Thermosetting resin composition

Abstract

To provide a heat-curable maleimide resin composition suitable for use in a substrate, and whose cured product has an excellent high-temperature property due to its high glass-transition temperature, an excellent dielectric property and excellent dimension stability; and uncured and cured resin films comprising such a composition and having an excellent handling property.SOLUTION: The heat-curable maleimide resin composition contains: (A) a maleimide resin having a number average molecular weight of 3,000 or more; (B) an organic compound having, in one molecule, at least one allyl group and at least one isocyanuric ring; and (C) a reaction initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting maleimide resin composition and uncured and cured films made from the resin composition. [Background technology]

[0002] In recent years, the next generation mobile communication system known as 5G has become popular, aiming to realize high speed, large capacity, and low latency communications. To achieve this, materials for high frequency bands are required, and since reducing transmission loss is essential as a noise countermeasure, there is a demand for the development of insulating materials with excellent dielectric properties.

[0003] Among these, insulating materials with excellent dielectric properties are in demand for circuit board applications, particularly for rigid and flexible circuit boards.Reactive polyphenylene ether resins (PPE) are becoming popular for rigid circuit boards, while liquid crystal polymers (LCPs) and modified polyimides (MPIs) with improved properties are becoming popular for flexible printed circuit boards (FPCs).

[0004] Although these materials have excellent characteristics, they also have many issues. For example, reactive PPE resins have excellent dielectric properties and a high glass transition temperature (Tg), but they have poor adhesive strength and have recently shown issues with insulation resistance in long-term reliability tests (e.g., Patent Documents 1 and 2). Regarding LCPs, many inventions have been disclosed, including those aimed at further improving LCP performance and base films and coverlay films for FPCs that use LCP (e.g., Patent Documents 3 and 4). However, LCPs have limited use due to the difficulty of mass-producing them to meet demand. Furthermore, LCPs require high-temperature molding at temperatures above 300°C, a problem unique to thermoplastic resins, and require adhesives with low dielectric properties to bond copper-clad laminates. Many areas remain that need improvement.

[0005] Therefore, the use of MPIs has been considered for some frequency bands, and many inventions related to MPIs have been disclosed (e.g., Patent Documents 5 and 6). While these MPIs offer improved dielectric properties compared to current polyimides, they are thermoplastic resins like LCPs, and therefore suffer from similar issues. Furthermore, their inherent hygroscopicity has been known to significantly impair their dielectric properties. To address these issues, MPIs with dimer diamine structures have been disclosed (Patent Document 7). However, compared to conventional MPIs, they have significantly lower glass transition temperatures (Tg) and poorer dimensional stability. Furthermore, the production of MPIs requires the use of large amounts of aprotic polar solvents, such as N-methylpyrrolidone (NMP), which is undesirable from an environmental perspective.

[0006] Therefore, in recent years, maleimide resins have been attracting attention as a material similar to polyimide. Among maleimide resins, bismaleimide resins are the most common, and many low-molecular-weight types are known. They have excellent high-temperature properties such as a high Tg, but the uncured products have poor film properties, and the cured products are hard and brittle. In addition, their dielectric properties are not as satisfactory as those of LCP or MPI, so there is still room for improvement.

[0007] In response to this, a composition using a maleimide compound essentially having a dimer diamine skeleton as an FPC material and its cured product have been disclosed (Patent Document 8). However, while the composition has excellent dielectric properties, contrary to the characteristics of general maleimide resins, it has a low Tg and a high coefficient of thermal expansion (CTE), and still lacks dimensional stability. In addition, since it is a mixture of a bismaleimide resin with a long-chain alkyl group and a hard, low-molecular-weight aromatic maleimide resin, it has poor compatibility, and the properties and curing of the composition and its cured product are prone to unevenness.

[0008] On the other hand, a liquid resin composition for semiconductor encapsulation containing the above-mentioned special maleimide and an allyl compound has been disclosed (Patent Document 9). [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2019 / 65940 [Patent Document 2] International Publication No. 2019 / 65941 [Patent Document 3] International Publication No. 2013 / 65453 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-74129 [Patent Document 5] Japanese Patent Application Publication No. 2017-78102 [Patent Document 6] Japanese Patent Application Laid-Open No. 2019-104818 [Patent Document 7] Japanese Patent Publication No. 2020-56011 [Patent Document 8] International Publication No. 2016 / 114287 [Patent Document 9] Japanese Patent Application Laid-Open No. 2014-1289 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the resin composition described in Patent Document 9 was insufficient as an insulating material having excellent dielectric properties for use in substrates. Therefore, an object of the present invention is to provide an insulating material with excellent dielectric properties, particularly a thermosetting maleimide resin composition suitable for substrate applications, which has a high glass transition temperature (Tg) of the cured product, resulting in excellent high-temperature properties, excellent dielectric properties, and excellent dimensional stability, as well as an uncured resin film and a cured resin film made therefrom that are easy to handle. Another object of the present invention is to provide a substrate using the same. [Means for solving the problem]

[0011] As a result of extensive research to solve the above problems, the present inventors have found that the following thermosetting maleimide resin composition can achieve the above object, and have thus completed the present invention.

