Bismaleimide compound, method for producing bismaleimide compound, resin composition, cured product thereof, semiconductor element, dry film resist, and cured film

Abstract

The purpose of the present invention is to provide a bismaleimide compound which has good compatibility with other resins, has a high Tg value and can be developed by an alkali. This bismaleimide compound is represented by general formula (1). In formula (1), X moieties are each independently a divalent hydrocarbon group having 6-200 carbon atoms, Y moieties are each independently a divalent hydrocarbon group having 6-50 carbon atoms, and Z moieties are each independently a hydrogen atom or a monovalent group that is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. However, at least one Z moiety is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units, and represents an integer between 1 and 100.

Description

Bismaleimide compound, method for producing bismaleimide compound, resin composition, cured product thereof, semiconductor element, dry film resist, and cured film

[0001] The present invention relates to a bismaleimide compound, a method for producing the bismaleimide compound, a resin composition, a cured product thereof, a semiconductor device, a dry film resist, and a cured film. The resin composition of the present invention can be used as a protective film for semiconductor devices, an interlayer insulating film, an insulating film for rewiring layers, etc.

[0002] In recent years, electronic devices have become smaller and more powerful, and there is a demand for finer and denser wiring in the surface protection films, interlayer insulating films, and redistribution layer insulating films of semiconductor elements. Furthermore, materials for high-frequency bands will be required in the next generation, and reducing transmission loss as a noise countermeasure will be essential, so there is a demand for the development of insulating materials with excellent dielectric properties.

[0003] Conventionally, polyimide resins and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, have been widely used for surface protection films and interlayer insulating films of semiconductor devices (Patent Document 1). When using polyimide resins or polybenzoxazole resins as surface protection films or interlayer insulating films, a known method for forming through-holes and the like is to use a positive photoresist containing these resins for etching. However, this method requires cumbersome processes such as applying and removing the photoresist. Therefore, heat-resistant materials with photosensitivity have been investigated to streamline the work process (Patent Document 2). It has been found that these materials do not provide satisfactory dielectric properties for high-frequency band applications, such as those associated with 5G. In response, Patent Document 3 reports that an epoxy resin composition containing an epoxy resin, an active ester compound, and a triazine-containing cresol novolac resin is effective in reducing dielectric loss tangent, but even this material requires even lower dielectric constant for high-frequency applications.

[0004] On the other hand, Patent Document 4 reports that a resin film made of a resin composition containing a bismaleimide resin having a long-chain alkyl group as a non-epoxy material and a curing agent has excellent low dielectric properties.

[0005] Furthermore, Patent Documents 5 and 6 disclose polyimides made from dimer diamines and alicyclic diamines derived from dimer acids, which are dimers of aromatic tetracarboxylic acids and unsaturated fatty acids such as oleic acid.

[0006] Bismaleimide compounds are suitable materials for surface protection films, interlayer insulating films, and insulating films for redistribution layers of semiconductor devices. While bismaleimide compounds are resins with excellent heat resistance, flame retardancy, and dielectric properties, known bismaleimide compounds that do not exhibit curing reactivity with epoxy resins suffer from the problem of insufficient heat resistance when used in combination with epoxy-curing curable resins. Therefore, it has been proposed to use an amine-modified bismaleimide compound obtained by reacting the amino group of a monoamine compound such as aminophenol with the unsaturated N-substituted maleimide group of the bismaleimide compound in combination with an epoxy-curing curable resin (Patent Document 7). However, due to their insufficient alkaline developability, these compounds are insufficient as insulating film materials, particularly as required for redistribution layers with increasingly miniaturized circuits in recent years.

[0007] It has also been proposed to use a bismaleimide compound modified with an amine compound having a carboxy group, such as aminobenzoic acid, in combination with an epoxy-curable resin (Patent Document 8). However, this compound has a low thermal decomposition temperature, and heat resistance to lead-free solder, which has been in demand in recent years, is still required.

[0008] Japanese Patent Application Publication No. 11-199557 Japanese Patent Application Publication No. 11-24271 Japanese Patent Application Publication No. 2011-132507 International Publication No. 2016 / 114287 Japanese Patent Application Publication No. 2017-119361 Japanese Patent Application Publication No. 2019-104843 Japanese Patent Application Publication No. 2012-166515 Japanese Patent Application Publication No. 2007-302843

[0009] Therefore, an object of the present invention is to provide a bismaleimide compound capable of giving a cured product having excellent dielectric properties, alkali developability, and heat resistance; a curable resin composition containing the compound; a cured product thereof; and a protective film for semiconductor elements, an interlayer insulating film, an insulating film for rewiring layers, and the like.

[0010] As a result of extensive research to solve the above problems, the present inventors have found that the following bismaleimide compound (1) can achieve the above object, and have thus completed the present invention.

[0011] That is, the present invention relates to the following: [1] A bismaleimide compound represented by the following general formula (1):

[0012] In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group, and n is the average number of repeating units and represents an integer of 1 to 100.

[0013] [2] The bismaleimide compound according to [1], wherein X in formula (1) is one or more divalent hydrocarbon groups represented by the following formulae (2-1) to (4):

[0014] In formulas (2-1) to (4), n1 and n2 each represent a number from 5 to 30 and may be the same or different. R independently represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 4 to 40 carbon atoms. * represents a bonding site to the maleimide group. [3] A resin composition in which the weight-average molecular weight of the bismaleimide compound of formula (1) is 1,000 to 50,000, and a cured product obtained by addition polymerization of the bismaleimide compound of formula (1) has a dielectric dissipation factor of 0.010 or less. [4] The bismaleimide compound according to [1] or [2], wherein, in general formula (1), the hydrocarbon group constituting Y represents a hydrocarbon group having an aromatic ring structure represented by the following formula (5) or one hydrocarbon group having an alicyclic structure selected from the group represented by the following formula (6):

[0015] In formula (5), R １each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each 1 independently represents an integer of 1 to 4. * represents the bond to N.

[0016] In formula (6), R ２ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each p independently represents an integer of 1 to 4. * represents the bond to N.

[0017] [5] The bismaleimide compound according to [1] or [2], wherein in the general formula (1), Z is derived from maleic anhydride, trimellitic anhydride, phthalic anhydride, 4-methylhexahydrophthalic anhydride, methyl-endomethylenetetrahydrophthalic anhydride, or tetrahydrophthalic anhydride.

[0018] [6] The bismaleimide compound according to [1] or [2], wherein in the general formula (1), the carboxyl group-containing organic group constituting Z has any one of the following structures:

[0019] In the formula, the wavy line represents a bond to N. [7] The bismaleimide compound according to [1] or [2], wherein in the general formula (1), the ethylenically unsaturated group-containing organic group constituting Z has a partial structure represented by the following formula (7):

[0020] In formula (7), R ３represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents a bond to N. [8] A method for producing a bismaleimide compound represented by the following general formula (1), comprising: a step of reacting a bismaleimide compound (A) represented by the following general formula (8) with a diamino compound (B) represented by the following general formula (9) to obtain a bismaleimide compound (C) represented by the following general formula (10); and a step of reacting the bismaleimide compound (C) represented by the general formula (10) with a protecting agent (D) selected from an acid anhydride or an ethylenically unsaturated group-containing compound.

[0021] In formula (8), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms.

[0022] In formula (9), Y represents a divalent hydrocarbon group having 6 to 50 carbon atoms.

[0023] In formula (10), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, and each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms. n is the average number of repeating units and represents an integer of 1 to 100.

[0024] In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units and represents an integer of 1 to 100.

[0025] [9] A composition containing a bismaleimide compound represented by the following general formula (1) and a bismaleimide compound represented by the following general formula (8), wherein the content of the bismaleimide compound represented by the following general formula (8) is 50% or less when the total of the maleimide compound represented by the following general formula (1) and the bismaleimide compound represented by the following general formula (8) is 100%.

[0026] In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group, and n is the average number of repeating units and represents an integer of 1 to 100.

[0027] In formula (8), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms.

[0028]

[10] A composition containing the bismaleimide compound according to [1] or [2] and a compound capable of reacting with a maleimide group.

[11] A resin composition containing the bismaleimide compound (1) according to [1] or [2] and one or more selected from the group consisting of maleimide compounds other than the bismaleimide compound (1), cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

[12] A resin composition containing the bismaleimide compound (1) according to [1] or [2] and a photopolymerization initiator or a curing catalyst.

