azobis(1-cyclohexanecarboxylate).

[0036] Examples of thermal anionic polymerization initiators include amine compounds such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; and amine compounds such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2-phenyl-4-hydroxy-5-methylimidazole. Midazole compounds include organophosphorus compounds such as triphenylphosphine, tributylphosphine, trioctylphosphine, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenyl borate, tetrabutylphosphonium acetate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogen phthalate, bis(tetraphenylphosphonium) dihydrogen pyromelitate, and bis(tetrabutylphosphonium) dihydrogen pyromelitate. Among these, thermal anionic polymerization initiators are preferred, and among them, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2-phenyl-4-hydroxy-5-methylimidazole are particularly preferred.

[0037] These curing catalysts may be used individually or in combination of two or more types.

[0038] The amount of component (C) is 0.01 to 10 parts by mass per 100 parts by mass of component (A), preferably 0.1 to 5 parts by mass. If the amount of component (C) is less than 0.01 parts by mass per 100 parts by mass of component (A), the resin composition will not harden sufficiently. Os There is a problem. If the amount of component (C) is greater than 10 parts by mass per 100 parts by mass of component (A), it will adversely affect the physical properties of the cured resin composition.

[0039] [Inorganic fillers] The curable resin composition of the present invention may further contain an inorganic filler, if necessary. There are no particular restrictions on the inorganic fillers, but examples include: silica, titanium dioxide, yttrium oxide, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide and other metal oxides; metal nitrides such as boron nitride, aluminum nitride, silicon nitride; carbon-containing particles such as silicon carbide, diamond, graphene; hollow particles such as silica balloons (hollow silica), carbon balloons, alumina balloons, aluminosilicate balloons; elemental metals such as gold, silver, copper, palladium, aluminum, nickel, iron, cobalt, titanium, manganese, zinc, tungsten, platinum, lead, tin; alloys such as solder and steel; stainless steel. Examples of magnetic metal alloys include stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Si alloy, Fe-Si alloy, Fe-Si-B(-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, and Fe-Si-Al-Ni-Cr alloy; and ferrites such as hematite (Fe2O3), magnetite (Fe3O4), Mn-Zn ferrite, Ni-Zn ferrite, Mg-Mn ferrite, Zr-Mn ferrite, Ti-Mn ferrite, Mn-Zn-Cu ferrite, barium ferrite, and strontium ferrite. These may be used individually or in combination of two or more.

[0040] Adding metal oxides, metal nitrides, or carbon-containing particles can lower the coefficient of linear expansion of the cured resin material and increase its thermal conductivity. Adding hollow particles can lower the relative permittivity, dielectric loss tangent, density, etc., of the cured resin material. Adding metals or alloys can increase the electrical conductivity, thermal conductivity, etc., of the cured resin material. Furthermore, adding ferrites can impart electromagnetic wave absorption capabilities to the cured resin material.

[0041] There are no particular restrictions on the shape of the inorganic filler, and examples include spherical, flaky, needle-shaped, rod-shaped, and elliptical shapes. Among these, spherical, flaky, flake-shaped, elliptical, and rod-shaped are preferred, and spherical, flaky, flake-shaped, and elliptical are even more preferred.

[0042] There are no particular restrictions on the primary particle size of the inorganic filler, but a median diameter of 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as measured by a laser diffraction particle size distribution analyzer, is preferred. Within this range, it is easy to uniformly disperse the inorganic filler in the curable resin composition, and the inorganic filler does not settle, separate, or become unevenly distributed over time, which is preferable.

[0043] There are no particular restrictions on the amount of the inorganic filler used, but it is preferably 5 to 300 parts by mass, more preferably 10 to 250 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of component (A) in the curable resin composition of the present invention.