[0012] <1> (A) A maleimide resin represented by the following formula (1) and having a number average molecular weight of 3,000 or more: (B) An organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule and (C) Reaction initiator A thermosetting maleimide resin composition comprising: [ka] (In formula (1), A is independently a tetravalent organic group having a cyclic structure, B is independently a divalent hydrocarbon group having 6 to 200 carbon atoms, Q is independently represented by the following formula (2): [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x1 and x2 are each independently a number from 0 to 4. is a divalent alicyclic hydrocarbon group having 6 to 60 carbon atoms and a cyclohexane skeleton, represented by W is B or Q; n is 1 to 100, m is 0 to 100; The order of the repeating units bounded by n and m is not limited, and the bonding pattern may be alternating, block, or random. <2> A in formula (1) is any of the tetravalent organic groups represented by the following structural formulas: <1> 1. The thermosetting maleimide resin composition according to claim 1. [ka] (The bond not bonded to a substituent in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in general formula (1).) <3> B in formula (1) is a divalent hydrocarbon group derived from a diamine derived from a dimer acid. <1> or <2> 1. The thermosetting maleimide resin composition according to claim 1. <4> (A) A maleimide resin represented by the following formula (3) and having a number average molecular weight of 3,000 or more: (B) An organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule and (C) Reaction initiator A thermosetting maleimide resin composition comprising: [ka] (In formula (3), X 1 are independently expressed by the following formula: [ka] (a is a number between 1 and 6.) [ka] is a divalent group selected from k is a number between 1 and 30, l is a number between 0 and 10, A 1 and A 2 are each independently a divalent aromatic group represented by the following formula (4) or (5): [ka] (In formula (4), X 2 are independently expressed by the following formula: [ka] (a is a number between 1 and 6.) [ka] is a divalent group selected from R 2are independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. [ka] (In formula (5), X 1 indicates the same as above.) <5> The organic compound of component (B) has two or more allyl groups in one molecule. <1> from <4> 1. The thermosetting maleimide resin composition according to claim 1 . <6> The reaction initiator of component (C) is a radical polymerization initiator. <1> from <5> 1. The thermosetting maleimide resin composition according to claim 1 . <7> <1> or <4> An uncured resin film comprising the thermosetting maleimide resin composition according to claim 1. <8> <1> or <4> 1. A cured resin film comprising a cured product of the thermosetting maleimide resin composition according to claim 1. <9> <1> or <4> A prepreg comprising the thermosetting maleimide resin composition according to claim 1 and a fiber substrate. <10> <1> or <4> 1. An adhesive comprising the thermosetting maleimide resin composition according to claim 1. <11> <1> or <4> A substrate comprising the thermosetting maleimide resin composition according to claim 1. [Effects of the Invention]

[0013] The thermosetting maleimide resin composition of the present invention has a high glass transition temperature and excellent dielectric properties and dimensional stability after curing. Furthermore, the thermosetting maleimide resin composition of the present invention can be produced without using an aprotic polar solvent such as NMP, and exhibits excellent handleability as a film or sheet before and after curing. Therefore, the thermosetting maleimide resin composition of the present invention is particularly useful as a substrate material. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in more detail below.

[0015] (A) Maleimide resin with a number average molecular weight of 3,000 or more The component (A) used in the present invention is a maleimide resin having a number-average molecular weight of 3,000 or more, and is represented by general formula (1) or (3). Generally, maleimide compounds have a number-average molecular weight of 2,000 or less. While many of these maleimide compounds with a number-average molecular weight of 2,000 or less have a high Tg, they are poor in processability and moldability into films before and after curing, making them particularly difficult to handle as the main component of a substrate composition. For these reasons, the present invention uses a high-molecular-weight maleimide resin having a number-average molecular weight of 3,000 or more.

[0016] The properties of the maleimide resin of component (A) at room temperature are not particularly limited, but the number average molecular weight (Mn) is preferably 3,000 or more, more preferably 3,500 to 50,000, and particularly preferably 4,000 to 40,000, as calculated against a polystyrene standard by gel permeation chromatography (GPC) measurement under the following measurement conditions: If the molecular weight is 3,000 or more, the resulting composition can be easily formed into a film and has good handleability.

[0017] [Measurement conditions] Developing solvent: tetrahydrofuran (THF) Flow rate: 0.35mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-L TSKgel SuperHZ4000(4.6mmI.D.×15cm×1) TSKgel SuperHZ3000(4.6mmI.D.×15cm×1) TSKgel SuperHZ2000(4.6mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 5 μL (0.2% by mass THF solution)

[0018] Furthermore, when a maleimide resin represented by the following formula (1) or (3) is used as the maleimide resin of component (A), not only does the resulting film have good mechanical properties and is easy to handle both before and after curing, but it also has high compatibility with component (B), which will be described later, and a composition can be obtained whose properties are consistent from location to location.

[0019] Maleimide resin represented by formula (1) [ka]

[0020] In formula (1), A independently represents a tetravalent organic group having a cyclic structure, and is preferably any of the tetravalent organic groups represented by the following structural formulas. [ka] (The bond not bonded to a substituent in the above structural formula is bonded to the carbonyl carbon that forms the cyclic imide structure in general formula (1).)

[0021] In formula (1), B independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms. B is preferably a divalent hydrocarbon group having 8 to 100 carbon atoms, more preferably 10 to 50 carbon atoms. Among these, a branched divalent hydrocarbon group in which one or more hydrogen atoms in the divalent hydrocarbon group are substituted with an alkyl or alkenyl group having 6 to 200 carbon atoms, preferably 8 to 100 carbon atoms, more preferably 10 to 50 carbon atoms is preferred. The branched divalent hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated hydrocarbon group, and may have an alicyclic structure or an aromatic ring structure in the middle of the molecular chain. Specific examples of the branched divalent hydrocarbon group include divalent hydrocarbon groups derived from diamines at both ends, known as dimer diamines. Dimer diamines are compounds derived from dimers (dimer acids) of unsaturated fatty acids such as oleic acid. Dimer acids are liquid dibasic acids primarily composed of dicarboxylic acids with 36 carbon atoms, produced by dimerization of unsaturated fatty acids with 18 carbon atoms, derived from natural products such as vegetable oils and fats. The dimer acid (dimer diamine) skeleton refers to the structure obtained by removing the carboxyl group (amino group) from the dimer acid. Therefore, the dimer acid skeleton is not a single skeleton but has multiple structures, and it is known that several types of isomers exist. Representative dimer acids are classified as linear (a), monocyclic (b), aromatic (c), and polycyclic (d). That is, preferred examples of B include branched divalent hydrocarbon groups obtained by removing two carboxy groups from dimer acids represented by the following (a) to (d). [ka]

[0022] In formula (1), Q independently represents the following formula (2): [ka] (In formula (2), R 1 are independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and x1 and x2 are each independently a number from 0 to 4. Q is a divalent alicyclic hydrocarbon group having 6 to 60 carbon atoms and one or more cyclohexane skeletons, represented by the following formula: Q is preferably a divalent alicyclic hydrocarbon group having 8 to 30 carbon atoms, more preferably 10 to 20 carbon atoms. where R 1 Specific examples of R include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Among these, a hydrogen atom and a methyl group are preferred. 1 may be the same or different. Furthermore, the x1 and x2 each independently represent a number from 0 to 4, and preferably a number from 0 to 2. Note that x1 and x2 may be the same or different.