[13] The resin composition according to [9], further containing a filler.

[14] A resin composition containing the bismaleimide compound according to [1] or [2] and at least one selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, an anionic curing accelerator, and a cationic curing accelerator.

[15] A cured product of a resin composition containing the bismaleimide compound according to [1] or [2].

[16] A semiconductor element comprising a surface protective film, an interlayer insulating film, or an insulating film for a redistribution layer, which contains the bismaleimide compound according to [1] or [2].

[17] A dry film resist comprising a composition containing the bismaleimide compound according to [1] or [2] and a photopolymerization initiator.

[18] A cured film obtained by subjecting a resin composition containing the bismaleimide compound according to [1] or [2] to a heating step.

[0029] The bismaleimide compound of the present invention represented by general formula (1) has a divalent hydrocarbon group X having 6 to 200 carbon atoms, and therefore has excellent dielectric properties; the monovalent group that is a carboxy group-containing organic group or an ethylenically unsaturated group-containing organic group allows alkaline development; and the maleimide groups at both ends enable the production of cured products having excellent heat resistance. The present invention also provides a curable resin composition containing the compound, a cured product thereof, and a protective film for semiconductor elements, an interlayer insulating film, an insulating film for rewiring layers, and the like.

[0030] TG / DTA curve obtained by simultaneously performing thermogravimetry (TG) and differential thermal analysis (DTA) on the cured film obtained in Reference Example Y-1. Mass spectrum chart of the gas generated from the sample when the cured film obtained in Reference Example Y-1 was heated to 180°C.

[0031] The present invention will be described in detail below. (Bismaleimide Compound) The bismaleimide compound according to the present invention is a compound having two maleimide groups at its terminals, and is represented by the following formula (1).

[0032]

[0033] In the formula, each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms; when there are multiple Ys, each independently represents a residue obtained by removing two amino groups from a diamino compound; and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units and represents an integer of 1 to 100.

[0034] It is preferable that X in formula (1) is one or more divalent hydrocarbon groups represented by the following structural formulae (2-1) to (4).

[0035]

[0036] In formulas (2-1) to (4), n1 and n2 each represent a number from 5 to 30 and may be the same or different. R independently represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 4 to 40 carbon atoms. R independently represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 4 to 40 carbon atoms, preferably 5 to 20, and more preferably 6 to 15 carbon atoms. * represents the bonding site to the maleimide group.

[0037] Examples of the linear or branched alkyl or alkenyl group having 4 to 40 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, a stearyl group, a 3-octenyl group, and structural isomers thereof.

[0038] Y in formula (1) represents a residue obtained by removing two amino groups from a diamino compound, and is preferably a divalent hydrocarbon group, more preferably a divalent hydrocarbon group having 6 to 50 carbon atoms, and even more preferably a structure having an aromatic ring or an alicyclic structure.

[0039] In the general formula (1), it is preferable that Y is a hydrocarbon group having an aromatic ring structure represented by the following formula (5), or a hydrocarbon group having an aliphatic ring structure selected from the group represented by the following formula (6):

[0040]

[0041] In formula (5), R １ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each 1 independently represents an integer of 1 to 4. * represents the bond to N.

[0042]

[0043] In formula (6), R ２each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each p independently represents an integer of 1 to 4. * represents the bond to N.

[0044] In formula (1), n ​​is an integer of 1 to 100, preferably 1 to 50, and more preferably 1 to 20.

[0045] In formula (1), each Z is independently a monovalent group that is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group. However, at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. It is preferable that at least one Z is a carboxyl group-containing organic group.

[0046] In the general formula (1), it is preferable that Z has a carboxyl group-containing organic group or a partial structure represented by the following formula (7).

[0047]

[0048] In the formula (7), R ３ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents the bond to N.

[0049] The number average molecular weight of the bismaleimide compound of formula (1) is preferably 1,000 to 50,000. In this specification, the molecular weight refers to a value calculated in terms of polystyrene based on the results of GPC measurement described below.

[0050] The dielectric loss tangent of a cured product obtained by addition polymerization of the bismaleimide compound of formula (1) is preferably 0.010 or less.

[0051] The polymer compound represented by formula (1) of the present invention is a reaction product obtained by synthesizing (I) a polyaddition product (C) (bismaleimide compound (C) represented by formula (10)) of a diamino compound (B) (hereinafter simply referred to as "compound (B)") and a bismaleimide compound (A) of a specific structure (hereinafter simply referred to as "compound (A)") in a molar excess over compound (B), and then (II) reacting 5% to 100% of the secondary amino groups in the polyaddition product (C) with an anhydride group or an isocyanate group in a protecting agent (D) having a dibasic acid anhydride, an isocyanate group, and a (meth)acrylic group (hereinafter simply referred to as "protecting agent (D)"). The term "excess" as used herein means that the amount of compound (A) relative to compound (B) is sufficient, and is preferably 1.1 to 2.5 equivalents, and more preferably 1.3 to 2.3 equivalents. First, the polyadduct (C), which is an intermediate raw material for the polymer compound of the present invention, will be explained.

[0052] The polyadduct (C) is a polyaddition reaction product (Michael addition reaction product) of the compound (B) and a molar excess of the compound (A) over the compound (B).

[0053] Compound (A), the raw material for polyadduct (C), is a compound having two maleimide groups per molecule. In formula (1), X is independently a divalent hydrocarbon group having 6 to 200 carbon atoms, preferably 8 to 100 carbon atoms, and 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, and 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 molecular chain. Specific examples of the branched divalent hydrocarbon group include hydrocarbon groups derived from diamines at both ends, known as dimer diamines. Dimer diamines are compounds in which two carboxy groups of a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, have been substituted with primary amino groups, as shown in the following formulas (11) to (16) (see, for example, Japanese Patent Application Laid-Open No. 9-12712). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.) and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These compounds may be used alone or in combination of two or more. Non-limiting general formulas of dimer diamines are shown below. In each formula, m+n preferably represents 6 to 17, and p+q preferably represents 8 to 19. The dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0054]

[0055] The residues obtained by removing the amino group from the dimer diamines represented by the above formulas (11) to (16) are specifically divalent hydrocarbon groups represented by the following formulas (11') to (16'). In each formula, m+n preferably represents 6 to 17, and p+q preferably represents 8 to 19. The dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. * represents the bond to N.

[0056] The residue (divalent linking group) obtained by removing the two maleimide groups of compound (A) corresponds to X in formula (1). That is, compound (A) is a bismaleimide compound represented by the following formula (8).

[0057]

[0058] In the formula (8), X represents a divalent hydrocarbon group having 6 to 200 carbon atoms.

[0059] The compound (B) used as the raw material is not particularly limited as long as it is a compound having two amino groups in one molecule, but is preferably a diamino compound represented by the following general formula (9):

[0060]

[0061] In the formula (9), Y represents a divalent hydrocarbon having 6 to 50 carbon atoms.

[0062] Specific examples of the compound (B) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenebiscyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, norbornenediamine, and dimer diamine. amine, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,5-diaminobenzoic acid, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diamino 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5- dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 2,3-diaminonaphthalene, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, 2,2-bis(4,(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane Examples of suitable amino groups include bis(4-aminophenoxy)butane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine; 3,3',5,5'-tetramethylbenzidine, 2,2-bis(4-aminophenyl)hexafluoropropane, m-xylylenediamine, p-xylylenediamine, bis(4-amino-3-methylcyclohexyl)methane, and 1,2-bis(2-aminoethoxy)ethane. The residue (divalent linking group) obtained by removing the two amino groups from compound (B) corresponds to Y in formula (1).

[0063] Compound (B) is preferably an aliphatic diamino compound having two or more carbon atoms, and specific examples thereof include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenebiscyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, metaxylenediamine, isophoronediamine, norbornenediamine, tricyclodecanediamine, and dimer diamine. Y in formula (1) is preferably a residue (divalent linking group) obtained by removing two amino groups from the above-mentioned aliphatic diamino compound having two or more carbon atoms.

[0064] The hydrocarbon group constituting Y is preferably a hydrocarbon group having an aromatic ring structure represented by the following formula (5) or a hydrocarbon group having an alicyclic structure selected from the group represented by the following formula (6):

[0065]

[0066] In formula (5), R １ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each 1 independently represents an integer of 1 to 4. * represents the bond to N.

