Curable resin composition

Abstract

To provide a curable resin composition that yields a cured product having low dielectric constant and low dielectric loss tangent, exhibiting excellent adhesion to copper and superior chemical resistance (desmear resistance).SOLUTION: There is provided a curable resin composition comprising (A-1) a cyclic imide resin, (B) a triazine thiol represented by formula (3) (where R2 is a group selected from the group consisting of hydrogen, a C1-C18 alkyl group, a C2-C18 alkenyl group, a C6-C12 aromatic hydrocarbon group, and a group represented by formula (4); in formula (4), R2' is hydrogen, a C1-C18 alkyl group, a C2-C18 alkenyl group, or the like), and (C) a curing catalyst.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, the speed and capacity of signals used in electronic devices such as mobile phones, their base station equipment, servers, routers, and other network infrastructure equipment, and large-scale computers have been increasing year by year. Accordingly, printed wiring boards mounted on these electronic devices use high frequencies in the 20 GHz range, and insulating materials for printed wiring boards are therefore required to have properties such as a low dielectric constant and a low dielectric loss tangent. Materials that may satisfy these properties include epoxy resins, modified polyphenylene ether resins, aromatic maleimide resins, and aliphatic maleimide resins (Patent Documents 1 to 4).

[0003] Furthermore, conventional methods for bonding insulating materials involve roughening the conductor circuit and increasing adhesive strength through the anchor effect. However, at high frequencies, the skin effect causes more electricity to flow on the surface of the conductor, resulting in longer paths for electrical signals in roughened conductor circuits, resulting in delays. Therefore, for high-frequency applications, the surface of the conductor circuit must be as smooth as possible, and the anchor effect cannot be expected to improve adhesive strength.

[0004] On the other hand, triazine thiol is known as a bonding material that increases the adhesive strength between metal and insulating material, but has not been studied as a bonding material that increases the adhesive strength between metal and maleimide resin (Patent Documents 5 to 8). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-1965 [Patent Document 2] Japanese Patent Application Publication No. 2018-28044 [Patent Document 3] Japanese Patent Application Publication No. 2020-176190 [Patent Document 4] Japanese Patent Publication No. 2020-12026 [Patent Document 5] Japanese Patent Application Laid-Open No. 2005-109363 [Patent Document 6] Japanese Patent Application Laid-Open No. 2011-63715 [Patent Document 7] Japanese Patent Application Laid-Open No. 2007-204679 [Patent Document 8] Japanese Patent Application Laid-Open No. 2005-002334 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a curable resin composition that gives a cured product having a low relative dielectric constant and a low dielectric loss tangent, yet exhibiting high adhesion to metals, particularly copper, and excellent chemical resistance (desmear resistance). [Means for solving the problem]

[0007] As a result of extensive research to solve the above problems, the present inventors have found that the following curable resin composition can achieve the above object, and have completed the present invention. That is, the present invention provides the following curable resin composition and the like.

[0008] [1] (A-1) 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 an alicyclic hydrocarbon group represented by the following formula (2), and B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X represents a hydrogen atom or a methyl group, n represents 1 to 200, m represents 0 to 200, and when m is 1 or more, the ratio n:m=1:1 to 4:1. The order of the repeating units bracketed by n and m is not limited.) [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4. (B) Triazine thiol represented by the following formula (3): 1 to 10 parts by mass per 100 parts by mass of the component (A) [ka] (In formula (3), R 2 is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, a hydroxy group, and a group represented by the following formula (4): [ka] (In formula (4), R 2' is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, and a hydroxy group. and (C) Curing catalyst: 0.01 to 10 parts by mass per 100 parts by mass of component (A) A curable resin composition comprising: [2] The curable resin composition according to [1], further comprising (A-2) a cyclic imide resin represented by the following formula (5): [ka] (In formula (5), A independently represents a tetravalent organic group containing a cyclic structure. B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom (excluding the alicyclic hydrocarbon group represented by formula (2) below). X represents a hydrogen atom or a methyl group, and s represents 0 to 200.) [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4. [3] The curable resin composition according to [2], wherein the mass ratio of the component (A-1) to the component (A-2) is (A-1):(A-2)=99:1 to 60:40. [Effects of the Invention]

[0009] The curable resin composition of the present invention forms a cured product having a low dielectric constant and a low dielectric loss tangent, excellent adhesion to metals, particularly copper, and excellent chemical resistance (desmear resistance). 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 encapsulants. DETAILED DESCRIPTION OF THE INVENTION

[0010] The curable resin composition of the present invention will be described in detail below. [(A) Cyclic imide resin] The component (A) of the present invention is characterized by containing (A-1) a cyclic imide resin represented by the following formula (1), which will be explained below.