[0023] Specific examples of Q include divalent alicyclic hydrocarbon groups represented by the following structural formulas. [ka] (The bond not bonded to a substituent in the above structural formula is bonded to the nitrogen atom that forms the cyclic imide structure in formula (1).)

[0024] In formula (1), W is B or Q. The structural unit W is either B or Q, which is determined depending on the manufacturing method described below.

[0025] In formula (1), n ​​is 1 to 100, preferably 2 to 60, and more preferably 5 to 50. Furthermore, m is 0 to 100, preferably 1 to 50, and more preferably 3 to 40. If n or m is too small, the cured product will be brittle and prone to cracking, whereas if n or m is too large, the flowability will decrease, and moldability may be poor. Furthermore, in the maleimide resin represented by formula (1), the order of the repeating units bracketed by n and m in the formula is not limited, and the bonding mode may be alternating, block, or random, but is preferably a block bond.

[0026] There are no particular limitations on the method for producing the maleimide resin represented by formula (1), but it can be efficiently produced, for example, by the following two methods. Manufacturing method (1)-1 One method includes a step A of synthesizing an amic acid from an acid anhydride represented by the following formula (6) and an alicyclic diamine represented by the following formula (7), and then ring-closing and dehydrating the amic acid. Following the step A, there is a step B in which an amic acid is synthesized from the reaction product obtained in the step A and a diamine represented by the following formula (8), and the amic acid is subjected to ring-closing dehydration. This method for producing a maleimide resin includes, following step B, step C of synthesizing maleamic acid from the reaction product obtained in step B and maleic anhydride, and capping the molecular chain terminals with maleimide groups by ring-closing dehydration.

[0027] Manufacturing method (1)-2 Another method includes a step A' of synthesizing an amic acid from an acid anhydride represented by the following formula (6) and a diamine represented by the following formula (8), and then ring-closing and dehydrating the amic acid. Following the step A', there is a step B' in which an amic acid is synthesized from the reaction product obtained in the step A' and an alicyclic diamine represented by the following formula (7), and the amic acid is subjected to ring-closing dehydration. This method for producing a maleimide resin includes, subsequent to step B', step C' in which maleamic acid is synthesized from the reaction product obtained in step B' and maleic anhydride, and the resulting maleamic acid is subjected to ring-closing dehydration to cap the molecular chain terminals.

[0028] [ka] (In formula (6), A is the same as that shown in formula (1) above.) [ka] (In formula (7), R 1 , x1 and x2 are the same as those shown in formula (2). H2N-B-NH2(8) (In formula (8), B is the same as that shown in formula (1) above.)

[0029] The two manufacturing methods described above are basically the same: synthesizing an amic acid from a tetracarboxylic dianhydride and a diamine, followed by step A (or step A') of ring-closing dehydration; adding a different diamine from step A (or step A') after step A (or step A') to synthesize an amic acid, followed by step B (or step B') of ring-closing dehydration; reacting with maleic anhydride after step B (or step B') to synthesize a maleamic acid, and finally step C (or step C') of capping the molecular chain ends with maleimide groups by ring-closing dehydration, thereby obtaining the maleimide resin represented by formula (1). The difference between the two manufacturing methods is primarily the order in which the diamines are added.

[0030] In the above two production methods, each step can be roughly divided into two: a synthesis reaction of amic acid or maleamic acid, and a ring-closing dehydration reaction, which will be described in detail below.

[0031] In step A (or step A'), a specific tetracarboxylic dianhydride is first reacted with a specific diamine to synthesize an amic acid. This reaction generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25°C) to 100°C. The subsequent ring-closing dehydration reaction of the amic acid is carried out at 90 to 120°C, and then the water by-produced in the condensation reaction is removed from the system. To promote the ring-closing dehydration reaction, an organic solvent (e.g., a nonpolar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst can be added. Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). These may be used alone or in combination of two or more. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These may be used alone or in combination of two or more. The molar ratio of tetracarboxylic dianhydride to diamine is preferably tetracarboxylic dianhydride / diamine=1.01 to 1.50 / 1.0, and more preferably tetracarboxylic dianhydride / diamine=1.01 to 1.35 / 1.0. By blending at this ratio, a copolymer containing imide groups at both ends can be synthesized.

[0032] In step B (or step B'), the copolymer containing imide groups at both ends obtained in step A (or step A') is first reacted with a specific diamine to synthesize an amic acid. This reaction also generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25°C) to 100°C. Similarly, the subsequent ring-closing dehydration reaction of the amic acid is carried out at 95 to 120°C, and then the water by-produced by the condensation reaction is removed from the system. To promote the ring-closing dehydration reaction, an organic solvent (e.g., a nonpolar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst can be added. Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). These may be used alone or in combination of two or more. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These may be used alone or in combination of two or more. The molar ratio of the copolymer containing imide groups at both ends to the diamine is preferably 1.0:1.6-2.5, and more preferably 1.0:1.8-2.2.