[0044] [Organic fillers] The curable resin composition of the present invention may further contain an organic filler. There are no particular restrictions on the organic fillers, but examples include thermoplastic resin particles such as acrylic-butadiene copolymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, and acrylic block copolymers, as well as carbon fibers, cellulose fibers, silicone powder, acrylic powder, polytetrafluoroethylene powder, polyethylene powder, and polypropylene powder. These may be used individually or in combination of two or more.

[0045] There are no particular restrictions on the shape of the organic filler, and examples include spherical, fibrous, flake-shaped, needle-shaped, rod-shaped, and elliptical shapes. Among these, spherical, fibrous, flake-shaped, elliptical, and rod-shaped are preferred, and spherical, fibrous, flake-shaped, and elliptical are even more preferred.

[0046] There are no particular restrictions on the primary particle size of the organic filler, but a median diameter of 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as measured by a laser diffraction particle size distribution analyzer, is preferred. Within this range, it is easy to uniformly disperse the organic particles in the curable resin composition, and the organic particles do not settle, separate, or become unevenly distributed over time, which is preferable.

[0047] There are no particular restrictions on the amount of the organic filler used, but it is preferably 1 to 400 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of component (A) in the curable resin composition of the present invention. Within this range, the strength of the curable resin composition can be increased.

[0048] [Adhesion-enhancing agent] The curable resin composition of the present invention may contain an adhesion promoter as needed to impart adhesiveness or tackiness (pressure-sensitive adhesion). Examples of adhesion promoters include epoxy resins, acrylic resins, urethane resins, phenolic resins, terpene resins, and silane coupling agents. Among these, epoxy resins, acrylic resins, and silane coupling agents are preferred for imparting adhesiveness, and terpene resins are preferred for imparting tackiness (pressure-sensitive adhesion).

[0049] There are no particular restrictions on the epoxy resin, but examples include known epoxy resins that are liquid or solid at room temperature, such as biphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, 3,3',5,5'-tetramethyl-4,4'-biphenol type epoxy resin and 4,4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakisphenylolethane type epoxy resin and phenol dicyclopentadiene novolac type epoxy resin, and alicyclic epoxy resins.

[0050] There are no particular restrictions on the acrylic resin, but examples include lauryl acrylate, stearyl acrylate, isostearyl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol diacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, and dipentaerythritol. Examples include xaacrylate, dioxane glycol diacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate, lauryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol dimethacrylate, dimethylol tricyclodecane dimethacrylate, and the like.

[0051] There are no particular restrictions on the terpene resin, but examples include homopolymers of terpenes such as monoterpenes like α-pinene, β-pinene, dipentene, and limonene; sesquiterpenes like cedrene and farnesene; and diterpenes like abietic acid; aromatic modified terpene resins, which are copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene with the aforementioned terpenes; and terpene phenol resins, which are copolymers of phenols such as phenol, cresol, hydroquinone, naphthol, and bisphenol A with the aforementioned terpenes. Hydrogenated terpene resins, which are obtained by hydrogenating these terpene resins, can also be used.

[0052] There are no particular restrictions on the silane coupling agent, but examples include silane coupling agents such as n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane, methoxytri(ethyleneoxy)propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltrimethoxysilane.

[0053] There are no particular restrictions on the amount of the adhesion-imparting agent, but it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass per 100 parts by mass of component (A). Within this range, the adhesive strength or tackiness of the curable resin composition can be further improved without changing the mechanical properties of the resin composition.

[0054] [Antioxidant] The resin composition of the present invention may optionally contain an antioxidant. There are no particular restrictions on the antioxidants used, but examples include n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)acetate, neododecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, dodecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and ethyl acetate. α-(4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α-(4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α-(4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2-(n-octylthio)ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl-3, 5-di-t-butyl-4-hydroxyphenyl acetate, 2-(n-octadecylthio)ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-(2-stearoyloxyethylthio)ethyl-7-(3-methyl-5-t-butyl-4-hydroxyphenyl)heptanoate, 2-hydroxyethyl-7-(3-methyl-5-t-butyl-4-hydroxyphenyl)propionate, pentae Phenolic antioxidants such as lysritol tetrakiss [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and pentaerythrityl tetrakiss (3-laurylthiopropionate);Examples of phosphorus-based antioxidants include tridecyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, 2-ethylhexyl diphenyl phosphite, diphenyl tridecyl phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, distearyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]-ethyl]ethanamine.