[0067]

[0068] In formula (6), R ２ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each p independently represents an integer of 1 to 4. * represents the bond to N.

[0069] R in the formula (5) １ and R in the formula (6) ２ Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The linear or branched alkyl group having 3 to 6 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups, ethyl groups, n-propyl groups, and i-propyl groups are more preferred, as they exhibit excellent adhesion to chips, substrates, and the like, as well as good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] The linear alkoxy group having 1 to 6 carbon atoms or the branched alkoxy group having 3 to 6 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and a tert-butoxy group. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group are more desirable, since they exhibit excellent adhesion to chips, substrates, and the like, as well as good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins. R １ and R ２ As the alkyl group, a hydrogen atom, a methyl group, an ethyl group, a hydroxy group, a methoxy group, and an ethoxy group are preferred, a hydrogen atom, a methyl group, and a hydroxy group are more preferred, and a hydrogen atom is even more desirable, because these groups exhibit good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins in addition to excellent adhesion to chips, substrates, etc.

[0071] l in the formula (4) and p in the formula (5) each independently represent an integer of 1 to 4. l and p are preferably selected from R １ and R ２ are preferably all hydrogen atoms, and therefore, 4 is preferred.

[0072] Specific examples of the hydrocarbon group having an aromatic ring represented by formula (5) include hydrocarbon groups obtained by removing the amine group from metaxylenediamine (formula (5-1) below), paraxylenediamine (formula (5-2) below), and orthoxylenediamine (formula (5-3) below). The hydrocarbon group having an aromatic ring represented by formula (5) is preferably a hydrocarbon group represented by formula (5-1) below. In formulas (5-1) to (5-3), * represents a bond to N.

[0073]

[0074] The hydrocarbon group having an aliphatic ring represented by the formula (6) is preferably a hydrocarbon group obtained by removing an amine group from 1,3-bis(aminomethyl)cyclohexane (formula (6-1) below), norbornanediamine (formula (6-2) below), tricyclodecanediamine (formula (6-3) below), or isophoronediamine (formula (6-4) below). (* represents a bond.)

[0075]

[0076] The amounts of compound (A) and compound (B) used when synthesizing polyadduct (C) are usually such that the molar amount of compound (B) is smaller than that of compound (A), preferably 0.2 to 0.98 mol, more preferably 0.4 to 0.96 mol, of compound (B) per 1 mol of compound (A). The reaction temperature during synthesis is usually 40 to 140°C, preferably 60 to 120°C, and the reaction time is usually 0.5 to 20 hours, preferably 1 to 10 hours. A reaction catalyst may be used. The reaction may be terminated when the molecular weight measured by GPC (gel permeation chromatography) no longer increases from a certain value. The solvent used in the reaction may be distilled off under reduced pressure with heating, or may be used as is in a resin composition containing the solvent.

[0077] It is preferable to use a solvent for the polyaddition reaction of compound (A) and compound (B), and examples of usable solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, anisole, gamma-cyclohexanone, propylene glycol monomethyl ether acetate, etc. The amount of the solvent used is preferably 10 to 300 mass %, more preferably 20 to 200 mass %, based on the solid content of the raw materials used in the copolymerization reaction.

[0078] The weight-average molecular weight of the polyadduct (C) is usually 5,000 to 100,000, preferably 10,000 to 50,000. To obtain a polyadduct (C) having a weight-average molecular weight within the above range, the raw material components may be charged in the above-mentioned ratio. By measuring this number-average molecular weight, the value of n in formula (1) can be calculated. n is the average number of repeating units and is in the range of 1 to 100. If it is within this range, the effects of the bismaleimide compound of the present invention can be exhibited. In this specification, the molecular weight refers to a value calculated in polystyrene equivalent based on the results of GPC measurement.

[0079] In general formula (1), n ​​represents the number of repeats, and n in general formula (1) represents an integer from 1 to 100. However, at least one of the n's (one molecule) is an integer of 1 or greater. That is, the maleimide resin of the present invention may be a mixture of maleimide compounds having various repeat numbers n, or a pure substance consisting of compounds having the same n. It may also contain a maleimide resin represented by general formula (8) above. Even if this mixture contains a maleimide compound represented by general formula (8) above, by containing a maleimide compound represented by general formula (1) having n of 1 or greater, it becomes an alkali-developable maleimide resin with extremely good alkali developability.

[0080] In the composition of the present invention comprising the bismaleimide compound represented by general formula (1) above and the bismaleimide compound represented by general formula (8) above, the content of the composition of the bismaleimide compound represented by general formula (8) above is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less, when the total of the composition of the bismaleimide compound represented by general formula (1) above and the bismaleimide compound represented by general formula (8) above is taken as 100%, from the viewpoint of making the alkaline developability of the maleimide resin itself excellent.

[0081] Next, the bismaleimide compound of the present invention will be described. In the bismaleimide compound of the present invention, each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group.

[0082] In the present invention, the carboxyl group-containing organic group Z is a group derived from the dibasic acid anhydride protecting agent (D), and refers to a partial structure other than the structure of the chemical bond formed between the acid anhydride and a nitrogen atom. The dibasic acid anhydride protecting agent (D) is not limited, but is preferably a residue of a carboxylic acid anhydride from the viewpoint of successfully obtaining the maleimide compound of the present invention. Specific examples of the dibasic acid anhydride protecting agent (D) include, for example, any compound having an acid anhydride structure in one molecule, and examples thereof include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate (trade name: Rikaresin (registered trademark) TMEG, manufactured by New Japan Chemical Co., Ltd.), glycerol tristrimellitate (trade name: Rikaresin TMTA, manufactured by New Japan Chemical Co., Ltd.), endomethylenetetrahydrophthalic anhydride (trade name: KAYAHARD (registered trademark) CD, manufactured by Nippon Kayaku Co., Ltd.), methyl endomethylenetetrahydrophthalic anhydride (trade name: KAYAHARD (registered trademark) CD, manufactured by Nippon Kayaku Co., Ltd.), and methyl endomethylenetetrahydrophthalic anhydride (trade name: KAYAHARD (registered trademark) CD, manufactured by Nippon Kayaku Co., Ltd.). Particularly preferred are methylbutenyltetrahydrophthalic anhydride (trade name: YH-306, manufactured by Nippon Kayaku Co., Ltd.), methylbutenyltetrahydrophthalic anhydride (trade name: YH-306), dodecenylsuccinic anhydride (trade name: DSA (registered trademark), manufactured by Sanyo Chemical Industries, Ltd.), methylhexahydrophthalic anhydride (trade name: RIKACID (registered trademark) MH-700, manufactured by New Japan Chemical Co., Ltd.), methylcyclohexene dicarboxylic anhydride (trade name: EPICLON (registered trademark) EXB-4400, manufactured by DIC Corporation), alkylstyrene-maleic anhydride copolymer (SUMICURE MS-1), chlorendic anhydride (KAYAHARD CLA), polyazelaic anhydride (trade name: RIKACID PAZ-90, manufactured by New Japan Chemical Co., Ltd.), trimellitic anhydride, hydrogenated trimellitic anhydride, methyl-endo-methylenetetrahydrophthalic anhydride, and maleic anhydride. When a heating step is applied to a resin composition containing a bismaleimide compound, a liquid acid anhydride is particularly preferred, since it is less likely to stain the inside of a heating furnace when the acid anhydride component volatilizes during the heating step.Examples of liquid acid anhydrides include 4-methyl-hexahydrophthalic anhydride and methyl-end-methylenetetrahydrophthalic anhydride.

[0083] Specific examples of the carboxyl group-containing organic group having a carboxyl group derived from a dibasic acid anhydride include groups having any of the following structures: In the following formula, the wavy line represents the bond to N.

[0084] In Z of the present invention, the ethylenically unsaturated group-containing organic group is obtained by reacting with an isocyanate group in a protecting agent (D), which is an ethylenically unsaturated group-containing compound represented by the following formula (7-1):

[0085]

[0086] In addition, R in formula (7-1) ５ is R in formula (7) ３ That is, R in formula (7) ３ is derived from a hydrogen atom or an alkyl group having 1 to 3 carbon atoms contained in the protecting agent (D).