[0033] In step C (or step C'), the diamine having amino groups at both ends obtained in step B (or step B') is reacted with maleic anhydride at room temperature (25°C) to 100°C to synthesize maleamic acid, and finally, the molecular chain ends are blocked with maleimide groups by ring-closing dehydration while removing the water by-product in the system at 95 to 120°C, thereby obtaining the desired maleimide resin. It is preferable to carry out the blocking reaction of the molecular chain ends with maleimide groups at 120°C or below, as this reduces the likelihood of side reactions and high molecular weight products. According to this production method, the maleimide resin obtained has a block copolymer structure, and therefore the compatibility of the synthesized resin can be made uniform and improved. The molar ratio of the diamine having amino groups at both ends to maleic anhydride is preferably 1.0:1.6-2.5, and more preferably 1.0:1.8-2.2.

[0034] After step C (or step C'), the product may be purified by a conventional method, for example, by reprecipitation.

[0035] Maleimide resin represented by formula (3) [ka]

[0036] In formula (3), X 1 are independently divalent groups selected from the following formulae: [ka] (a is a number between 1 and 6.) [ka] X in equation (3) 1 As the alkyl group, -CH2- and -C(CH3)2- are preferred from the viewpoint of easy availability of raw materials.

[0037] In formula (3), k is a number from 1 to 30, and preferably a number from 2 to 20. When k is within this range, the maleimide resin represented by formula (3) has a good balance between its solubility in solvents and film-forming ability when uncured, and the toughness and heat resistance of the resulting cured product. 1 is a number from 0 to 10, preferably 0 to 5, and more preferably 1.

[0038] In formula (3), A 1 and A 2 are each independently a divalent aromatic group represented by the following formula (4) or (5): [ka] (In formula (4), X 2 are independently expressed by the following formula: [ka] (a is a number between 1 and 6.) [ka] is a divalent group selected from 2 are independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. [ka] (In formula (5), X 1 is the same as above.)

[0039] X in equation (4) 2 As the alkyl group, -CH2- and -C(CH3)2- are preferred from the viewpoint of easy availability of raw materials. R in equation (4) 2 Examples of the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a cyclohexyl group, and also include groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, and Br, such as a trifluoromethyl group. 2From the viewpoint of availability of raw materials, A is preferably a hydrogen atom or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 3 carbon atoms. 1 and A 2 In the formula (3), A is preferably different from A. 1 When the formula (4) is 2 is the formula (5), or A 1 When the formula (5) is 2 may be the above formula (4).

[0040] In addition, X in the formula (3) 1 and X in the above formula (5) 1 It is preferable that the maleimide resin represented by formula (3) has the same divalent group. This means that the maleimide resin has two or more identical bisphenol skeletons, and that the maleimide resin represented by formula (3) is produced using a divalent acid anhydride and a diamine having the same bisphenol skeleton.

[0041] There are no particular limitations on the method for producing the maleimide resin represented by formula (3), but it can be efficiently produced, for example, by the following two methods. Manufacturing method (3)-1 One method includes a step D of synthesizing an amic acid from an aromatic diphthalic anhydride represented by the following formula (9) and an aromatic diamine represented by the following formula (10), and then ring-closing and dehydrating the amic acid. Following the step D, a step E is carried out in which an amic acid is synthesized from the reaction product obtained in the step D and an aromatic diamine represented by the following formula (11), and the amic acid is subjected to ring-closing dehydration. This method for producing a maleimide resin comprises, following step E, step F of reacting the reaction product obtained in step E with maleic anhydride to synthesize maleamic acid, and then capping the molecular chain terminals with maleimide groups by ring-closing dehydration.

[0042] Manufacturing method (3)-2 Another method includes a step D' of synthesizing an amic acid from an aromatic diphthalic anhydride represented by the following formula (9) and an aromatic diamine represented by the following formula (11), and then ring-closing and dehydrating the amic acid. Following the step D', a step E' is carried out in which an amic acid is synthesized from the reaction product obtained in the step D' and an aromatic diamine represented by the following formula (10), and the amic acid is subjected to ring-closing dehydration. This method for producing a maleimide resin includes, subsequent to step E', step F' in which the reaction product obtained in step E' is reacted with maleic anhydride to synthesize maleamic acid, and the resulting maleamic acid is subjected to ring-closing dehydration to cap the molecular chain terminals with maleimide groups.

[0043] [ka] (In formula (9), X 1 is the same as that shown in equation (3) above.) [ka] (In formula (10), R 2 and X 2 is the same as that shown in equation (4) above.) [ka] (In formula (11), X 1 is the same as that shown in equation (3) above.)

[0044] The two manufacturing methods described above are basic steps: synthesizing an amic acid from an aromatic diphthalic acid and an aromatic diamine, then undergoing ring-closing dehydration in step D (or step D'); after step D (or step D'), adding an aromatic diamine different from that used in step D (or step D') to synthesize an amic acid, then undergoing ring-closing dehydration in step E (or step E'); after step E (or step E'), reacting with maleic anhydride to synthesize a maleamic acid, and finally undergoing ring-closing dehydration in step F (or step F') to cap the molecular chain ends with maleimide groups, thereby obtaining the maleimide resin represented by formula (3). The difference between the two manufacturing methods described above is mainly the order in which the types of aromatic diamines are added.

[0045] In the above two production methods, each step can be roughly divided into two: a synthesis reaction of amic acid or maleamic acid, and a ring-closing dehydration reaction, which will be described in detail below.

