Thermosetting maleimide 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 to 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 realize this, materials for high frequency bands are required, and since reduction of 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 required for circuit board applications.In circuit board applications, insulating materials with excellent dielectric properties are particularly required for rigid and flexible circuit boards, and reactive polyphenylene ether resins (PPE) have come to be used for rigid circuit boards, while liquid crystal polymers (LCPs) and products with improved properties called modified polyimides (MPIs) have come to be used for flexible printed circuit boards (FPCs).

[0004] Although these materials have excellent characteristics, it is also true that they have many problems. 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 had problems with insulation resistance in long-term reliability tests (e.g., Patent Documents 1 and 2). Many inventions have been disclosed regarding LCPs, such as further improving the performance of LCPs and base films and coverlay films for FPCs that use LCPs (e.g., Patent Documents 3 and 4). However, LCPs are difficult to mass-produce in response to demand, so their use is limited, and molding at high temperatures of 300°C or higher is necessary, which is a problem specific to thermoplastic resins, and an adhesive with low dielectric properties is required to bond copper-clad laminates. There are many areas that need to be improved.

[0005] Therefore, the use of MPIs has been considered depending on the frequency band, and many inventions related to MPIs have been disclosed (for example, Patent Documents 5 and 6). Although these MPIs have improved dielectric properties compared to current polyimides, they are thermoplastic resins like LCPs, and therefore have the same problems as LCPs. In addition, it is known that the dielectric properties become very poor due to the moisture absorption inherent to polyimides. In order to solve these problems, MPIs having a dimer diamine skeleton have also been disclosed (Patent Document 7), but they have a significantly lower glass transition temperature (Tg) than conventional MPIs and lack dimensional stability. In addition, when producing MPIs, it is necessary to use a large amount of aprotic polar solvents, such as N-methylpyrrolidone (NMP), but the use of aprotic polar solvents is not preferable from the viewpoint of environmental conservation.

[0006] In recent years, maleimide resins have been attracting attention as being similar to polyimides. Among maleimide resins, bismaleimide resins are the most common, and many of them are known to be low molecular weight, and 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, the dielectric properties are not sufficient compared to LCP or MPI, and there is still room for improvement.

[0007] In response to this, a composition and its cured product using a maleimide compound having a dimer diamine skeleton as a material for FPCs have been disclosed (Patent Document 8), but although it has excellent dielectric properties, it has a low Tg and a high coefficient of thermal expansion (CTE), which is the opposite of the characteristics of general maleimide resins, and it still lacks dimensional stability.In addition, since it is a mixture of a bismaleimide resin having a long-chain alkyl group and a hard low-molecular 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] WO 2019 / 65940 [Patent Document 2] WO 2019 / 65941 [Patent Document 3] WO 2013 / 65453 [Patent Document 4] JP 2013-74129 A [Patent Document 5] JP 2017-78102 A [Patent Document 6] JP 2019-104818 A [Patent Document 7] JP 2020-56011 A [Patent Document 8] International Publication No. 2016 / 114287 [Patent Document 9] JP 2014-1289 A Summary of the Invention [Problem to be solved by the invention]

[0010] However, the resin composition described in Patent Document 9 is 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 having excellent dielectric properties, in particular a thermosetting maleimide resin composition suitable for substrate applications, which has a high glass transition temperature (Tg) of the cured product, excellent high-temperature properties, excellent dielectric properties, and excellent dimensional stability, and an uncured resin film and a cured resin film made of the same, which have excellent handleability, and also to provide a substrate using the same. [Means for solving the problem]