[0011] [(A-1) Cyclic imide resin represented by the following formula (1)] The cyclic imide resin of component (A-1) is the main component of the curable resin composition of the present invention and is represented by the following formula (1): By including component (A) in the curable resin composition of the present invention, the cured product of the curable resin composition will have a low relative dielectric constant, a low dielectric loss tangent, low warpage, and high chemical resistance. [ka] (In formula (1), A independently represents a tetravalent organic group containing a cyclic structure. Q independently represents an alicyclic hydrocarbon group represented by the following formula (2), and B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X represents a hydrogen atom or a methyl group, n represents 1 to 200, m represents 0 to 200, and when m is 1 or more, the ratio n:m=1:1 to 4:1. The order of the repeating units bracketed by n and m is not limited.) [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4.

[0012] Here, the organic groups represented by A in formula (1) are independently tetravalent organic groups containing a cyclic structure, and are particularly preferably any of the tetravalent organic groups represented by the following formulae: [ka] (The bond not bonded to a substituent in the above formula is bonded to the carbonyl carbon that forms the cyclic imide structure in formula (1).)

[0013] In formula (1), Q is independently an alicyclic hydrocarbon group represented by the following formula (2). [ka]

[0014] In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0015] In formula (2), x is independently 0 to 4, and preferably 0 to 2. The x's may be the same or different.

[0016] Specific examples of formula (2) include the following structures: [ka]

[0017] The bond to which no substituent is bonded in the above formula is bonded to the nitrogen atom that forms the cyclic imide structure in formula (2).

[0018] In formula (1), each B is independently a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom, and is preferably a divalent hydrocarbon group represented by any of the following structural formulas or a divalent hydrocarbon group derived from a dimer acid skeleton. [ka]

[0019] The bond to which no substituent is bonded in the above formula is bonded to the nitrogen atom that forms the cyclic imide structure in formula (1).

[0020] In the above formula, R 3 R independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. 3 is preferably 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 formula, p 1 and p 2 are each a number of 5 or more, preferably a number of 5 to 12, more preferably a number of 6 to 10, and may be the same or different. In the above formula, p 3 and p 4are each a number of 0 or more, preferably a number of 0 to 4, more preferably a number of 0 to 3, and may be the same or different. In the above formula, p 5 and p 6 are each a number of 0 or more, preferably a number of 0 to 4, more preferably a number of 0 to 2, and may be the same or different. If B is Q, it becomes a unit bracketed by n.

[0021] The divalent hydrocarbon group derived from a dimer acid skeleton is a group derived from dimer acid, a liquid fatty acid primarily composed of a 36-carbon dicarboxylic acid, produced by dimerization of an 18-carbon unsaturated fatty acid derived from natural sources such as vegetable oils. Dimer acids do not have a single skeleton but have multiple structures, resulting in several isomers. The dimer acid skeleton refers to a group derived from a dimer diamine, which has a structure in which the carboxyl group of such a dimer acid is substituted with a primary aminomethyl group. From the standpoint 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 a hydrogenation reaction. Generally, dimer acids may contain trimers (trimer acids) due to the use of natural products such as vegetable oils and fats as raw materials. However, it is preferable that the proportion of hydrocarbon groups derived from dimer acids among the hydrocarbon groups derived from dimer acids and trimer acids be, for example, 95 mass % or more, as this results in excellent dielectric properties, excellent moldability due to a tendency for the viscosity to decrease when heated, and reduced influence of moisture absorption. As described above, the dimer acid skeleton has a plurality of structures, and therefore, in this specification, the divalent hydrocarbon group derived from the dimer acid skeleton is referred to as the average structure, i.e., -C 36 H 70 It may be written as -.

[0022] In formula (1), X is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In formula (1), n ​​is 1 to 200, preferably 2 to 100, and more preferably 2 to 50. In formula (1), m is 0 to 200, preferably 1 to 50, and more preferably 1 to 20. When m is 1 or more, the ratio of n to m is 1:1 to 4:1, preferably 1:1 to 3:1, and more preferably 1:1 to 2:1. This range is preferable because the chemical resistance of the cured product of the curable resin composition of the present invention is enhanced. Furthermore, the order of the repeating units bracketed by n and m is not limited.