[0046] In step D (or step D'), a specific aromatic diphthalic anhydride is reacted with a specific aromatic diamine to synthesize an amic acid. This reaction generally proceeds in a high-boiling aprotic polar solvent at room temperature (25°C) to 100°C. However, in the reaction between aromatic diphthalic anhydride and aromatic diamine, anisole and its derivatives (e.g., o-methylanisole, p-methylanisole, etc.) can be used as the solvent instead of a high-boiling aprotic polar solvent. The subsequent ring-closing dehydration reaction of the amic acid is carried out at 120 to 180°C, and then the water by-produced in the condensation reaction is removed from the system. A high-boiling aprotic polar solvent or an acid catalyst can be added to accelerate the ring-closing dehydration reaction. Examples of high-boiling aprotic polar solvents include N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). These solvents can be used alone or in combination. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These solvents can be used alone or in combination. The blending ratio of aromatic diphthalic anhydride to aromatic diamine is preferably aromatic diphthalic anhydride / aromatic diamine=1.01 to 1.50 / 1.0 by mole, and more preferably aromatic diphthalic anhydride / aromatic diamine=1.01 to 1.15 / 1.0 by mole. Blending at this ratio ultimately enables the synthesis of a copolymer containing imide groups at both ends.

[0047] In step E (or step E'), the copolymer containing imide groups at both ends obtained in step D (or step D') is first reacted with a specific aromatic diamine to synthesize an amic acid. This reaction also generally proceeds in a high-boiling aprotic polar solvent at room temperature (25°C) to 100°C. However, in the reaction between the copolymer containing imide groups at both ends and the specific aromatic diamine, it is preferable to use anisole or its derivatives (e.g., o-methylanisole, p-methylanisole, etc.) as the solvent rather than a high-boiling aprotic polar solvent. These solvents may be used alone or in combination of two or more. Similarly, the subsequent ring-closing dehydration reaction of the amic acid is carried out at 120 to 180°C, and then the water by-produced in the condensation reaction is removed from the system. A high-boiling aprotic polar solvent or an acid catalyst can be added to promote the ring-closing dehydration reaction. Examples of high-boiling aprotic polar solvents include N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). These solvents may be used alone or in combination. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These solvents may be used alone or in combination. The blending ratio of the copolymer containing imide groups at both ends to the aromatic diamine is preferably 1.0:1.6-2.5 by molar ratio, and more preferably 1.0:1.8-2.2 by molar ratio.

[0048] In step F (or step F'), the diamine having amino groups at both ends obtained in step E (or step E') is reacted with maleic anhydride at room temperature (25°C) to 100°C to synthesize maleamic acid, and finally, the molecular chain ends are blocked with maleimide groups by ring-closing dehydration while removing the water by-product in the system at 120 to 180°C, thereby obtaining the desired maleimide resin. The blending ratio of the diamine having amino groups at both ends to maleic anhydride is preferably 1.0:1.6-2.5 by molar ratio, and more preferably 1.0:1.8-2.2 by molar ratio.

[0049] After step F (or step F'), the product may be purified by a conventional method, for example, reprecipitation.

[0050] The maleimide resin (A) may be used alone or in combination of two or more. The content of component (A) in the composition of the present invention is preferably 5 to 95 mass %, more preferably 20 to 90 mass %.

[0051] (B) An organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule The component (B) used in the present invention is an organic compound having one or more allyl groups and one or more isocyanuric rings per molecule, and is used as a crosslinking agent. Therefore, it has one or more, preferably two or more, allyl groups per molecule. In addition, the isocyanuric rings have high heat resistance and act to improve mechanical properties and dielectric characteristics after curing.

[0052] Component (B) may be one having an epoxy group, an acryloyl group, or a carboxyl group, one that has been silicone-modified, or one that has been ether-modified. From the viewpoint of dielectric properties, however, alkyl diallyl isocyanurates such as triallyl isocyanurate and diallylmethyl isocyanurate are preferred.

[0053] The blend amount of component (B) is preferably 3 to 50 parts by mass, and more preferably 5 to 25 parts by mass, per 100 parts by mass of the total of components (A) and (B).

[0054] (C) Reaction initiator The reaction initiator (C) used in the present invention is added to promote the independent crosslinking reaction of the maleimide group in component (A) and the allyl group in component (B) or the crosslinking reaction between components (A) and (B). Component (C) is not particularly limited as long as it promotes the crosslinking reaction. Examples include ionic catalysts such as imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organophosphines, and organophosphonium salts; and radical polymerization initiators such as organic peroxides, hydroperoxides, and azoisobutyronitrile. Among these, organic peroxides are preferred, particularly from the viewpoint of promoting crosslinking between components (A) and (B). Examples of organic peroxides include dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, dibenzoyl peroxide, and dilauroyl peroxide. The reaction initiator of the component (C) may use one type alone, or two or more types in combination.

[0055] The amount of the reaction initiator is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of components (A) and (B). Outside this range, the balance between heat resistance and moisture resistance of the cured product may be poor, and the curing rate during molding may be either very slow or very fast. It is also well known that the hardening speed during molding varies depending on the type of reaction initiator, and when using an organic peroxide, for example, check the half-life temperature of the organic peroxide. There is a strong correlation between the half-life temperature and the reaction initiation temperature.

[0056] <Other additives> The thermosetting maleimide resin composition of the present invention may further contain various additives as needed, provided that the effects of the present invention are not impaired. Examples of other additives are listed below.

[0057] Thermosetting resin having a reactive group capable of reacting with a maleimide group In the present invention, in addition to the component (B), a thermosetting resin having a reactive group capable of reacting with a maleimide group may also be added. The thermosetting resin is not limited to any particular type, and examples include various resins other than component (A), such as epoxy resins, phenolic resins, melamine resins, silicone resins, cyclic imide resins, urea resins, thermosetting polyimide resins, modified polyphenylene ether resins, thermosetting acrylic resins, and epoxy-silicone hybrid resins. Reactive groups that can react with maleimide groups include epoxy groups, maleimide groups, hydroxyl groups, acid anhydride groups, alkenyl groups such as allyl groups and vinyl groups, (meth)acrylic groups, and thiol groups. Compounds containing allyl groups as other additives do not have an isocyanuric ring and are therefore distinct from component (B).