[0011] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that the following thermosetting maleimide resin composition can achieve the above object, thereby completing 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 1. 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 bracketed by n and m is not limited, and the bonding pattern may be alternating, block, or random. <2> In formula (1), A is any of the tetravalent organic groups represented by the following structural formulas: <1> 2. 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 a cyclic imide structure in general formula (1).) <3> In formula (1), B is a divalent hydrocarbon group derived from a diamine derived from a dimer acid. <1> or <2> 2. 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 1. A thermosetting maleimide resin composition comprising: [ka] (In formula (3), X 1 are independently expressed by the following formula: [ka] (a is a number from 1 to 6.) [ka] is a divalent group selected from k is a number from 1 to 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 the following formula (5). [ka] (In formula (4), X 2 are independently expressed by the following formula: [ka] (a is a number from 1 to 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> 13. The thermosetting maleimide resin composition according to claim 12. <6> The reaction initiator of component (C) is a radical polymerization initiator. <1> from <5> 13. The thermosetting maleimide resin composition according to claim 12. <7> <1> or <4> 2. An uncured resin film comprising the thermosetting maleimide resin composition according to claim 1. <8> <1> or <4> 2. 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> 2. An adhesive comprising the thermosetting maleimide resin composition according to claim 1. <11> <1> or <4> 2. A substrate comprising the thermosetting maleimide resin composition according to claim 1. Effect of the Invention

[0013] The thermosetting maleimide resin composition of the present invention has a high glass transition temperature of the cured product, and is also excellent in dielectric properties and dimensional stability. In addition, the thermosetting maleimide resin composition of the present invention can be produced without using an aprotic polar solvent such as NMP, and has 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 material for substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[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 general formula (3). In general, many maleimide compounds have a number average molecular weight of 2,000 or less. Many of these maleimide compounds having a number average molecular weight of 2,000 or less have a high Tg, but are poor in processability and moldability into films before and after curing, and are 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) calculated using polystyrene standards by gel permeation chromatography (GPC) measurement under the following measurement conditions is 3,000 or more, more preferably 3,500 to 50,000, and particularly preferably 4,000 to 40,000. If the molecular weight is 3,000 or more, the resulting composition is 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 in THF solution)

[0018] Furthermore, when the maleimide resin of component (A) is represented by the following formula (1) or (3), not only does the resulting film have good mechanical properties and easy handling 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 uniform from location to location.

[0019] A 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 a 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 them, it is preferable that the divalent hydrocarbon group is a branched divalent hydrocarbon group in which one or more hydrogen atoms 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. 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, called 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 mainly composed of dicarboxylic acids with 36 carbon atoms, which are produced by dimerizing unsaturated fatty acids with 18 carbon atoms, the raw materials of which are natural products such as vegetable oils and fats, and the dimer acid (dimer diamine) skeleton refers to a structure obtained by removing a carboxy 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 the dimer acids shown in (a) to (d) below. [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 having 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. Here, 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 preferable. 1 may be the same or different. Moreover, the above 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 forming a cyclic imide structure in formula (1).)

[0024] In formula (1), W is B or Q. Regarding W, whether it is a structural unit having B or Q is determined depending on the production method described later.

[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. 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 alternate, block, or random, but is preferably a block bond.

[0026] The maleimide resin represented by formula (1) can be produced efficiently by any of the following two methods, although there are no particular limitations on the production method. 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 ring-closing and dehydrating the amic acid. Following the step A, a step B is carried out 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. The method for producing a maleimide resin includes, subsequent to step B, a step C of synthesizing maleamic acid using 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', a step B' is carried out 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. The method for producing a maleimide resin includes, subsequent to the step B', a step C' of synthesizing maleamic acid using the reaction product obtained in the step B' and maleic anhydride, and capping the molecular chain ends by ring-closing dehydration.

[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) above.) H2N-B-NH2(8) (In formula (8), B is the same as that shown in formula (1) above.)

[0029] The above two manufacturing methods are shown, but the basic flow is to synthesize an amic acid from a tetracarboxylic dianhydride and a diamine, go through step A (or step A') where they perform ring-closing dehydration, after step A (or step A'), add a diamine different from the previous step A (or step A') to synthesize an amic acid, go through step B (or step B') where they perform ring-closing dehydration, after step B (or step B'), react with maleic anhydride to synthesize a maleamic acid, and finally go through step C (or step C') where the molecular chain end is blocked with a maleimide group by ring-closing dehydration, thereby obtaining the maleimide resin represented by formula (1). The main difference between the above two manufacturing methods is only the order of the types of diamines added.