[0023] The weight-average molecular weight (Mw) of the cyclic imide resin of component (A-1) is not particularly limited, but is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and even more preferably 3,000 to 50,000. If the weight-average molecular weight (Mw) is within this range, the curable resin composition will have sufficient strength and the terminal cyclic imide groups can be reacted efficiently. The weight average molecular weight (Mw) referred to in this specification refers to the weight average molecular weight measured by GPC under the following conditions using polystyrene as the standard. [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 in tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0024] The method for producing the cyclic imide resin of component (A-1) is not particularly limited. For example, it may be produced by reacting an amine compound with an excess of maleic anhydride or citraconic anhydride, or it may be produced by 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.

[0025] Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride. These acid anhydrides may be used alone or in combination depending on the purpose, application, etc. From the viewpoint of the electrical properties of the cyclic imide resin, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride are preferred.

[0026] Examples of diamines include tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,12-diaminododecane, 1,10-diaminodecane, dimer diamine, octyldiamine, 1,3-di(aminomethyl)cyclohexane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, 2-methylpentane-1,5-diamine, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, etc. These diamines may be used alone or in combination of two or more depending on the purpose, application, etc. From the viewpoint of the electrical properties of the cyclic imide resin, the diamine is preferably an aliphatic diamine such as tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,12-diaminododecane, 1,10-diaminodecane, dimerdiamine, octyldiamine, 1,3-di(aminomethyl)cyclohexane, 1-amino-4-(aminomethyl)cyclohexane, 1,3-diaminoadamantane, isophoronediamine, 2,4,4-trimethylhexane-1,6-diamine, or 2-methylpentane-1,5-diamine, with dimerdiamine and isophoronediamine being particularly preferred.

[0027] The equivalent weight of the cyclic imide group in the component (A-1) is preferably 0.001 to 0.5 mol / 100 g, more preferably 0.003 to 0.4 mol / 100 g, even more preferably 0.01 to 0.3 mol / 100 g, and even more preferably 0.02 to 0.2 mol / 100 g. This range is preferable because the cured product of the curable resin composition has a low dielectric constant and a low dielectric loss tangent.

[0028] The component (A-1) may be used alone or in combination of two or more types. The amount of component (A-1) in the curable resin composition of the present invention is not particularly limited, but is preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass. This range is preferable because it provides a low relative dielectric constant and a low dielectric loss tangent, while also providing sufficiently high chemical resistance and adhesive strength to copper.

[0029] [(B) Triazine thiol represented by the following formula (3)] The triazine thiol of the component (B) is a compound represented by the following formula (3): By including the component (B), the curable resin composition of the present invention has excellent adhesion to copper and high chemical resistance. [ka] (In formula (3), R 2 is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, a hydroxy group, and a group represented by the following formula (4): [ka] (In formula (4), R 2' is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, and a hydroxy group.

[0030] Here, the above R 2 and R 2' are independently a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, and a hydroxy group. Preferred are an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, and a thiol group, and more preferred are an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a thiol group.

[0031] The blending amount of component (B) is 1 to 10 parts by mass, preferably 2 to 8 parts by mass, and more preferably 3 to 6 parts by mass, per 100 parts by mass of component (A). If the blending amount of component (B) is less than 1 part by mass, chemical resistance will be reduced, and peeling from copper may occur when treated with a desmear solution. If the blending amount of component (B) is more than 10 parts by mass, the relative dielectric constant and dielectric loss tangent will be high. One type of triazine thiol for component (B) may be used alone, or two or more types may be used in combination.

[0032] Examples of triazine thiols represented by the above formula (3) include 2,4,6-trimercapto-s-triazine, 2,4-dimercapto-6-methyl-s-triazine, 2,4-dimercapto-6-ethyl-s-triazine, 2,4-dimercapto-6-phenyl-s-triazine, 2,4-dimercapto-6-vinyl-s-triazine, 2,4-dimercapto-6-amino-s-triazine, 2,4-dimercapto-6-hydroxy-s-triazine, etc. Among these, 2,4,6-trimercapto-s-triazine and 2,4-dimercapto-6-amino-s-triazine are preferred.

[0033] Examples of triazine thiols having a group represented by the above formula (4) include 2-di-n-butylamino-4,6-dimercapto-s-triazine, 2-di-n-isopropylamino-4,6-dimercapto-s-triazine, 2-di-n-allylamino-4,6-dimercapto-s-triazine, 2-di-n-phenylamino-4,6-dimercapto-s-triazine, etc. Among these, 2-di-n-butylamino-4,6-dimercapto-s-triazine and 2-di-n-isopropylamino-4,6-dimercapto-s-triazine are preferred.