[0058] From the viewpoint of reactivity, the reactive group of the thermosetting resin is preferably selected from an epoxy group, a maleimide group, a hydroxyl group, an acid anhydride group, and an alkenyl group, and from the viewpoint of dielectric properties, an alkenyl group or a (meth)acrylic group is more preferable. However, the blending amount of the thermosetting resin having a reactive group capable of reacting with a maleimide group is 0 to 30 mass % of the total amount of component (A), component (B), and the thermosetting resin having a reactive group capable of reacting with a maleimide group.

[0059] inorganic filler In the present invention, an inorganic filler may also be added. It can be incorporated to enhance the strength and rigidity of the cured product of the thermosetting maleimide resin composition of the present invention, or to adjust the thermal expansion coefficient and dimensional stability of the cured product. Examples of inorganic fillers that can be used include those typically incorporated into epoxy resin compositions and silicone resin compositions. Examples include silicas such as spherical silica, fused silica, and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, barium sulfate, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass fibers, and glass particles. Furthermore, fluorine-containing resins, coating fillers, and / or hollow particles may be used to improve dielectric properties, and conductive fillers such as metal particles, metal-coated inorganic particles, carbon fibers, and carbon nanotubes may be added to impart conductivity. The inorganic fillers may be used alone or in combination of two or more.

[0060] The average particle size and shape of the inorganic filler are not particularly limited, but when molding a film or substrate, spherical silica with an average particle size of 0.5 to 5 μm is particularly suitable. The average particle size is the mass average particle size D 50 (or median diameter).

[0061] Furthermore, in order to improve the properties of the inorganic filler, it is preferable that the surface of the filler is treated with a silane coupling agent having an organic group capable of reacting with a maleimide group, such as an epoxy group-containing alkoxysilane, an amino group-containing alkoxysilane, a (meth)acrylic group-containing alkoxysilane, or an alkenyl group-containing alkoxysilane. As the silane coupling agent, a (meth)acrylic group- and / or amino group-containing alkoxysilane is preferably used, and specific examples thereof include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.

[0062] others In addition to the above, non-functional silicone oil, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber, photosensitizer, light stabilizer, polymerization inhibitor, flame retardant, pigment, dye, adhesive aid, etc. may be blended, and an ion trapping agent, etc. may be blended to improve electrical properties.

[0063] The thermosetting maleimide resin composition of the present invention can also be dissolved in an organic solvent and treated as a varnish. Forming the composition into a varnish facilitates film formation and facilitates application and impregnation of glass cloth made of E-glass, low-dielectric glass, quartz glass, and the like. Any organic solvent can be used as long as it dissolves the thermosetting resins containing reactive groups capable of reacting with maleimide groups, such as components (A) and (B), and other additives. Examples of such organic solvents include anisole, tetralin, xylene, toluene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and acetonitrile. These solvents may be used alone or in combination.

[0064] This thermosetting maleimide resin composition can be formed into an uncured resin sheet or uncured resin film by applying the varnish to a substrate and volatilizing the organic solvent, and can be further cured to form a cured resin sheet or cured resin film. Examples of methods for producing sheets and films are given below, but the methods are not limited to these.

[0065] For example, a thermosetting maleimide resin composition (varnish) dissolved in an organic solvent is applied to a substrate, and then the organic solvent is removed by heating the composition at a temperature of typically 80°C or higher, preferably 100°C or higher, for 0.5 to 5 hours, and then further heating the composition at a temperature of 130°C or higher, preferably 150°C or higher, for 0.5 to 10 hours, thereby forming a strong maleimide resin cured coating having a flat surface. The temperatures in the drying step for removing the organic solvent and the subsequent heat curing step may be constant, but it is preferable to increase the temperature stepwise, which allows the organic solvent to be efficiently removed from the composition and the curing reaction of the resin to proceed efficiently. The method for applying the varnish includes, but is not particularly limited to, a spin coater, a slit coater, a spray coater, a dip coater, a bar coater, and the like.

[0066] The substrate may be a commonly used material, such as polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, and polystyrene (PS) resin, and polyester resins such as polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, and polycarbonate (PC) resin. The surface of the substrate may be subjected to a release treatment. The thickness of the coating layer is not particularly limited, but is preferably in the range of 1 to 100 μm, and more preferably 3 to 80 μm, after solvent removal. A cover film may also be used on the coating layer.

[0067] Alternatively, the components may be premixed in advance and extruded into a sheet or film using a melt kneader, and then used as is.

[0068] The cured coatings obtained by curing the thermosetting maleimide resin composition of the present invention have excellent heat resistance, mechanical properties, electrical properties, adhesion to substrates, and solvent resistance, as well as a low dielectric constant. Therefore, they can be used in semiconductor devices, specifically, as passivation films or protective films on the surfaces of semiconductor elements, junction protective films for diodes, transistors, etc., alpha-ray shielding films for VLSIs, interlayer insulating films, ion implantation masks, etc., as well as conformal coatings on printed circuit boards, alignment films for liquid crystal surface elements, protective films for glass fibers, and surface protective films for solar cells. Furthermore, the thermosetting maleimide resin composition can be used in a wide range of paste compositions, such as printing paste compositions containing inorganic fillers and conductive paste compositions containing conductive fillers. Among these, adhesive applications are preferred.

[0069] Furthermore, since it can be formed into a film or sheet in an uncured state, has good handling properties, self-adhesiveness, and excellent dielectric properties, it is particularly suitable for use as a bonding film for flexible printed circuit boards (FPCs), etc. The cured resin film can also be used as a coverlay film.

[0070] Alternatively, the thermosetting maleimide resin composition can be used as a prepreg by impregnating glass cloth made from E-glass, low-dielectric glass, quartz glass, etc. with the varnish, removing the organic solvent, and leaving it in a semi-cured state. Furthermore, rigid substrates can be fabricated by laminating the prepreg with copper foil, etc.