[0087] The amounts of the polyadduct (C) and the protecting agent (D) used in synthesizing the polymer compound of the present invention are preferably 0.05 to 1.2 mol, more preferably 0.1 to 1.0 mol, of the protecting agent (D) relative to 1 molar equivalent of the secondary amino group in the polyadduct (C). The reaction temperature is preferably 10 to 90° C., and the reaction time is preferably 30 minutes to 5 hours.

[0088] Specific examples of the protecting agent (D) that is an ethylenically unsaturated group-containing compound include those represented by the formula (7-1) R ５ is a methyl group. Commercially available 2-isocyanatoethyl methacrylate products include Karenz MOI (manufactured by Resonac Co., Ltd.) and Karenz AOI (manufactured by Resonac Co., Ltd.).

[0089] The amounts of the polyadduct (C) and the protecting agent (D) used in synthesizing the bismaleimide compound of the present invention are preferably 0.05 to 1.2 mol, more preferably 0.1 to 1.0 mol, of the protecting agent (D) per 1 molar equivalent of the secondary amino group in the polyadduct (C). The reaction temperature is preferably 10 to 90°C, and the reaction time is preferably 30 minutes to 5 hours. Furthermore, a dibasic acid anhydride and an ethylenically unsaturated group-containing compound may be used in combination as the protecting agent (D).

[0090] In the bismaleimide compound of the present invention, the protecting agent (D) bonds to the nitrogen atom of formula (10) to become Z in formula (1), stabilizing the reactivity of the nitrogen atom as a tertiary amine. Therefore, the bismaleimide compound of the present invention does not undergo high molecular weight or gelation at temperatures below the curing temperature, and has excellent thermal stability. Furthermore, the curing time can be easily adjusted.

[0091] The bismaleimide compound of this embodiment is not particularly limited as long as it exhibits the effects of the present invention, but from the viewpoints of good solubility in solvents, a low melting point, low water absorbency, and good compatibility with other resins, the weight average molecular weight is preferably 100 to 100,000, and more preferably 1,000 to 50,000. In this embodiment, the "weight average molecular weight" refers to the weight average molecular weight calculated as a polystyrene standard by gel permeation chromatography (GPC).

[0092] The compound of the present invention can be purified by a conventional method, such as reprecipitation.

[0093] The composition containing the bismaleimide compound (1) preferably contains a compound capable of reacting with a maleimide group.

[0094] The compound capable of reacting with a maleimide group can include one or more compounds selected from the group consisting of maleimide compounds other than the bismaleimide compound (1) of the present embodiment (hereinafter also referred to as “other maleimide compounds”), cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

[0095] The bismaleimide compound (1) component preferably accounts for 1 to 99% by mass, more preferably 5 to 95% by mass, of the solid content of the resin composition of the present invention. Each component of the compound capable of reacting with a maleimide group will be described below.

[0096] (Maleimide Compounds Other than Bismaleimide Compound (1)) The other maleimide compounds are not particularly limited as long as they are compounds other than the bismaleimide compound (1) of the present embodiment and have one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-diphenyl)maleimide, bis(4-maleimidophenyl)methane ... methyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl) Propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 1,5-bismaleimidopentane, 1,5-bismaleimido-2-methylpentane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,8-bismaleimido-3,6-dioxaoctane, 1,11-bismaleimido-3, 6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,Examples of such maleimide compounds include bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethane maleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used alone or in appropriate mixtures of two or more.

[0097] As the other maleimide compound represented by formula (19), commercially available products may be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. As the other maleimide compound represented by formula (20), commercially available products may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the other maleimide compound represented by formula (21), commercially available products may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0098] In this embodiment, in order to efficiently induce the photoradical reaction of the bismaleimide compound (A), a chloroform solution containing 1% by mass of the other maleimide compound is prepared, and when the transmittance of this chloroform solution is measured using active energy rays having a wavelength of 365 nm (i-line), it is preferable that the transmittance be 5% or more. In this case, the transmittance is more preferably 8% or more, and even more preferably 10% or more. Furthermore, in order to efficiently induce the photoradical reaction of the bismaleimide compound (A), it is preferable that a 1% by mass chloroform solution of the other maleimide compound exhibits an optical transmittance of 5% or more using active energy rays having a wavelength of 405 nm (h-line). By using such other maleimide compound, for example, when producing a printed wiring board having a high-density, high-definition wiring formation (pattern) using a direct writing exposure method, the photoradical reaction of the maleimide efficiently occurs even when active energy rays having a wavelength of 405 nm (h-line) are used. The light transmittance is more preferably 8% or more, and even more preferably 10% or more, since a resin composition having superior photocurability can be obtained.

[0099] Examples of such other maleimide compounds include maleimide compounds represented by formula (25), such as maleimide compounds represented by formula (22), maleimide compounds represented by formula (23), and maleimide compounds represented by formula (24), maleimide compounds represented by formula (26), maleimide compounds represented by formula (27), maleimide compounds represented by formula (28), 1,6-bismaleimide-(2,2,4-trimethyl)hexane (maleimide compound represented by formula (29)), maleimide compounds represented by formula (30), and fluorescein-5-maleimide.

[0100] In formula (18), n (average) is 1 or more, preferably 1 to 21, and more preferably 1 to 16 from the viewpoint of exhibiting excellent photocurability.

[0101] In formula (23), the number of x is 10 to 35. In formula (23), the number of y is 10 to 35.

[0102] In formula (24), R ａ represents a linear alkyl group having 1 to 16 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, or a linear alkenyl group having 2 to 16 carbon atoms or a branched alkenyl group having 3 to 16 carbon atoms. ａ The alkyl group is preferably a linear or branched alkyl group, and is more preferably a linear alkyl group because it exhibits excellent photocurability. The number of carbon atoms in the alkyl group is preferably 4 to 12 because it exhibits excellent photocurability. The number of carbon atoms in the alkenyl group is preferably 4 to 12 because it exhibits excellent photocurability.

[0103] The linear or branched alkyl group may be R ３ can be referred to. Among these, an n-heptyl group, an n-octyl group, and an n-nonyl group are preferred, with an n-octyl group being more preferred, as they exhibit excellent photocurability. As the linear or branched alkenyl group, a 2-heptenyl group, a 2-octenyl group, and a 2-nonenyl group are preferred, with a 2-octenyl group being more preferred, as they exhibit excellent photocurability.

[0104] In formula (24), R ｂ represents a linear alkyl group having 1 to 16 carbon atoms or a branched alkyl group having 3 to 16 carbon atoms, or a linear alkenyl group having 2 to 16 carbon atoms or a branched alkenyl group having 3 to 16 carbon atoms. ｂ The alkyl group is preferably a linear or branched alkyl group, and is more preferably a linear alkyl group because it exhibits excellent photocurability. The number of carbon atoms in the alkyl group is preferably 4 to 12 because it exhibits excellent photocurability. The number of carbon atoms in the alkenyl group is preferably 4 to 12 because it exhibits excellent photocurability.

[0105] Specific examples of the alkyl group include R ａ Among these, n-heptyl, n-octyl and n-nonyl groups are preferred, with n-octyl being more preferred, as they exhibit excellent photocurability. Specific examples of alkenyl groups include R ａAmong these, 2-heptenyl, 2-octenyl and 2-nonenyl groups are preferred, with 2-octenyl being more preferred, as they exhibit excellent photocurability.

[0106] In formula (24), n ａ The number is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

[0107] In formula (24), n ｂ The number is 1 or more, preferably 2 to 16, and more preferably 3 to 14 from the viewpoint of exhibiting excellent photocurability.

[0108] n ａ and ｂ The numbers may be the same or different.

[0109] In formula (25), n (average) is 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 8 from the viewpoint of exhibiting excellent photocurability.

[0110] In formula (26), n represents an integer of 1 or more, and preferably an integer of 1 to 10.

[0111] In formula (27), n represents an integer of 1 or more, and preferably an integer of 1 to 10.

[0112] In formula (28), n represents an integer of 1 or more, and preferably an integer of 1 to 10.

[0113] In the above formula (30), R １０ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R １１ each independently represents a hydrogen atom or a methyl group.