[0030] In the above two production methods, each step can be roughly divided into two: a synthesis reaction of an amic acid or a 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 reacted with a specific diamine to synthesize an amic acid. This reaction generally proceeds in an organic solvent (e.g., a non-polar 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 by the condensation reaction is removed from the system. In order to promote the ring-closing dehydration reaction, an organic solvent (e.g., a non-polar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst can be added. Examples of the organic solvent 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 the acid catalyst 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 tetracarboxylic dianhydride to the diamine is preferably tetracarboxylic dianhydride / diamine=1.01 to 1.50 / 1.0, more preferably tetracarboxylic dianhydride / diamine=1.01 to 1.35 / 1.0. By mixing them in this ratio, a copolymer containing imide groups at both ends can be synthesized.

[0032] In step B (or step B'), first, the copolymer containing imide groups at both ends obtained in step A (or step A') is reacted with a specific diamine to synthesize an amic acid. This reaction also generally proceeds in an organic solvent (e.g., a non-polar 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. In order to promote the ring-closing dehydration reaction, an organic solvent (e.g., a non-polar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst can be added. Examples of the organic solvent 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 the acid catalyst 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-produced in the system at 95 to 120°C to obtain 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 less, since this makes it difficult for side reactions and high molecular weight substances to occur. According to such a 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 according to a conventional method, for example, by reprecipitation.

[0035] A maleimide resin represented by formula (3) [ka]

[0036] In formula (3), X 1 are independently a divalent group selected from the following formulas: [ka] (a is a number from 1 to 6.) [ka] X in formula (3) 1 From the viewpoint of availability of raw materials, -CH2- and -C(CH3)2- are preferred.

[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 a solvent and film-forming ability when uncured, and the toughness and heat resistance of the resulting cured product. l 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 from 1 to 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 formula (4) 2 From the viewpoint of availability of raw materials, -CH2- and -C(CH3)2- are preferred. 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, a cyclohexyl group, and the like, 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, Br, and the like, 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 It is more preferable that A is different from A in the formula (3). 1 When is the above formula (4), A 2 is the above formula (5), or A 1 When is the above formula (5), A 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) is produced using a divalent acid anhydride and a diamine having the same bisphenol skeleton.

[0041] The method for producing the maleimide resin represented by formula (3) is not particularly limited, 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 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, subsequent to step E, a step F of reacting the reaction product obtained in step E with maleic anhydride to synthesize maleamic acid and 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 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. The method for producing a maleimide resin includes, subsequent to step E', step F' of reacting the reaction product obtained in step E' with maleic anhydride to synthesize maleamic acid, and capping the molecular chain terminals with maleimide groups by ring-closing dehydration.

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

[0044] The two manufacturing methods described above are shown, but the basic flow is to synthesize an amic acid from an aromatic diphthalic acid and an aromatic diamine, go through step D (or step D') where they perform ring-closing dehydration, and after step D (or step D'), add an aromatic diamine different from the previous step D (or step D') to synthesize an amic acid, and then go through step E (or step E') where they perform ring-closing dehydration, and after step E (or step E'), react with maleic anhydride to synthesize a maleamic acid, and finally go through step F (or step F') where they perform ring-closing dehydration to block 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 only in the order in which the types of aromatic diamine are added.