[0034] [(C) Curing catalyst] Component (C) is a curing catalyst that promotes the curing of the resin composition. The curing catalyst of component (C) is not particularly limited, but examples thereof include thermal radical polymerization initiators and thermal anionic polymerization initiators. Examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methylacetoacetate 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, 2,2-bis(4,4-di-t -butylperoxycyclohexyl)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 2,5-Dimethyl-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)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl Pyl 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-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy Peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy Organic peroxides such as 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-methylethyl ... ethyl)-2-methylpropionamide], 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 the azo compounds include 2'-azobis[N-(2-propenyl)-2-methylpropionamide] and dimethyl-1,1'-azobis(1-cyclohexanecarboxylate).

[0035] Examples of the thermal anionic polymerization initiator 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 imidazoles 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; and organic phosphorus compounds such as triphenylphosphine, tributylphosphine, trioctylphosphine, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium acetate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium laurate, tetraphenylphosphonium hydrogen phthalate, bis(tetraphenylphosphonium)dihydrogenpyromellitate, and bis(tetrabutylphosphonium)dihydrogenpyromellitate.

[0036] Among these, thermal anionic polymerization initiators are preferred, and among these, 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. These polymerization initiators may be used alone or in combination of two or more.

[0037] The amount of the curing catalyst for component (C) is not particularly limited, but is generally 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass, per 100 parts by mass of component (A). This range allows for sufficient curing without adversely affecting the physical properties of the curable resin composition.

[0038] [(A-2) Cyclic imide resin represented by the following formula (5)] The curable resin composition of the present invention may contain a cyclic imide resin represented by the following formula (5) as the component (A-2). [ka] (In formula (5), A independently represents a tetravalent organic group containing a cyclic structure. B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom (excluding the alicyclic hydrocarbon group represented by formula (2) below). X represents a hydrogen atom or a methyl group, and s represents 0 to 200.) [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4.

[0039] In formula (5), A, B, and X are the same as those in formula (1). s is 0 to 200, preferably 0 to 100, and more preferably 0 to 50. The repeating units bracketed by s may be the same or different, and the order thereof is not limited.

[0040] The component (A-2) may be used alone or in combination of two or more types. The weight-average molecular weight (Mw) of the cyclic imide resin of component (A-2) is not particularly limited, but is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and even more preferably 3,000 to 50,000. If the weight-average molecular weight (Mw) is within this range, the curable resin composition will have sufficient strength and the terminal cyclic imide groups can be reacted efficiently. The weight average molecular weight is measured by GPC under the same conditions as those for the component (A-1) above, using polystyrene as the standard.

[0041] The method for producing the cyclic imide resin of component (A-2) is not particularly limited. For example, it may be produced by reacting an amine compound with an excess of maleic anhydride or citraconic anhydride, or it may be produced by 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.

[0042] Examples of acid anhydrides include pyromellitic anhydride, maleic anhydride, succinic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-diphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride. These acid anhydrides may be used alone or in combination depending on the purpose, application, etc. From the viewpoint of the electrical properties of the cyclic imide resin, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride are preferred.

[0043] Examples of diamines include tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,12-diaminododecane, 1,10-diaminodecane, dimerdiamine, octyldiamine, 2,4,4-trimethylhexane-1,6-diamine, and 2-methylpentane-1,5-diamine. These diamines may be used alone or in combination depending on the purpose and application. From the viewpoint of the electrical properties of the cyclic imide resin, aliphatic diamines such as tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,12-diaminododecane, 1,10-diaminodecane, dimerdiamine, octyldiamine, 2,4,4-trimethylhexane-1,6-diamine, and 2-methylpentane-1,5-diamine are preferred, with dimerdiamine being particularly preferred.

[0044] The equivalent weight of the cyclic imide group in component (A-2) is preferably 0.001 to 0.5 mol / 100 g, more preferably 0.003 to 0.4 mol / 100 g, even more preferably 0.01 to 0.3 mol / 100 g, and even more preferably 0.02 to 0.2 mol / 100 g. This range is preferable because the cured product of the curable resin composition has a low dielectric constant, a low dielectric loss tangent, and high adhesion.

[0045] Although the blending amount of component (A-2) may be zero, the mass ratio of component (A-1) to component (A-2) is preferably (A-1):(A-2)=99:1 to 60:40, more preferably (A-1):(A-2)=95:5 to 70:30, and even more preferably (A-1):(A-2)=90:10 to 75:25. Within this range, adhesive strength to copper can be increased while maintaining chemical resistance.