[0114] Other maleimide compounds may also be commercially available. Examples of the maleimide compound represented by formula (22) include BMI-1000P (trade name, n = 13.6 (average) in formula (22)) manufactured by K.I. Chemical Co., Ltd., BMI-650P (trade name, n = 8.8 (average) in formula (22)) manufactured by K.I. Chemical Co., Ltd., BMI-250P (trade name, n = 3 to 8 (average) in formula (22)) manufactured by K.I. Chemical Co., Ltd., and CUA-4 (trade name, n = 1 in formula (22)) manufactured by K.I. Chemical Co., Ltd., etc. Examples of the maleimide compound represented by formula (23) include BMI-6100 (trade name, x = 18, y = 18) manufactured by Designer Molecules Inc., etc. Examples of the maleimide compound represented by formula (24) include BMI-689 (trade name, formula (31) below, functional group equivalent: 346 g / eq.) manufactured by Designer Molecules Inc.

[0115] Examples of the maleimide compound represented by formula (25) include BMI-1500 (trade name, n = 1.3 in formula (25), functional group equivalent: 754 g / eq.) manufactured by Designer Molecules Inc. As the maleimide compound represented by formula (26), commercially available products can be used, for example, BMI-1700 (trade name) manufactured by Designer Molecules Inc. (DMI). As the maleimide compound represented by formula (27), commercially available products can be used, for example, BMI-3000 (trade name) manufactured by Designer Molecules Inc. (DMI), BMI-5000 (trade name) manufactured by Designer Molecules Inc. (DMI), and BMI-6000 (trade name) manufactured by Designer Molecules Inc. (DMI). Examples of the maleimide compound represented by formula (28) include BMI-9000 (trade name) manufactured by DMI Co., Ltd. Commercially available products can be used as the maleimide compound represented by formula (28), such as MIZ-001 (trade name) manufactured by Nippon Kayaku Co., Ltd. Commercially available products can be used as the maleimide compound represented by formula (29), such as BMI-TMH (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. Commercially available products can be used as the maleimide compound represented by formula (30), such as BMI-70 (trade name) manufactured by K.I. Kasei Co., Ltd. These other maleimide compounds can be used alone or in appropriate mixtures of two or more.

[0116] In the composition according to the present embodiment, the total content of the other maleimide compounds is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin solid content in the composition according to the present embodiment.

[0117] (Cyanate Ester Compound) The cyanate ester compound is a cyanate ester compound obtained by reacting a phenolic resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups, but are not limited thereto. Furthermore, the cyanate ester compound, whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154, is particularly preferred as a cyanate ester compound due to its low moisture absorption, flame retardancy, and excellent dielectric properties. The cyanate ester compound may optionally contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate to trimerize the cyanate group to form a sym-triazine ring. The catalyst is typically used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the total composition.

[0118] In the composition according to this embodiment, the total content of the cyanate ester compounds is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin solid content in the composition according to this embodiment.

[0119] (Phenol Resin) As the phenol resin, any known phenol resin can be used as long as it has two or more hydroxyl groups in one molecule. For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, and hydroxyl group-containing silicone resin can be mentioned, but not particularly limited. These phenolic resins may be used singly or in a suitable mixture of two or more.

[0120] In the composition according to this embodiment, the total content of the phenolic resin is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin solid content in the composition according to this embodiment.

[0121] The epoxy resin is not particularly limited, and generally known epoxy resins can be used. For example, bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, xylene novolac type epoxy resins, multifunctional phenol type epoxy resins, naphthalene type epoxy resins, naphthalene skeleton modified novolac type epoxy resins, naphthylene ether type epoxy resins, phenol aralkyl type epoxy resins, anthracene type epoxy resins, trifunctional phenol type epoxy resins, tetrafunctional phenol type epoxy resins, triglyceride type epoxy resins, and the like can be used. Examples of epoxy resins include glycidyl isocyanurate, glycidyl ester-type epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac-type epoxy resins, biphenyl novolac-type epoxy resins, phenol aralkyl novolac-type epoxy resins, naphthol aralkyl novolac-type epoxy resins, aralkyl novolac-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-type epoxy resins, polyol-type epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds in which the double bond of butadiene or the like has been epoxidized, compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used alone or in combination of two or more.

[0122] In the composition according to the present embodiment, the total content of the epoxy resin is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin solid content in the composition according to the present embodiment.

[0123] (Oxetane Resin) As the oxetane resin, generally known ones can be used. Examples include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), and OXT-121 (manufactured by Toagosei Co., Ltd., trade name), but are not particularly limited thereto. These oxetane resins can be used alone or in an appropriate mixture of two or more types.

[0124] In the composition according to this embodiment, the total content of the oxetane resin is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of the resin solid content in the composition according to this embodiment.

[0125] (Benzoxazine Compound) As the benzoxazine compound, any generally known compound can be used as long as it has two or more dihydrobenzoxazine rings in one molecule. Examples include bisphenol A-type benzoxazine BA-BXZ (trade name, manufactured by Konishi Chemical Co., Ltd.), bisphenol F-type benzoxazine BF-BXZ (trade name, manufactured by Konishi Chemical Co., Ltd.), bisphenol S-type benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical Co., Ltd.), and phenolphthalein-type benzoxazine, but are not particularly limited thereto. These benzoxazine compounds can be used alone or in appropriate mixtures of two or more.

[0126] In the composition according to the present embodiment, the total content of the benzoxazine compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of the resin solid content in the composition according to the present embodiment.

[0127] (Carbodiimide Compound) The carbodiimide compound is not particularly limited as long as it has at least one carbodiimide group in the molecule, and generally known compounds can be used. Examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimide, polycarbodiimides such as Carbodilite (registered trademark: manufactured by Nisshinbo Chemical Inc.), and Stabaxol (registered trademark: manufactured by LANXESS Deutschland GmbH). These carbodiimide compounds can be used alone or in combination of two or more.

[0128] In the composition according to this embodiment, the total content of the carbodiimide compounds is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of the resin solid content in the composition according to this embodiment.

[0129] (Compound Having an Ethylenically Unsaturated Group) The compound having an ethylenically unsaturated group is not particularly limited as long as it has an ethylenically unsaturated group in one molecule. Specific examples of the compound having an ethylenically unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, and polypropylene glycol di(meth)acrylate. , adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid neopen glycol di(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tri(meth)acrylate, and ethylene oxide adducts thereof; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene oxide adducts thereof.

[0130] Other specific examples of the compound having an ethylenically unsaturated group include urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy (meth)acrylates derived from epoxy resins and having both a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0131] Examples of urethane (meth)acrylates include reaction products of a hydroxyl group-containing (meth)acrylate with a polyisocyanate and other alcohols used as needed. Examples include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; glycerin (meth)acrylates such as glycerin mono(meth)acrylate and glycerin di(meth)acrylate; pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; Examples of the urethane (meth)acrylates include those obtained by reacting sugar alcohol (meth)acrylates such as urethane (meth)acrylate with polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates and biuret reaction products.

[0132] Examples of polyester (meth)acrylates include monofunctional (poly)ester (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)acrylate, ethylene oxide-modified succinic acid (meth)acrylate, and caprolactone-modified tetrahydrofurfuryl (meth)acrylate; di(poly)ester (meth)acrylates such as hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, and epichlorohydrin-modified phthalic acid di(meth)acrylate; and mono-, di-, or tri(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of trimethylolpropane or glycerin.

[0133] Further examples include mono-, di-, tri-, or tetra(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono- or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols, or mono- or poly(meth)acrylates of triols obtained by adding 1 mole or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mole of dipentaerythritol, or poly(meth)acrylates.

[0134] Further examples include polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of polyester polyols which are reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, and hexanediol with polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and anhydrides thereof; and (meth)acrylates of cyclic lactone-modified polyester diols formed from diol components, polybasic acids, anhydrides thereof, and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc.

[0135] The epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples thereof include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, trishydroxyphenylmethane epoxy (meth)acrylate, dicyclopentadienephenol epoxy (meth)acrylate, bisphenol A epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, biphenol epoxy (meth)acrylate, bisphenol A novolac epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and the acid anhydride-modified epoxy acrylates thereof.

[0136] Specific examples of the compound having an ethylenically unsaturated group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; and compounds having a vinyl group such as triallyl isocyanurate, trimethallyl isocyanurate, and bisallylnadimide.