[0045] In the above two production methods, each step can be roughly divided into two: a synthesis reaction of an amic acid or a 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, but 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 under conditions of 120 to 180°C, and then the water by-produced by the condensation reaction is removed from the system while the reaction proceeds. In order to promote the ring-closing dehydration reaction, a high-boiling aprotic polar solvent or an acid catalyst can be added. Examples of high-boiling aprotic polar solvents include 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 blending ratio of aromatic diphthalic anhydride and aromatic diamine is preferably aromatic diphthalic anhydride / aromatic diamine=1.01-1.50 / 1.0 by mole, more preferably aromatic diphthalic anhydride / aromatic diamine=1.01-1.15 / 1.0 by mole. Blending at this ratio results in the synthesis of a copolymer containing imide groups at both ends.

[0047] In step E (or step E'), first, the copolymer containing imide groups at both ends obtained in step D (or step D') is 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, but in the reaction between the copolymer containing imide groups at both ends and a specific aromatic diamine, it is preferable to use anisole and its derivatives (e.g., o-methylanisole, p-methylanisole, etc.) as a solvent rather than a high-boiling aprotic polar solvent. These 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 under conditions of 120 to 180°C, and then the water by-produced by the condensation reaction is removed from the system while the reaction proceeds. In order to promote the ring-closing dehydration reaction, a high-boiling aprotic polar solvent or an acid catalyst can be added. Examples of high-boiling aprotic polar solvents include 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 blending ratio of the copolymer containing imide groups at both ends to the aromatic diamine is preferably 1.0:1.6-2.5, more preferably 1.0:1.8-2.2, in terms of 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 at 120 to 180°C while removing the water by-produced in the system, thereby obtaining the desired maleimide resin. The compounding ratio of the diamine having amino groups at both ends to maleic anhydride is preferably 1.0:1.6-2.5, more preferably 1.0:1.8-2.2, in terms of molar ratio.

[0049] After step F (or step F'), purification may be performed according to a conventional method, for example, by reprecipitation.

[0050] The maleimide resin of component (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 in one molecule, and is used as a crosslinking agent. Therefore, it has one or more, preferably two or more, allyl groups in one molecule. In addition, the isocyanuric ring has high heat resistance and acts to improve mechanical properties and dielectric properties after curing.

[0052] Examples of the component (B) include those having an epoxy group, an acryloyl group or a carboxyl group, silicone-modified ones, and ether-modified ones. From the viewpoint of dielectric properties, however, alkyl diallyl isocyanurates such as triallyl isocyanurate and diallyl methyl isocyanurate are preferred.

[0053] The blend amount of the 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 the components (A) and (B).

[0054] (C) Reaction initiator The reaction initiator of the component (C) used in the present invention is added to promote the single crosslinking reaction of the maleimide group of the component (A) and the allyl group of the component (B) or the crosslinking reaction between the component (A) and the component (B). The component (C) is not particularly limited as long as it promotes the crosslinking reaction, and examples thereof include ion 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 from the viewpoint of promoting the crosslinking between the component (A) and the component (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 either a single type alone, or a combination of two or more types.

[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 the components (A) and (B). Outside this range, the balance between the heat resistance and moisture resistance of the cured product may become poor, and the curing speed during molding may become very slow or fast. In addition, as is well known, the hardening speed during molding differs 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 required, provided that the effects of the present invention are not impaired. Examples of other additives are given below.

[0057] Thermosetting resin having a reactive group capable of reacting with a maleimide group In the present invention, a thermosetting resin having a reactive group capable of reacting with a maleimide group may be further added in addition to the component (B). The thermosetting resin is not limited to a specific type, and examples thereof 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. Examples of 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 having allyl groups as other additives do not have an isocyanuric ring and are distinguished from component (B).

[0058] From the viewpoint of reactivity, the reactive group of the thermosetting resin is preferably selected from among 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 % in the total amount of the component (A), the 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 be further added. It may be blended for the purpose of increasing the strength or rigidity of the cured product of the thermosetting maleimide resin composition of the present invention, or adjusting the thermal expansion coefficient or dimensional stability of the cured product. As the inorganic filler, those usually blended in epoxy resin compositions or silicone resin compositions can be used. For example, 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 fiber, and glass particles may be mentioned. 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 for the purpose of imparting conductivity. The inorganic filler may be used alone or in combination of two or more types.