[0046] [Inorganic filler] The curable resin composition of the present invention may further contain an inorganic filler, if necessary. The inorganic filler is not particularly limited, and examples thereof include metal oxides such as silica, titanium dioxide, yttrium oxide, aluminum oxide, magnesium oxide, zinc oxide, and beryllium oxide; metal nitrides such as boron nitride, aluminum nitride, and silicon nitride; carbon-containing particles such as silicon carbide, diamond, and graphene; hollow particles such as silica balloons (hollow silica), carbon balloons, alumina balloons, and aluminosilicate balloons; elemental metals such as gold, silver, copper, palladium, aluminum, nickel, iron, cobalt, titanium, manganese, zinc, tungsten, platinum, lead, and tin; and alloys such as solder, steel, and stainless steel. Examples of such materials include magnetic metal alloys such as stainless steel, Fe-Cr-Al-Si alloys, Fe-Si-Al alloys, Fe-Ni alloys, Fe-Cu-Si alloys, Fe-Si alloys, Fe-Si-B(-Cu-Nb) alloys, Fe-Si-Cr-Ni alloys, Fe-Si-Cr alloys, and Fe-Si-Al-Ni-Cr alloys; and ferrites such as hematite (Fe2O3), magnetite (Fe3O4), Mn-Zn ferrites, Ni-Zn ferrites, Mg-Mn ferrites, Zr-Mn ferrites, Ti-Mn ferrites, Mn-Zn-Cu ferrites, barium ferrites, and strontium ferrites. These may be used alone or in combination of two or more.

[0047] By adding metal oxides, metal nitrides, or carbon-containing particles, the linear expansion coefficient of the cured product of the curable resin composition can be reduced and the thermal conductivity can be increased; by adding hollow particles, the relative dielectric constant, dielectric loss tangent, density, etc. of the cured product of the curable resin composition can be reduced; by adding metals or alloys, the electrical conductivity, thermal conductivity, etc. of the cured product of the resin composition can be increased; and by adding ferrites, electromagnetic wave absorption ability can be imparted to the cured product of the curable resin composition.

[0048] The shape of the inorganic filler is not particularly limited, and examples thereof include spherical, scale-like, flake-like, needle-like, rod-like, and elliptical shapes. Among these, spherical, scale-like, flake-like, elliptical, and rod-like shapes are preferred, and spherical, scale-like, flake-like, and elliptical shapes are more preferred.

[0049] The primary particle size of the inorganic filler is not particularly limited, but is preferably 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as a median diameter measured with a laser diffraction particle size distribution analyzer. Within this range, the inorganic filler can be easily uniformly dispersed in the curable resin composition, and the inorganic filler does not settle, separate, or become unevenly distributed over time, which is preferable.

[0050] The amount of the inorganic filler to be added is not particularly limited, but 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.

[0051] [Organic filler] The curable resin composition of the present invention may further contain an organic filler. The organic filler is not particularly limited, and examples thereof include thermoplastic resin particles such as acrylic-butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, and acrylic block copolymer, carbon fiber, cellulose fiber, silicone powder, acrylic powder, polytetrafluoroethylene powder, polyethylene powder, and polypropylene powder. These may be used alone or in combination of two or more.

[0052] The shape of the organic filler is not particularly limited, and examples thereof include spherical, fibrous, flake-like, needle-like, rod-like, and elliptical shapes. Among these, spherical, fibrous, flake-like, elliptical, and rod-like shapes are preferred, and spherical, fibrous, flake-like, and elliptical shapes are more preferred.

[0053] The primary particle size of the organic filler is not particularly limited, but is preferably 0.05 to 500 μm, more preferably 0.1 to 300 μm, and even more preferably 1 to 100 μm, as a median diameter measured with a laser diffraction particle size distribution analyzer. Within this range, the organic particles can be easily dispersed uniformly in the curable resin composition, and the organic particles do not settle, separate, or become unevenly distributed over time, which is preferable.

[0054] The amount of the organic filler to be added is not particularly limited, but 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, it is possible to increase the strength of the curable resin composition.

[0055] [Adhesion promoter] The curable resin composition of the present invention may contain an adhesion promoter, if necessary, to impart adhesiveness or tackiness (pressure-sensitive adhesiveness). 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 adhesiveness).