[0137] As the compound having an ethylenically unsaturated group, commercially available products can be used, and examples thereof include KAYARAD (registered trademark) ZXR-801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene-type epoxy acrylate compounds (manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) ZXR-1806H (trade name), KAYARAD (registered trademark) ZXR-1810H (trade name), and KAYARAD (registered trademark) ZXR-1889H (trade name). These compounds having an ethylenically unsaturated group can be used alone or in appropriate mixtures of two or more types.

[0138] In the composition according to the present embodiment, the total content of the compounds having an ethylenically unsaturated group is not particularly limited, but is preferably 0.01 to 60 parts by mass per 100 parts by mass of the resin solid content in the composition according to the present embodiment.

[0139] The composition contains components other than the compound represented by the general formula (2). Examples of other components contained in the resin composition include an organic solvent, a photopolymerization initiator, a curing agent having a reactive group capable of reacting with a maleimide group, a curing catalyst, or an adhesion enhancer such as a coupling agent, and a filler. Various other components can be used without particular limitation depending on the application and usage of the resin composition. Resin compositions containing an organic solvent are preferred because they are easy to handle. Furthermore, since the compound of the present invention is capable of self-polymerization, it can be used without the use of a photopolymerization initiator, a curing agent, a curing catalyst, or the like.

[0140] (Photopolymerization initiator) The bismaleimide compound represented by the general formula (2) can self-polymerize by itself, but it can also be self-polymerized by using a photopolymerization initiator or a curing catalyst in combination with the compound represented by the general formula (2) to form a composition. The use of a photopolymerization initiator in combination makes it possible to self-polymerize by irradiation with light, and the use of a curing catalyst in combination makes it possible to lower the heating temperature during self-polymerization compared to when no curing catalyst is used.

[0141] The photopolymerization initiator that can be used in combination with the self-polymerization is not particularly limited, and conventionally used initiators can be appropriately used. Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler's ketone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzil dimethyl ketal, thioxathon, 2-chlorothioxathon, 2-methylthioxathon, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- Examples of such oxime include 2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), and 2,4-dimethylthioxanthone. These photopolymerization initiators may be used alone or in combination of two or more.

[0142] Among these, it is preferable to use a compound that efficiently generates radicals at an exposure wavelength of 310 to 436 nm (more preferably 365 nm) from the viewpoint that fine patterns can be formed using a stepper (light source wavelength: 365 nm, 436 nm) that is standardly used in the manufacturing process of semiconductor protective films and the like. Preferred examples of the photopolymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (manufactured by BASF Japan, "IRGACURE (registered trademark) OXE-01"), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02"), 2,4-dimethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins B.V., "Omirad 907"). The amount of the photopolymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the compound represented by formula (1).

[0143] A sensitizer may be used in combination with the photopolymerization initiator. The sensitizer that can be used in combination is not particularly limited as long as it is a conventionally known sensitizer, and examples thereof include 4,4'-bis(diethylamino)benzophenone. The amount of the sensitizer used is preferably 2 parts by mass or less, more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the compound represented by formula (2). By using a sensitizer in combination, it is possible to increase the sensitivity to light during self-polymerization.

[0144] (Curing Catalyst) The curing catalyst that can be used in combination during self-polymerization is not particularly limited as long as it can promote the self-polymerization of the maleimide groups at both ends of the compound represented by formula (1) of the present invention by heating, and conventionally used catalysts can be appropriately adopted. Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; triphenylphosphine; tributylphosphine; Examples of the curing catalyst include phosphines such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate, metal chlorides such as zinc chloride, aluminum chloride, and tin chloride, organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide, azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride. The amount of the curing catalyst used is preferably 10 parts by mass or less, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the compound represented by Formula (1).

[0145] The curing agent according to the present invention is not particularly limited, and conventionally used compounds can be appropriately used. The curing agent is not particularly limited as long as it has a functional group (or structure) capable of crosslinking with a maleimide compound, such as an amino group, a cyanate group, a phenolic hydroxyl group, or an alcoholic hydroxyl group. Furthermore, maleimide compounds other than the maleimide compound according to the present invention may be used in combination.

[0146] (Organic Solvent) The organic solvent is not particularly limited, but examples thereof include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methyl amyl ketone. These organic solvents can be used alone or in combination of two or more. The use of organic solvents in combination is a preferred embodiment in terms of improving the handleability of the composition. There are no particular limitations on the content of the organic solvent in the composition of the present invention, but the content of the solvent in the composition is typically 95% by mass or less, preferably 20 to 90% by mass.

[0147] (Coupling Agent) Examples of silane coupling agents include, but are not limited to, 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. These can be used alone or in combination of two or more. Since silane coupling agents are unreactive with the compounds of the present invention (compounds, self-polymerizing compounds, benzoxazole), components other than those acting at the substrate interface may remain as residual components after curing. Therefore, using large amounts of adhesion enhancers may have adverse effects such as reduced physical properties. Depending on the type of substrate, even a small amount can be effective, so it is appropriate to use it within a range that does not have adverse effects. The proportion of use is usually 15% by mass or less, preferably more than 0% by mass and 5% by mass or less, based on the composition, but the upper limit of the proportion may vary depending on the type of substrate.

[0148] (Thermoplastic Resin) Examples of thermoplastic resins include polyethersulfone, polystyrene, polycarbonate, etc. Colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Thickeners include orben, bentone, montmorillonite, etc. Thermal polymerization inhibitors include hydroquinone, 2,6-di-tert-butyl-p-methylphenol, etc. Antifoaming agents include silicone-based, fluorine-based, and polymer-based antifoaming agents. The amount of these additives used in the composition of the present invention is preferably 30% by mass or less, as a rough guideline, but this can be increased or decreased as appropriate depending on the intended use.

[0149] (Filler) The resin composition of the present embodiment may further contain a filler in order to improve various properties such as coating properties, heat resistance, etc. The filler is preferably one that has insulating properties and does not inhibit the transmittance of light with a wavelength of 405 nm (h-line). The filler is not particularly limited, but examples thereof include silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, aluminum nitride, etc.), boron compounds (e.g., boron nitride, etc.), magnesium compounds (e.g., magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), barium compounds (e.g., barium sulfate, barium silicate, etc.), talc (e.g., natural talc, calcined talc, etc.), mica, glass (e.g., short fiber glass, spherical glass, finely powdered glass (e.g., E-glass, T-glass, D-glass, etc.), etc.), silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber. These fillers can be used alone or in combination of two or more.

[0150] Among these, one or more selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and silicone rubber are preferred. These fillers may be surface-treated with a silane coupling agent or the like, which will be described later.

[0151] Silica is preferred, and fused silica is more preferred, from the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of this embodiment and obtaining good coating properties. Specific examples of silica include SFP-130MC manufactured by Denka Co., Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA manufactured by Admatechs Co., Ltd.

[0152] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, preferably 0.01 to 50 μm.

[0153] In the resin composition of this embodiment, the content of the filler is not particularly limited, but from the viewpoint of improving the heat resistance of the cured product, it is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. When a filler is contained, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is usually 1 part by mass per 100 parts by mass of the resin solid content in the resin composition.

[0154] Other components that may be contained in the resin composition of the present invention include various additives such as colorants, thickeners, thermal polymerization inhibitors, antifoaming agents, and leveling agents.

[0155] A cured product containing the bismaleimide compound (1) is obtained by curing the resin composition of this embodiment. The cured product is not particularly limited, but can be obtained, for example, by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, or the like. In the case of heat curing, the curing temperature is not particularly limited, but is preferably in the range of 80°C to 300°C, more preferably in the range of 120°C to 300°C, from the viewpoint of efficient curing and preventing deterioration of the resulting cured product. In the case of photocuring, the wavelength range of light is not particularly limited, but is preferably in the range of 100 nm to 500 nm, at which curing proceeds efficiently using a photopolymerization initiator, etc.

[0156] The heat-resistant resin coating formed from the resin composition of the present invention can be used in electronic components such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, it is suitably used for applications such as passivation films for semiconductors, surface protection films for semiconductor elements, interlayer insulating films, insulating films for rewiring layers, interlayer insulating films for multilayer wiring for high-density packaging, interlayer insulating films for electronic components such as inductors and SAW filters, and insulating films and flattening layers for organic electroluminescent devices, but is not limited thereto, and the coating can have a variety of structures.