[0055] There are no particular restrictions on the amount of the antioxidant added, but it is preferably 0.00001 to 5 parts by mass, more preferably 0.0001 to 4 parts by mass, and even more preferably 0.001 to 3 parts by mass per 100 parts by mass of component (A). Within this range, oxidation of the curable resin composition can be prevented without changing the mechanical properties of the resin composition.

[0056] [Flame retardant] The curable resin composition of the present invention may contain a flame retardant as needed to impart flame retardancy. There are no particular restrictions on the flame retardants, but examples include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and guanidine-based flame retardants. Examples of phosphorus-based flame retardants include red phosphorus, ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate, inorganic nitrogen-containing phosphorus compounds such as guanidine phosphate and phosphate amides, phosphoric acid, phosphine oxide, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene bis( Examples of phosphazene compounds include diphenylphosphate, divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, bis(2-allylphenoxy)phosphazene, dicresylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Examples of metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. Examples of halogenated flame retardants include hexabromobenzene, pentabromotoluene, ethylenebis(pentabromopenyne), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine. Examples of guanidine-based flame retardants include guanidine sulfamate and guanidine phosphate.

[0057] There are no particular restrictions on the amount of the flame retardant added, but it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass per 100 parts by mass of component (A). Within this range, flame retardancy can be imparted to the curable resin composition without changing its mechanical properties.

[0058] [Manufacturing method] A method for producing the curable resin composition of the present invention includes mixing components (A) to (C) and other additives as needed using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a stirrer (THINKY CONDITIONING MIXER, manufactured by Thinky Co., Ltd.). Preferably, an organic solvent (for example, cyclopentanone, cyclohexanone, mesitylene, anisole, dibutyl ether, diphenyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.) is added and mixed. Adding an organic solvent lowers the viscosity of the curable resin composition, allowing for more uniform mixing. The curable resin composition is obtained by distilling off the organic solvent under reduced pressure after mixing, but when used as a film or the like, it may be used as is without distillation, or adjusted to the desired concentration. [Examples]

[0059] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0060] The molecular weights shown in the following examples are weight-average molecular weights (Mw) measured by gel permeation chromatography (GPC) using polystyrene as the standard substance. The measurement conditions are shown below. [GPC measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (Sample concentration: 0.5% by mass - tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0061] (A) Cyclic imide resin (A-1) To 2,000 g of N-methylpyrrolidone (0.5% moisture content), 575 g (1.1 mol) of dimer amine and 520 g (1.0 mol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 5,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-1) represented by the following formula: (Weight-average molecular weight 70,000, maleimide equivalent 0.0077 mol / 100 g) [ka]

[0062] (A-2) To 2,000 g of N-methylpyrrolidone (0.5% moisture content), 210 g (1.05 mol) of 1,12-dodecanediamine and 218 g (1.0 mol) of pyromellitic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 5,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-2) represented by the following formula: (Weight-average molecular weight 80,000, maleimide equivalent 0.0043 mol / 100 g) [ka]

[0063] (A-3) To 2,000 g of N-methylpyrrolidone (0.6% moisture content), 94 g (0.55 mol) of isophorone diamine, 278 g (0.55 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 520 g (1.0 mol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride were added, and the mixture was stirred at 25°C for 3 hours, followed by stirring at 150°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added, and the mixture was stirred at 80°C for 1 hour. Then, 5,000 g of toluene was added, followed by further washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (A-3) represented by the following formula. (Weight average molecular weight 95,000, maleimide equivalent 0.0065mol / 100g) [ka]