[0060] The average particle size and shape of the inorganic filler are not particularly limited, but when forming a film or substrate, spherical silica with an average particle size of 0.5 to 5 μm is preferably used. 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 inorganic filler is surface-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, and an alkenyl group-containing alkoxysilane. As the silane coupling agent, an alkoxysilane containing a (meth)acrylic group and / or an amino group 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 be dissolved in an organic solvent and treated as a varnish. By forming the composition into a varnish, it becomes easier to form a film, and also easier to apply and impregnate glass cloth made of E glass, low dielectric glass, quartz glass, etc. The organic solvent can be used without limitation as long as it dissolves the thermosetting resin having a reactive group capable of reacting with the maleimide group as the component (A), the component (B), and other additives, and examples of the organic solvent include anisole, tetralin, xylene, toluene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, etc. These may be used alone or in combination of two or more.

[0064] This thermosetting maleimide resin composition can be made into an uncured resin sheet or uncured resin film by applying the above-mentioned varnish to a substrate and volatilizing the organic solvent, and can be further cured to make a cured resin sheet or cured resin film. Examples of the production methods for the sheet and film are given below, but the present invention is not limited thereto.

[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 substrate at a temperature of typically 80° C. or higher, and preferably 100° C. or higher, for 0.5 to 5 hours, and then the substrate is further heated at a temperature of 130° C. or higher, and preferably 150° C. or higher, for 0.5 to 10 hours, to form 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 each be constant, but it is preferable to increase the temperature stepwise, which allows the organic solvent to be efficiently removed from the composition and allows the curing reaction of the resin to proceed efficiently. The method for applying the varnish includes, but is not limited to, a spin coater, a slit coater, a spray, a dip coater, a bar coater, and the like.

[0066] The substrate may be one that is generally used, 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 the thickness after distillation of the solvent is in the range of 1 to 100 μm, preferably 3 to 80 μm. Furthermore, a cover film may be used on the coating layer.

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

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

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

[0070] In addition, the thermosetting maleimide resin composition in the form of a varnish can be used as a prepreg by impregnating glass cloth made of E-glass, low dielectric glass, quartz glass, etc., and removing the organic solvent to semi-harden it. In addition, a rigid substrate can be produced by laminating the prepreg and copper foil.

[0071] [Manufacturing method] Examples of a method for producing the thermosetting maleimide resin composition of the present invention include a method in which the components (A), (B), and (C) and other additives that are added as necessary are mixed using, for example, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) or a mixer such as a THINKY CONDITIONING MIXER (manufactured by Thinky Corporation). EXAMPLES

[0072] The present invention will be specifically described 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 under the following measurement conditions using polystyrene as the standard. 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 in THF solution)

[0074] (A) Maleimide resin [Synthesis Example 1] (Production of bismaleimide compound, reaction formula 1) 37.25g (0.219 mol) of isophoronediamine, 76.94g (0.35 mol) of pyromellitic anhydride, and 350g of toluene were added to a 2L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser, and a thermometer, 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 36 H 70 Amic acid was synthesized by adding 116.88 g (0.219 mol) of -NH2 (average composition formula) and stirring at 80°C for 3 hours. The temperature was then raised to 110°C and stirred for 4 hours while distilling off the by-product water, synthesizing a diamine at both ends. The flask containing the obtained diamine-terminated solution was cooled to room temperature, and then 18.88 g (0.193 mol) of maleic anhydride was added. The mixture was 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, and washed five times with 300 g of water to obtain a varnish of a bismaleimide compound. The varnish was then dropped into 3,000 g of hexane to perform a reprecipitation process, and the solvent was removed and 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] 65.06g (0.125 mol) of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 35.26g (0.115 mol) of 4,4-methylenebis(2,6-diethylaniline), and 250g of anisole were added to a 1L glass four-neck flask equipped with a stirrer, a Dean-Stark tube, a cooling condenser, and a thermometer, 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 that 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 at both ends. The flask containing the obtained solution of diamines at both ends was cooled to room temperature, and then 1.45 g (0.015 mol) of maleic anhydride was added and stirred at 80°C for 3 hours to synthesize maleamic acid. The temperature was then raised to 150°C and stirred for 2 hours while distilling off the by-product water, to obtain a varnish of a bismaleimide compound represented by the following formula (A-2). The anisole was not completely removed, and the non-volatile content was adjusted to 40 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 comparison) (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 Kasei Co., 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 comparison purposes) (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, NOF Corp.)