[0157] The compound and composition of the present invention can also be used in the form of a dry film resist. That is, the compound and composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, or the like, followed by drying in a drying oven set at 45 to 140°C to remove a predetermined amount of solvent, and optionally by laminating a cover film or the like to produce a dry film resist. In this case, the thickness of the resist on the base film is adjusted to 2 to 200 μm. Examples of the base film and cover film include films made of polyester, polypropylene, polyethylene, TAC, polyimide, and the like. These films may be treated with a silicone-based release agent or a non-silicone-based release agent, as needed. Supplying the photosensitive resin composition of the present invention as a dry film resist eliminates the steps of coating on a support and drying, making it easier to use the composition.

[0158] The cured film of this embodiment is obtained by subjecting a resin composition containing a bismaleimide compound represented by general formula (1) to a heating step. It is believed that the heating step causes a carboxy group to be eliminated from the bismaleimide compound represented by general formula (1) contained in the cured film, thereby reducing the polarity of the cured product and resulting in a low dielectric loss tangent.

[0159] The temperature in the heating step is preferably in the range of 40° C. to 400° C., more preferably in the range of 60° C. to 300° C., and most preferably in the range of 80° C. to 250° C., from the viewpoint of the progress of the carboxyl group elimination reaction and the heat resistance of the cured product. Note that a cured film may be formed by irradiating a resin composition containing a bismaleimide compound represented by general formula (1) with ultraviolet light.

[0160] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. In the examples, "parts" and "%" are based on mass. In each of Examples 1 to 10 and Comparative Examples 1 and 2, compatibility, alkaline developability, dielectric properties, and heat resistance (glass transition temperature (Tg)) were evaluated as follows. The molecular weight measurement conditions were as follows: Model: GPC TOSOH HLC-8220GPC Column: Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, 40°C Detector: RI (differential refractometer) Molecular weight standard: polystyrene

[0161] Example A (I-1) To a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Corporation) as a bismaleimide compound, 71.1 g (0.5 mol) of 1,3-bis(aminomethyl)cyclohexane (product name: 1,3-BAC, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a diamine compound, and 918.4 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80°C and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80°C for 8 hours, yielding a reaction solution containing a Michael adduct of bismaleimide and diamine. To the reaction solution containing the resulting Michael adduct, 152.15 g (1.0 mol) of tetrahydrophthalic anhydride (product name: THPA, manufactured by New Japan Chemical Co., Ltd.) was added as a protecting agent for secondary amines, and the protection reaction was carried out for 6 hours to obtain a maleimide compound of the present invention (I-1). GPC analysis of the resulting maleimide compound revealed that the n=0 component was 17.9%, and the weight average molecular weight (Mw) was 9,600 and the number average molecular weight (Mn) was 2,100, as determined in terms of polystyrene. The acid value (A.V.) of the solid content was 66.3 mg KOH / g.

[0162] Example B (I-2) Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 71.1 g (0.5 mol) of 1,3-bis(aminomethyl)cyclohexane (product name: 1,3-BAC, manufactured by Mitsubishi Gas Chemical Co., Inc.) as a diamine compound, and 958.4 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 192.13 g (1.0 mol) of trimellitic anhydride (product name: TMA, manufactured by Mitsubishi Gas Chemical Co., Inc.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain the maleimide compound of the present invention (I-2). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 7,100, a number average molecular weight Mn of 2,300, and an acid value (A.V.) of 138.4 mg KOH / g.

[0163] Example C (I-3) To a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Corporation) as a bismaleimide compound, 71.1 g (0.5 mol) of 1,3-bis(aminomethyl)cyclohexane (product name: 1,3-BAC, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a diamine compound, and 939.9 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80°C and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80°C for 8 hours, yielding a reaction solution containing a Michael adduct of bismaleimide and diamine. To the reaction solution containing the resulting Michael adduct, 96.1 g (1.0 mol) of trimellitic anhydride (product name: TMA, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a protecting agent for the secondary amine and 77.6 g (1.0 mol) of 2-isocyanatoethyl methacrylate (product name: Karenz MOI, manufactured by Resonac Corporation) were added, and the protection reaction was carried out for 6 hours to obtain a maleimide compound of the present invention (I-3). GPC analysis of the resulting maleimide compound revealed that the n=0 component was 11.9%. The weight average molecular weight (Mw) calculated in terms of polystyrene was 10,800, and the number average molecular weight (Mn) was 2,800. The acid value (A.V.) of the solid content was 75.1 mg KOH / g.

[0164] Example D (I-4) In a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Corporation) as a bismaleimide compound, 68.1 g (0.5 mol) of m-xylene diamine (product name: MXDA, manufactured by Mitsubishi Gas Chemical Company, Inc.) as a diamine compound, and 915.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 152.15 g (1.0 mol) of tetrahydrophthalic anhydride (product name: THPA, manufactured by New Japan Chemical Co., Ltd.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain the maleimide compound of the present invention (I-4). The resulting maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 11,700 and a number average molecular weight Mn of 2,400, as determined by GPC analysis. The acid value (A.V.) of the solid content was 61.3 mg KOH / g.

[0165] Example E (I-5) Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Corporation) as a bismaleimide compound, 77.1 g (0.5 mol) of bis(aminomethyl)norbornane (NBDA (registered trademark), manufactured by Mitsui Chemicals, Inc.) as a diamine compound, and 924.4 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 152.15 g (1.0 mol) of tetrahydrophthalic anhydride (product name: THPA, manufactured by New Japan Chemical Co., Ltd.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain a bismaleimide compound of the present invention (I-5). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 10,300 and a number average molecular weight Mn of 2,100, as determined by GPC analysis. The acid value (A.V.) of the solid content was 60.7 mg KOH / g.

[0166] Example F (I-6) Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 68.1 g (0.5 mol) of m-xylene diamine (product name: MXDA, manufactured by TCI Co., Ltd.) as a diamine compound, and 955.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 192.1 g (1.0 mol) of trimellitic anhydride (product name: TMA, manufactured by Mitsubishi Gas Chemical Co., Inc.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain the maleimide compound of the present invention (I-6). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 5589 and a number average molecular weight Mn of 2035, as determined by GPC analysis, and a solid acid value (A.V.) of 126.6 mg KOH / g.

[0167] Example G (I-7) In a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 77.1 g (0.5 mol) of bis(aminomethyl)norbornane (product name: NBDA, manufactured by Mitsui Chemicals, Inc.) as a diamine compound, and 870.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 98.1 g (1.0 mol) of maleic anhydride (manufactured by Junsei Chemical Co., Ltd.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain a bismaleimide compound of the present invention (I-7). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 9789 and a number average molecular weight Mn of 2693, as determined by GPC analysis. The acid value of the solid content (A.V.) was 64.8 mg KOH / g.

[0168] Example H (I-8) Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 77.1 g (0.5 mol) of bis(aminomethyl)norbornane (product name: NBDA, manufactured by Mitsui Chemicals, Inc.) as a diamine compound, and 920.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 98.1 g (1.0 mol) of phthalic anhydride (manufactured by Junsei Chemical Co., Ltd.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain the maleimide compound of the present invention (I-8). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 4592 and a number average molecular weight Mn of 1727. The acid value (A.V.) of the solid content was 63.3 mg KOH / g.

[0169] Example I (I-9) To a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Corporation) as a bismaleimide compound, 77.1 g (0.5 mol) of bis(aminomethyl)norbornane (product name: NBDA, manufactured by Mitsui Chemicals, Inc.) as a diamine compound, and 849.8 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80° C. for 8 hours, yielding a reaction solution containing a Michael adduct of bismaleimide and diamine. To the reaction solution containing the resulting Michael adduct, 96.0 g (0.5 mol) of trimellitic anhydride (product name: TMA, manufactured by Mitsubishi Gas Chemical Company, Inc.) and 77.6 g (0.5 mol) of 2-methacryloyloxyethyl isocyanate (product name: Karenz® MOI, manufactured by Resonac Corporation) were added as secondary amine protecting agents, and the protection reaction was carried out for 6 hours to obtain a maleimide compound of the present invention (I-9). GPC analysis of the resulting maleimide compound revealed that the n=0 component was 17.5%. The weight-average molecular weight (Mw) was 4879 and the number-average molecular weight (Mn) was 1903, as determined by polystyrene conversion. The acid value (A.V.) of the solid content was 76.8 mg KOH / g.