[0056] The epoxy resin is not particularly limited, and examples thereof include known epoxy resins that are liquid or solid at room temperature, such as biphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, 3,3',5,5'-tetramethyl-4,4'-biphenol-type epoxy resins and 4,4'-biphenol-type epoxy resins, biphenylaralkyl-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, naphthalenediol-type epoxy resins, trisphenylolmethane-type epoxy resins, tetrakisphenylolethane-type epoxy resins and phenoldicyclopentadiene novolac-type epoxy resins in which the aromatic rings are hydrogenated, and alicyclic epoxy resins.

[0057] The acrylic resin is not particularly limited, and examples thereof 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, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate. acrylate, dioxane glycol diacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, lauryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol dimethacrylate, dimethyloltricyclodecane dimethacrylate, and the like.

[0058] The terpene resin is not particularly limited, and examples thereof include homopolymers of terpenes such as monoterpenes such as α-pinene, β-pinene, dipentene, and limonene, sesquiterpenes such as cedrene and farnesene, and diterpenes such as abietic acid, aromatic modified terpene resins which are copolymers of the above-mentioned terpenes with aromatic vinyl compounds such as styrene and α-methylstyrene, and terpene phenol resins which are copolymers of the above-mentioned terpenes with phenols such as phenol, cresol, hydroquinone, naphthol, and bisphenol A. Hydrogenated terpene resins obtained by hydrogenating these terpene resins can also be used.

[0059] The silane coupling agent is not particularly limited, and examples thereof 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.

[0060] The amount of the adhesion promoter is not particularly limited, but 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). This range can further improve the adhesive strength or cohesive strength of the curable resin composition without changing the mechanical properties of the resin composition.

[0061] [Antioxidants] The resin composition of the present invention may contain an antioxidant, if necessary. The antioxidant is not particularly limited, and examples thereof 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, ethyl Octadecyl-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-hydroxyphenylacetate, 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, Pentaerythritol Phenolic antioxidants such as rhythritol tetrakis[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 tetrakis(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]dioxaphosphepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]-ethyl]ethanamine;

[0062] The amount of the antioxidant to be added is not particularly limited, but 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.

[0063] [Flame retardant] The curable resin composition of the present invention may contain a flame retardant as needed to impart flame retardancy. The flame retardant is not particularly limited, and examples thereof include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, guanidine-based flame retardants, etc. Examples of phosphorus-based flame retardants include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, inorganic nitrogen-containing phosphorus compounds such as guanidine phosphate and phosphoric acid amide, 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), 1,3-phenylene bis( Examples of suitable phosphazene compounds include bis(1-butenyl)phenylphosphonate, bis(2-allylphenoxy)phosphazene (diphenyl phosphate), divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl)phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, bis(2-allylphenoxy)phosphazene, and 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 suitable metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. Examples of halogen-based flame retardants include hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, etc. Examples of guanidine-based flame retardants include guanidine sulfamate, guanidine phosphate, etc.

[0064] The amount of the flame retardant to be added is not particularly limited, but 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 the mechanical properties of the resin composition.

[0065] [Manufacturing method] The curable resin composition of the present invention can be produced by mixing components (A) to (C) and other additives, if necessary, using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a THINKY CONDITIONING MIXER (manufactured by THINKY Corporation). Preferably, an organic solvent (e.g., cyclopentanone, cyclohexanone, mesitylene, anisole, dibutyl ether, diphenyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.) is further added and mixed. The addition of an organic solvent reduces the viscosity of the curable resin composition, allowing for more uniform mixing. The curable resin composition can be obtained by distilling off the organic solvent under reduced pressure after mixing. However, when used as a film, the organic solvent may be used as is without distilling off, or may be adjusted to a desired concentration before use. [Example]

[0066] EXAMPLES 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.

[0067] The molecular weights shown in the following examples are weight-average molecular weights (Mw) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are as follows: [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 in tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0068] (A) Cyclic imide resin (A-1) (A-1-1) To 263 g of N-methylpyrrolidone (water content 0.5%), 114 g (1.0 mol) of 1,4-cyclohexanediamine and 499 g (0.96 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, and the mixture was stirred at 25°C for 3 hours, followed by further 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. 500 g of toluene was then added, and the mixture was washed with water and dehydrated. The solvent was then distilled off under reduced pressure to obtain bismaleimide (A-1-1) represented by the following formula: (weight average molecular weight 5,000, maleimide equivalent 0.040 mol / 100 g) [ka]