[0064] (B) Cyclic imide resin (B-1) To 900 g of xylene, 300 g (1.5 mol) of 1,12-dodecanediamine and 310 g (1.0 mol) of 4,4'-oxydiphthalic anhydride were added and stirred at 25°C for 3 hours, then further stirred at 140°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 2,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (B-1) represented by the following formula. (Weight-average molecular weight 2,200, maleimide equivalent 0.16 mol / 100 g) [ka]

[0065] (B-2) Maleimide resin represented by the following formula (BMI-3000, manufactured by Designer Molecules Inc.) (weight-average molecular weight 10,000, maleimide equivalent 0.044 mol / 100g) [ka]

[0066] (B-3) Maleimide resin represented by the following formula (BMI-1500, manufactured by Designer Molecules Inc.) (weight-average molecular weight 3,000, maleimide equivalent 0.067 mol / 100g) [ka]

[0067] (B-4) Maleimide resin represented by the following formula (SLK-6895, manufactured by Shin-Etsu Chemical Co., Ltd.) (weight-average molecular weight 700, maleimide equivalent 0.29 mol / 100g) [ka]

[0068] (B-5) To 1,300 g of xylene, 150 g (0.75 mol) of 1,12-dodecanediamine, 258 g (0.75 mol) of 4,4'-(1,4-phenylenediisopropylidene)bisaniline, and 310 g (1.0 mol) of 4,4'-oxydiphthalic anhydride were added and stirred at 25°C for 3 hours, followed by stirring at 140°C for 5 hours. To the resulting solution, 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate, and 204 g (2.0 mol) of acetic anhydride were added and stirred at 80°C for 1 hour. Subsequently, 2,000 g of toluene was added, followed by washing with water, dehydration, and removal of the solvent under reduced pressure to obtain bismaleimide (B-5) represented by the following formula. (Weight-average molecular weight 3,300, maleimide equivalent 0.11 mol / 100 g) [ka]

[0069] (C) Curing catalyst (C-1)2-ethyl-4-methylimidazole

[0070] (D) Adhesion-improving agent (D-1) Bisphenol A type epoxy resin (product name "jER-828EL" (manufactured by Mitsubishi Chemical Corporation))

[0071] (E) Inorganic fillers (E-1) Silica "SFP-130MC" (primary particle size median diameter 0.6 μm) (manufactured by Denka Co., Ltd.)

[0072] [Method for preparing a curable resin composition] For Examples 1-11 and Comparative Examples 1-4, in addition to the formulations (parts by mass) shown in Table 1, 100 parts by mass of cyclopentanone was added to a total of 100 parts by mass of each component and mixed. The mixture was then kneaded at 80°C for 30 minutes using a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), and then cooled to 25°C. The resulting solution was transferred to a flask, and the solvent was removed by vacuum distillation to prepare a curable resin composition.

[0073] [Glass transition temperature (Tg), coefficient of linear expansion] A test sample was prepared by sandwiching the prepared curable resin composition between 30 mm × 40 mm × 100 μm thick mold frames and press-curing it at 180°C and 3 MPa for 1 hour. The prepared test sample was measured using a TMA Q400 (manufactured by TA Instruments Co., Ltd.) in the range of -50°C to 300°C, and the Tg and linear expansion coefficient (linear expansion coefficient α1 in the temperature range below Tg and linear expansion coefficient α2 in the temperature range above Tg) were calculated from the obtained graphs. The measurement conditions were a 20 mm × 3 mm × 100 μm thick test sample (cured product), a heating rate of 5°C / min, and tensile mode. The results are shown in Table 1.