[0071] [Manufacturing method] The thermosetting maleimide resin composition of the present invention can be produced by mixing the components (A), (B), and (C) and other additives that may be added as needed, using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a THINKY CONDITIONING MIXER (manufactured by THINKY CORPORATION). [Example]

[0072] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0073] The components used in the examples and comparative examples are shown below. In the following, the number average molecular weight (Mn) was measured using polystyrene as the standard under the following measurement conditions. Developing solvent: tetrahydrofuran (THF) Flow rate: 0.35mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-L TSKgel SuperHZ4000(4.6mmI.D.×15cm×1) TSKgel SuperHZ3000(4.6mmI.D.×15cm×1) TSKgel SuperHZ2000 (4.6mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 5 μL (0.2% by mass THF solution)

[0074] (A) Maleimide resin [Synthesis Example 1] (Production of bismaleimide compound, Reaction Scheme 1) A 2 L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser, and a thermometer was charged with 37.25 g (0.219 mol) of isophoronediamine, 76.94 g (0.35 mol) of pyromellitic anhydride, and 350 g of toluene, and the mixture was stirred at 80°C for 3 hours to synthesize an amic acid. The mixture was then heated to 110°C and stirred for 4 hours while distilling off the by-product water, to synthesize a block copolymer. After that, Priamine-1075 (CRODA, diamine compound containing dimer diamine: H2N-C) was added to the flask containing the block copolymer solution, which had been cooled to room temperature. 36 H 70 116.88 g (0.219 mol) of —NH (average composition formula) was added and stirred at 80°C for 3 hours to synthesize an amic acid. The temperature was then raised to 110°C and stirred for 4 hours while distilling off the by-product water, synthesizing a diamine compound at both ends. The flask containing the resulting diamine-terminated solution was cooled to room temperature, and 18.88 g (0.193 mol) of maleic anhydride was added. The mixture was then heated again and stirred at 80°C for 3 hours to synthesize an amic acid. The mixture was then heated to 110°C and stirred for 15 hours while distilling off the by-product water. The mixture was then washed five times with 300 g of water to obtain a bismaleimide compound varnish. The varnish was then reprecipitated by adding it dropwise to 3,000 g of hexane. The solvent was removed and the mixture was dried to obtain the desired dark brown solid bismaleimide compound represented by the following formula (A-1). The Mn of this bismaleimide compound was 8,000. [ka]

[0075] [Synthesis Example 2] A 1 L glass four-neck flask equipped with a stirrer, Dean-Stark tube, cooling condenser, and thermometer was charged with 65.06 g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 35.26 g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline), and 250 g of anisole, and the mixture was stirred at 80°C for 3 hours to synthesize an amic acid. The mixture was then heated to 150°C and stirred for 2 hours while distilling off the by-product water, to synthesize a block copolymer. After that, 7.05 g (0.015 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was added to the flask containing the block copolymer solution, which had been cooled to room temperature, and the mixture was stirred at 80°C for 3 hours to synthesize an amic acid.The mixture was then heated to 150°C and stirred for 2 hours while distilling off the by-product water, synthesizing a diamine-terminated compound. The flask containing the resulting solution of diamines at both ends was cooled to room temperature, and then 1.45 g (0.015 mol) of maleic anhydride was added. The mixture was stirred at 80°C for 3 hours to synthesize maleamic acid. The temperature was then raised to 150°C and the mixture was stirred for 2 hours while distilling off the by-product water, yielding a varnish of a bismaleimide compound represented by formula (A-2) below. The anisole was not completely removed, and the nonvolatile content was adjusted to 40% by mass. The Mn of the bismaleimide compound represented by formula (A-2) was 11,500. [ka]

[0076] (A-3): A linear alkylene group-containing bismaleimide compound represented by the following formula (BMI-3000J, manufactured by Designer Molecules Inc., Mn: 7500, for comparative purposes) [ka] (A-4): 4,4'-diphenylmethane bismaleimide (BMI-1000: manufactured by Daiwa Chemical Industry Co., Ltd., Mn: 358, for comparative example) (A-5): A linear alkylene group-containing bismaleimide compound represented by the following formula (BMI-1500, manufactured by Designer Molecules Inc., Mn: 2400, for comparative purposes) [ka]

[0077] (B) An organic compound having one or more allyl groups and one or more isocyanuric rings in one molecule (B-1): Triallyl isocyanurate (TAIC, manufactured by Mitsubishi Chemical Corporation) (B-2): Alkyl diallyl isocyanurate (L-DAIC, manufactured by Shikoku Chemical Industries, Ltd.) (B-3): Diallyl isophthalate (Daiso DAP 100 Monomer, manufactured by Osaka Soda Co., Ltd., for comparison) (B-4): Bifunctional acrylic monomer (KAYARADR-684, manufactured by Nippon Kayaku Co., Ltd., for comparative example) (B-5): Tris(2-acryloyloxyethyl) isocyanurate (FA-731A, manufactured by Hitachi Chemical Co., Ltd., for comparative purposes)

[0078] (C) Reaction initiator (C-1) Dicumyl peroxide (Percumyl D, manufactured by NOF Corporation)

[0079] <Film Preparation> An anisole varnish with a nonvolatile content of 50% by mass was prepared using the formulations shown in Tables 1 and 2. This varnish-like thermosetting maleimide resin composition was applied to a 38-μm-thick PET film using a roller coater so that the dried thickness would be 50 μm, and the film was dried at 120° C. for 10 minutes to obtain an uncured resin film. The uncured resin film was then placed on a 100-μm-thick tetrafluoroethylene-ethylene copolymer resin film (manufactured by AGC Inc., product name: Aflex) so that the resin layer of the uncured resin film was in contact with the tetrafluoroethylene-ethylene copolymer resin film, and the film was cured at 180° C. for 2 hours to obtain a cured resin film. In the following evaluation tests, the uncured resin film from which the PET film was peeled off, and the cured resin film from which the PET film and the tetrafluoroethylene-ethylene copolymer resin film were peeled off were subjected to each evaluation test. The results are shown in Tables 1 and 2.