[0069] (A-1-2) To 263 g of N-methylpyrrolidone (water content 0.5%), 113 g (0.67 mol) of isophoronediamine, 174 g (0.33 mol) of dimer diamine, and 209 g (0.96 mol) of pyromellitic anhydride were added, and the mixture was stirred at 25°C for 3 hours, followed by further 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, 500 g of toluene was added, and the mixture was washed with water and dehydrated. The solvent was then distilled off under reduced pressure to obtain bismaleimide (A-1-2) represented by the following formula: (weight average molecular weight 5,700, maleimide equivalent 0.035 mol / 100 g) [ka]

[0070] (A-1-3) To 263 g of N-methylpyrrolidone (water content 0.6%), 136 g (0.80 mol) of isophoronediamine, 104 g (0.20 mol) of dimer diamine, and 298 g (0.96 mol) of 4,4'-oxydiphthalic anhydride were added and stirred at 25°C for 3 hours, followed by further 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 stirred at 80°C for 1 hour. 500 g of toluene was then added, and the mixture was washed with water and dehydrated. The solvent was then distilled off under reduced pressure to obtain bismaleimide (A-1-3) represented by the following formula: (weight average molecular weight 10,000, maleimide equivalent 0.019 mol / 100 g). [ka]

[0071] (A-2) (A-2-1) Maleimide compound (BMI-1500, manufactured by Designer Molecules Inc.) represented by the following formula (weight average molecular weight: 3,000, maleimide equivalent: 0.067 mol / 100 g) [ka]

[0072] (A-2-2) Maleimide compound (BMI-689, manufactured by Designer Molecules Inc.) represented by the following formula (weight average molecular weight: 700, maleimide equivalent: 0.29 mol / 100 g) [ka]

[0073] (A'-1) (for comparative example) To 263 g of N-methylpyrrolidone (water content 0.6%), 310 g (1.0 mol) of 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane and 298 g (0.96 mol) of 4,4'-oxydiphthalic anhydride were added, and the mixture was stirred at 25°C for 3 hours, followed by stirring at 150°C for an additional 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. 500 g of toluene was then added, and the mixture was washed with water and dehydrated. The solvent was then distilled off under reduced pressure to obtain bismaleimide (A'-1) represented by the following formula: (weight average molecular weight 5,000, maleimide equivalent 0.040 mol / 100 g) [ka]

[0074] (B) Triazine thiol (B-1) ACTOR TSH (2,4,6-trimercapto-s-triazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.) (B-2) ACTOR BSH (2-di-n-butylamino-4,6-dimercapto-s-triazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.) (B-3) ACTOR IPSH (2-di-n-isopropylamino-4,6-dimercapto-s-triazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

[0075] (C) Curing catalyst (C-1) 2-Ethyl-4-methylimidazole

[0076] (D) Inorganic filler (D-1) Silica "SFP-130MC" (median primary particle size: 0.6 μm) (manufactured by Denka Co., Ltd.)

[0077] (E) Adhesion promoter (E-1) Bisphenol A epoxy resin (trade name "jER-828EL" (manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 0.55 mol / 100 g (183 g / eq))

[0078] [Method for preparing curable resin composition] For Examples 1 to 10 and Comparative Examples 1 to 4, 100 parts by mass of cyclopentanone was added to the formulation (parts by mass) shown in Table 1, based on a total of 100 parts by mass of each component, and the mixture was 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 distilled off under reduced pressure to prepare a curable resin composition.

[0079] [Tg, coefficient of linear expansion] The prepared curable resin composition was sandwiched between a 30 mm x 40 mm x 100 μm thick mold frame and press-cured at 180°C and 3 MPa for 1 hour to prepare a test sample. The prepared test sample was measured using a TMA Q400 (manufactured by TA Instruments) over a temperature range of -50°C to 300°C, and the Tg and linear expansion coefficient were calculated from the resulting graph. The measurement conditions were a 20 mm x 3 mm x 100 μm thick test sample (cured product), a heating rate of 5°C / min, and a tensile mode. The results are shown in Table 1.

[0080] [Dielectric constant and dielectric loss tangent] The prepared curable resin composition was sandwiched between a 30 mm x 40 mm x 100 μm thick mold frame and press-cured at 180°C and 3 MPa for 1 hour to prepare a test sample. A network analyzer (Keysight E5063-2D5) and a stripline (Keycom Corporation) were connected to the prepared test sample to measure the relative permittivity and dielectric loss tangent at a frequency of 10 GHz. The results are shown in Table 1.