[0074] [Relative permittivity and dielectric loss tangent] A test sample was prepared by sandwiching the prepared curable resin composition between 30 mm x 40 mm x 100 μm thick mold frames and press-curing it at 180°C and 3 MPa for 1 hour. A network analyzer (Keysight E5063-2D5) and a stripline (Keycom Corporation) were connected to the prepared test sample, and the relative permittivity and dielectric loss tangent at a frequency of 10 GHz were measured. The results are shown in Table 1.

[0075] [Peel strength] A resin film was prepared by coating a PET film with the prepared curable resin composition to a thickness of 25 μm. Using a vacuum laminator V-130 (manufactured by Nikko Materials Co., Ltd.), the PET film and the SUS plate were overlapped so that the opposite side was in contact, and laminated at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds. After cooling to room temperature, the PET film was peeled off, and an 18 μm thick copper foil (product name: TQ-M4-VSP, manufactured by Mitsui Metals Co., Ltd.) was placed on top. Lamination was performed again at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds, and then heated at 180°C for 1 hour to cure. In accordance with the JIS-C-6481:1996 standard for testing copper-clad laminates for printed circuit boards, the force (peel strength) required to peel the copper foil from the resin film at a speed of 50 mm / min in a 90° direction over a width of 10 mm was determined using a Tensilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: Strograph VE-1D). The results are shown in Table 1.

[0076] [Desmear resistance] On a substrate with a copper wiring pattern of L / S=100 / 100, a resin film prepared using the method described above under [Peel Strength] was laminated using a vacuum laminator V-130 (manufactured by Nikko Materials Co., Ltd.) with the opposite side of the PET film in contact with the substrate, at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds. After cooling to room temperature, the PET film was peeled off and the substrate was heat-cured at 180°C for 1 hour. After curing, a 100 μm diameter via was made in the substrate using a CO2 laser (manufactured by Via Mechanics Co., Ltd., model: LC-2Q252), desmeared, and the cross-section was cut out to measure the delamination distance of the resin and copper from the via bottom. The results are shown in Table 1.

[0077] [Table 1]

[0078] In Examples 1 to 11, the cured products of the curable resin compositions exhibited low dielectric constant and low dielectric loss tangent, and the delamination distance after desmearing was also very small. In Comparative Examples 1 and 2, because the high molecular weight component (A) was not present, the resin was easily decomposed by the desmear treatment, resulting in a large peeling distance after desmearing. Comparative Example 3 did not contain the low molecular weight component (B), resulting in low adhesion to copper and a large delamination distance after desmearing. In Comparative Example 4, the low molecular weight component (B) was present in a large amount, causing the resin to easily decompose during the desmear treatment, resulting in a large peeling distance after desmearing.

Claims

1. (A) A cyclic imide resin represented by the following formula (1), 【Chemistry 1】 (In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms, which may contain a heteroatom, or a divalent hydrocarbon group derived from a dimer acid skeleton. B independently represents an arylene group having 6 or more carbon atoms, which may contain a heteroatom. X is a hydrogen atom or a methyl group, n 1 It ranges from 0 to 200, and m 1 n is between 0 and 200, and n 1 and m 1 Each is n 1 +m 1 n is a number that satisfies the range of 21 to 400. 1 and m 1 The order of each repeating unit enclosed in quotation marks is not restricted. (B) A cyclic imide resin represented by the following formula (2): 1 to 40 parts by mass per 100 parts by mass of component (A), 【Chemistry 2】 (In formula (2), A, Q, B, and X are the same as described above, and n 2 is from 0 to 10, m 2 is from 0 to 10, and n 2 and m 2 are each such that n 2 + m 2 satisfies 0 to 20. Also, the order of each repeating unit enclosed by n 2 and m 2 is not limited.) and (C) Curing catalyst: 0.01 to 10 parts by mass per 100 parts by mass of component (A) A curable resin composition containing [a specific ingredient].

2. The curable resin composition according to claim 1, wherein component (B) is a cyclic imide resin represented by the following formula (3). 【Transformation 3】 (In formula (3), A, Q, X, n 2 (This is the same as above.)

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