[0079] <Film Preparation> An anisole varnish with a non-volatile content of 50% by mass was prepared with the formulation shown in Tables 1 and 2, and this varnish-like thermosetting maleimide resin composition was applied to a 38 μm-thick PET film with a roller coater so that the thickness after drying would be 50 μm, and dried for 10 minutes at 120° C. 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. 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 180° 100 times, and the film without defects such as cracks was marked with an ◯, and the film with defects such as cracks was marked with an X.

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

[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 made 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, it also had low solvent solubility to begin with, and some of the film 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 12.0g of (B-1) and 0.24g of (C-1) were added to 30g of the varnish having a non-volatile content of 40% by mass obtained in Synthesis Example 2, and the mixture was thoroughly stirred at room temperature. The varnish-like thermosetting maleimide resin composition was applied to a PET film having a thickness of 38 μm by a roller coater so that the thickness after drying was 50 μm, and the mixture was dried for 10 minutes at 150° C. to obtain an uncured resin film. Furthermore, the uncured resin film was placed on a tetrafluoroethylene-ethylene copolymer resin film having a thickness of 100 μm (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 mixture was cured at 180° C. for 2 hours to obtain a cured resin film.

[0087] Comparative Example 12 The same treatment as in Example 6 was carried out, except that (B-1) was not added and the amount of (C-1) was changed to 0.12 g, to obtain a cured resin film. (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 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 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 180° 100 times, and the film without defects such as cracks was marked with an ◯, and the film with defects such as cracks was marked with an X.

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

[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 made 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, the thermosetting maleimide resin composition of the present invention has been confirmed to be useful as an insulating material suitable for substrate applications, since the cured product has a high glass transition temperature, has excellent high-temperature characteristics, and has excellent dielectric characteristics, and the uncured resin films and cured resin films made of the composition have excellent handleability.

Claims

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 two or more allyl groups and one or more isocyanuric rings in one molecule. and (C) Reaction initiator A thermosetting maleimide resin composition comprising: A thermosetting maleimide resin composition, wherein the content of component (A) in the composition 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). 【Chemistry 1】 (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): 【Chemistry 2】 (In formula (2), R 1 are independently a hydrogen atom or a methyl group, 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 bracketed by n and m is not limited, and the bonding pattern may be alternating, block, or random.

2. 2. The thermosetting maleimide resin composition according to claim 1, wherein A in formula (1) is any one of tetravalent organic groups represented by the following structural formulas: 【Chemistry 3】 (The bond not bonded to a substituent in the above structural formula is bonded to the carbonyl carbon that forms a cyclic imide structure in general formula (1).)

3. 3. The thermosetting maleimide resin composition according to claim 1, wherein B in formula (1) is a divalent hydrocarbon group derived from a diamine derived from a dimer acid.

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

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

6. A cured resin film comprising a cured product of the thermosetting maleimide resin composition according to any one of claims 1 to 4.

7. A prepreg comprising the thermosetting maleimide resin composition according to any one of claims 1 to 4 and a fiber substrate.

8. An adhesive comprising the thermosetting maleimide resin composition according to any one of claims 1 to 4.

9. A substrate comprising the thermosetting maleimide resin composition according to any one of claims 1 to 4.

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