[0081] [Peel Strength] The prepared curable resin composition was coated onto a PET film to a thickness of 25 μm to produce a resin film. Using a vacuum laminator V-130 (manufactured by Nikko Materials Co., Ltd.), the resin film was laminated with a SUS plate on the opposite side of the PET film 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 18 μm thick copper foil (product name: TQ-M4-VSP, manufactured by Mitsui Metals Co., Ltd.) was placed on top. The laminate was then laminated again at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa for 60 seconds, and then heated to 180°C for 1 hour to cure. In accordance with JIS-C-6481:1996, a standard for testing copper-clad laminates for printed wiring boards, the force required to peel the copper foil from the resin film (peel strength) was measured using a Tensilon tester (manufactured by Toyo Seiki Seisakusho, product name: Strograph VE-1D) at a speed of 50 mm / min in a 90° direction over a 10 mm width. The results are shown in Table 1.

[0082] [Desmear resistance] The resin film prepared by the method described above under "Peel Strength" was placed on a substrate with a 100 / 100 L / S copper wiring pattern using a vacuum laminator V-130 (Nikko Materials Co., Ltd.) so that the side opposite the PET film was in contact with the substrate. The laminate was then laminated for 60 seconds at 80°C, a vacuum of 0.6 hPa, and a pressure of 0.3 MPa. After cooling to room temperature, the PET film was peeled off and the laminate was cured by heating at 180°C for 1 hour. A 100 μm diameter via hole was drilled in the cured substrate using a CO2 laser (Via Mechanics Co., Ltd., model LC-2Q252), which was then desmeared. The cross section was then cut and visually inspected for peeling from the copper. In addition, the prepared curable resin composition was sandwiched between a mold frame of 30 mm × 40 mm × 100 μm thickness and press-cured at 180°C and 3 MPa for 1 hour to prepare a test sample, and the weight loss rate of the test sample before and after the desmear treatment was calculated (weight loss (g) / surface area of ​​test sample (dm 2 )). The desmear treatment described above was carried out in the following order: swelling (70°C, 5 minutes), roughening (80°C, 10 minutes), neutralization (40°C, 5 minutes), and water rinsing (room temperature, 5 minutes). The test solutions used were swelling solution, desmear solution, and neutralization solution manufactured by Atotech, adjusted to the specified concentrations. The results are shown in Table 1.

[0083] [Table 1]

[0084] In Examples 1 to 10, the cured products of the curable resin compositions had low relative dielectric constants and low dielectric loss tangents, and were free from peeling and had excellent desmear resistance. In Comparative Example 1, the adhesive strength to copper was low because triazine thiol was not contained, and peeling occurred after desmearing. Component (A-1) has a high Tg, strong adhesion to copper, and high desmear resistance, but in Comparative Examples 2 and 4, component (A-2) was used instead of component (A-1), but its Tg was low, causing peeling after desmearing. In addition, the weight loss rate of the resin due to the desmear treatment was high. In Comparative Example 3, which did not contain the component (A-1), the adhesive strength to copper was low, and peeling occurred after desmearing.

Claims

1. (A-1) 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 an alicyclic hydrocarbon group represented by the following formula (2), and B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom. X represents a hydrogen atom or a methyl group, n represents 1 to 200, m represents 0 to 200, and when m is 1 or more, the n:m ratio is 1:1 to 4:

1. The order of the repeating units bracketed by n and m is not limited.) 【Chemistry 2】 (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4. (B) Triazine thiol represented by the following formula (3): 1 to 10 parts by mass per 100 parts by mass of component (A) 【Transformation 3】 (In formula (3), R 2 is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, a hydroxy group, and a group represented by the following formula (4): 【Chemistry 4】 (In formula (4), R 2' is a group selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, an amino group, a thiol group, and a hydroxy group. and (C) Curing catalyst: 0.01 to 10 parts by mass per 100 parts by mass of component (A) A curable resin composition comprising:

2. The curable resin composition according to claim 1, further comprising (A-2) a cyclic imide resin represented by the following formula (5): 【Transformation 5】 (In formula (5), each A independently represents a tetravalent organic group containing a cyclic structure. Each B independently represents a divalent aliphatic hydrocarbon group having 6 or more carbon atoms which may contain a heteroatom (excluding the alicyclic hydrocarbon group represented by formula (2) below). X represents a hydrogen atom or a methyl group, and s is 0 to 200.) 【Transformation 6】 (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x is independently a number from 0 to 4.

3. 3. The curable resin composition according to claim 2, wherein the mass ratio of the component (A-1) to the component (A-2) is (A-1):(A-2)=99:1 to 60:40.

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