[0080] <Film handling> The uncured resin film and the cured resin film were folded 100 times at 180°, and films with no cracks or other defects were marked with a circle, and films with cracks or other defects were marked with an x.

[0081] <Relative permittivity, dielectric loss tangent> Using the cured resin film, a network analyzer (E5063-2D5 manufactured by Keysight) and a strip line (manufactured by Keycom Corporation) were connected, and the relative dielectric constant and dielectric loss tangent of the cured resin film at a frequency of 10 GHz were measured.

[0082] <Glass transition temperature> The glass transition temperature (Tg) of the cured resin film was measured using a DMA-800 manufactured by TA Instruments.

[0083] <Coefficient of thermal expansion (CTE)> The coefficient of thermal expansion (CTE) of the cured resin film was measured using a TMA-Q400 manufactured by TA Instruments Co., Ltd. Values ​​in the range of 0 to 40°C were used as the coefficient of thermal expansion.

[0084] [Table 1]

[0085] [Table 2] *1: Not only was the film difficult to handle, but it also had low solvent solubility, and some of it remained undissolved at the varnish stage. *2: It was liquid and had strong tack, so it could not be handled as a film. *3: The viscosity was too low to obtain a cured product.

[0086] <Film Preparation> Example 6 To 30 g of the varnish with a nonvolatile content of 40% by mass obtained in Synthesis Example 2, 12.0 g of (B-1) and 0.24 g of (C-1) were added and stirred thoroughly at room temperature. This varnish-like thermosetting maleimide resin composition was applied to a 38 μm-thick PET film using a roller coater so that the dried thickness would be 50 μm, and then dried at 150° C. for 10 minutes to obtain an uncured resin film. Furthermore, the uncured resin film was placed on a 100 μm-thick tetrafluoroethylene-ethylene copolymer resin film (manufactured by AGC Inc., product name: Aflex) so that the resin layer of the uncured resin film was in contact with the tetrafluoroethylene-ethylene copolymer resin film, and cured at 180° C. for 2 hours to obtain a cured resin film.

[0087] (Comparative Example 12) A cured resin film was obtained in the same manner as in Example 6, except that (B-1) was not added and the amount of (C-1) was changed to 0.12 g. (Comparative Examples 13 to 15) Cured resin films were obtained in the same manner as in Example 6, except that (B-3) to (B-5) were used instead of (B-1).

[0088] For each of the films produced in Example 6 and Comparative Examples 12 to 15, the uncured resin film from which the PET film was removed, and the cured resin film from which the PET film and the tetrafluoroethylene-ethylene copolymer resin film were removed were subjected to the following evaluation tests. The results are shown in Table 3.

[0089] <Film handling> The uncured resin film and the cured resin film were folded 100 times at 180°, and films with no cracks or other defects were marked with a circle, and films with cracks or other defects were marked with an x.

[0090] <Relative permittivity, dielectric loss tangent> Using the cured resin film, a network analyzer (E5063-2D5 manufactured by Keysight) and a strip line (manufactured by Keycom Corporation) were connected, and the relative dielectric constant and dielectric loss tangent of the cured resin film at a frequency of 10 GHz were measured.

[0091] <Glass transition temperature> The glass transition temperature (Tg) of the cured resin film was measured using a DMA-800 manufactured by TA Instruments.

[0092] <Coefficient of thermal expansion (CTE)> The coefficient of thermal expansion (CTE) of the cured resin film was measured using a TMA-Q400 manufactured by TA Instruments Co., Ltd. Values ​​in the range of 0 to 40°C were used as the coefficient of thermal expansion.

[0093] [Table 3]

[0094] From the above results, it has been confirmed that the thermosetting maleimide resin composition of the present invention has a high glass transition temperature of the cured product, excellent high-temperature properties, and excellent dielectric properties, and that uncured resin films and cured resin films made from the composition have excellent handleability, and therefore, its usefulness as an insulating material suitable for substrate applications has been confirmed.

Claims

1. (A) A maleimide resin represented by the following formula (3) and having a number average molecular weight of 3,000 or more: (B) An organic compound having two or more allyl groups and one or more isocyanuric rings in one molecule and (C) Reaction initiator wherein the content of component (A) is 5 to 95 mass %, and the blending amount of component (B) is 3 to 50 parts by mass per 100 parts by mass of the total of component (A) and component (B). 【Chemical 1】 (In formula (3), X 1 are independently expressed by the following formula: 【Chemistry 2】 (a is a number from 1 to 6.) 【Chemistry 3】 is a divalent group selected from k is a number from 1 to 30, l is a number from 0 to 10, A 1 and A 2 are each independently a divalent aromatic group represented by the following formula (4) or (5): 【Chemistry 4】 (In formula (4), X 2 are independently expressed by the following formula: 【Chemistry 5】 (a is a number from 1 to 6.) 【Chemistry 6】 is a divalent group selected from R 2 are independently a hydrogen atom, a chlorine atom, or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms. 【Chemistry 7】 (In formula (5), X 1 indicates the same as above.)

2. 2. The thermosetting maleimide resin composition according to claim 1, wherein the reaction initiator of component (C) is a radical polymerization initiator.

3. 3. The thermosetting maleimide resin composition according to claim 1, wherein the content of the component (A) in the composition is 5 to 95 mass%, and the blending amount of the component (B) is 3 to 50 mass parts per 100 mass parts of the total of the components (A) and (B).

4. An uncured resin film comprising the thermosetting maleimide resin composition according to any one of claims 1 to 3.

5. A cured resin film comprising a cured product of the thermosetting maleimide resin composition according to any one of claims 1 to 3.

6. A prepreg comprising the thermosetting maleimide resin composition according to any one of claims 1 to 3 and a fiber substrate.

7. An adhesive comprising the thermosetting maleimide resin composition according to any one of claims 1 to 3.

8. A substrate comprising the thermosetting maleimide resin composition according to any one of claims 1 to 3.

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