[0170] Example J (I-10) Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI) as a bismaleimide compound, 68.1 g (0.5 mol) of m-xylene diamine (product name: MXDA, manufactured by TCI) as a diamine compound, and 911.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80°C to achieve a uniform solution. After dissolution, a Michael addition reaction was carried out at 80°C for 8 hours, yielding a reaction solution containing a Michael adduct of bismaleimide and diamine. To the resulting reaction solution containing the Michael adduct, 148.1 g (1.0 mol) of phthalic anhydride (manufactured by Junsei Chemical Co., Ltd.) as a secondary amine protecting agent was added, and the protection reaction was carried out for 6 hours to obtain the maleimide compound of the present invention (I-10). The obtained maleimide compound had a polystyrene-equivalent weight average molecular weight Mw of 5483 and a number average molecular weight Mn of 1975, as determined by GPC analysis. The acid value of the solid content (A.V.) was 63.0 mg KOH / g.

[0171] Comparative Example A (BMI-1) 120 g of toluene and 40 g of N-methylpyrrolidone were added to a 500 ml round-bottom flask equipped with a fluororesin-coated stir bar. Next, 92.2 g (0.17 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) was added, followed by the slow addition of 16.3 g (0.17 mol) of methanesulfonic anhydride to form the salt. After stirring for approximately 10 minutes, 40.0 g (0.41 mol) of maleic anhydride was slowly added to the stirred mixture. A Dean-Stark trap and condenser were attached to the flask. The mixture was heated to reflux for 8 hours, yielding the expected amount of water. After cooling to room temperature, an additional 200 ml of toluene was added to the flask. The diluted organic layer was then washed with water (100 ml x 3 times) to remove salts and unreacted raw materials. Thereafter, the solvent was removed under vacuum to obtain 107.4 g (yield 90%, Mw=1,100, Mn=900) of a brown liquid bismaleimide compound.

[0172] The bismaleimide compound of Comparative Example A is readily available from Designer Molecules Inc. as "BMI-689."

[0173] Comparative Example B (BMI-2) In a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 68.6 g (0.5 mol) of p-aminobenzoic acid (manufactured by TCI Co., Ltd.) as an amine compound, and 763.6 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80 ° C. and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80 ° C. for 8 hours, and 1527.2 g (Mw = 1,200, Mn = 1,000) of a brown liquid bismaleimide compound solution containing a Michael adduct of bismaleimide and amine was obtained. The acid value of the solids (A.V.) was 36.7 mg KOH / g.

[0174] The materials used in this example are as follows: [Component (I): Bismaleimide Compound] I: Bismaleimide compounds (I-1) to (I-5) obtained in Examples A to E and bismaleimide compounds (BMI-1) to (BMI-2) obtained in Comparative Examples A and B.

[0175] [Component (II-1); Photopolymerization initiator] II-1: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02") [Component (II-2); Photopolymerization initiator] II-2: 2,4-dimethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S")

[0176] (Examples 1 to 10 and Comparative Examples 1 and 2) The components (I) and (II) in the amounts (parts by mass) shown in Table 1 and 50 parts by mass of propylene glycol monomethyl ether acetate as a solvent were blended as needed to prepare the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2.

[0177] <Evaluation of Photosensitive Resin Compositions> The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated as follows. The results are summarized in Tables 1 and 2.

[0178]

[0179] (Compatibility) <Compatibility with MIR-3000> 20 g of each bismaleimide resin composition prepared above, 20 g of the bismaleimide resin represented by formula (16) (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.), and 20 g of propylene glycol monomethyl ether acetate were blended in a 100 mL transparent glass bottle and heated and mixed at 80°C for 30 minutes. The mixture was then cooled to room temperature, and the appearance was observed. The evaluation results are shown in Table 1.

[0180] <Compatibility with ZXR-1889H> 20 g of each bismaleimide resin composition prepared above, 20 g of an alkali-developable dicyclopentadiene-type epoxy acrylate resin (ZXR-1889H, manufactured by Nippon Kayaku Co., Ltd.), and 20 g of propylene glycol monomethyl ether acetate were blended in a 100 mL transparent glass bottle and heated and mixed at 80°C for 30 minutes. The mixture was then cooled to room temperature, and the appearance was observed. The evaluation results are shown in Table 1.

[0181] (Photosensitivity and Development Residue Evaluation) The photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were spin-coated onto a silicon substrate and heated at 110°C for 5 minutes to form a coating film with a thickness of 10 to 15 μm. Next, using a USHIO "ultra-high pressure mercury lamp 500W Multilight" and a Kodak Step Tablet No. 2 Step Tablet, the coating film was subjected to reduced projection exposure with i-line (365 nm). The exposure dose was 500 mJ / cm. ２ After exposure, the film was developed with 1% sodium carbonate.

[0182] (Patterning Performance) Sensitivity (number of steps) was determined by how many steps of density remained in the exposed area that had passed through a Kodak Step Tablet No. 2 step tablet during development. The larger the number of steps (value), the higher the sensitivity in the darker areas of the tablet (unit: step). Furthermore, the developability was evaluated by visually observing the remaining state of the coating film after development. The unexposed area was marked as "Good" when the coating film was completely dissolved, marked as "1" when some remained, and marked as "Poor" when all remained. The resist pattern was then heat-treated (thermally cured) in nitrogen at 250°C for 60 minutes.

[0183] The photosensitive resin compositions obtained in Examples 6 to 10 were applied to a copper needle laminate (ELC4765, manufactured by Sumitomo Bakelite Co., Ltd.) using an applicator and heated at 80°C for 30 minutes to form a coating film with a thickness of 15 to 25 μm. The film was then projected and exposed using a USHIO "ultra-high pressure mercury lamp 500W multilight" via a 21-step step tablet manufactured by Stoffer. The exposure dose was 500 mJ / cm. ２ After exposure, the film was developed using 1% sodium carbonate. Sensitivity was determined by determining up to which step of density remained in the exposed area after development, which had passed through a 21-step step tablet manufactured by Stouffer. The larger the step number (value), the higher the sensitivity, which is determined to be the darker part of the tablet (unit: step). Furthermore, the developability was evaluated by visually observing the remaining state of the coating film after development, and alkaline developability was evaluated. When the coating film in the unexposed area was completely dissolved, it was marked "Good", when it was partially dissolved, it was marked "1", and when it was completely dissolved, it was marked "Poor". The results of sensitivity and developability are shown in Tables 1 and 2.

[0184] (Evaluation of Dielectric Properties (Dielectric Constant: Dk, Dielectric Loss Tangent: Df)) For the evaluation of dielectric properties, the resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were coated and dried on copper foil using a desktop coater so that the thickness after drying was 50 μm, to obtain a resin film (semi-cured). Next, 500 mJ / cm was applied to the obtained resin film (semi-cured). ２The resin film was then irradiated with UV light of 1000 nm. The resulting resin film was then heat-treated (thermally cured) in nitrogen at 250°C for 60 minutes. The copper foil support was then removed by physical peeling or etching to obtain a resin film for evaluation. A resin film was similarly formed and laminated on the prepared resin film, resulting in a resin film with a thickness of 300 μm. The resin film was then cut into test pieces measuring 60 mm in length, 2 mm in width, and 0.3 mm in thickness, and the dielectric properties were measured using a cavity resonator perturbation method. The measuring instrument used was an AET vector network analyzer ADMSO10c1, and the cavity resonator was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd. The measurement conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0185] The resin compositions obtained in Examples 6 to 10 were applied to copper foil with an applicator so that the thickness after drying was 20 μm, and then dried to obtain a resin film (semi-cured). Next, 3000 mJ / cm ２ The cured product was irradiated with UV of 1000 W. The copper foil support was then removed by physical peeling or etching to obtain a cured product for evaluation. The cured product was then cut into test pieces measuring 80 mm in length, 3 mm in width, and 0.02 mm in thickness, and the dielectric properties were measured using a cavity resonator perturbation method. The measuring instrument used was an AET vector network analyzer ADMSO10c1, and the cavity resonator was an AET 10 GHz band resonator. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C. The results are shown in Tables 1 and 2.

[0186] (Evaluation of Glass Transition Temperature (Tg)) To evaluate the glass transition temperature, the resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were coated on copper foil using a desktop coater and dried to a thickness of 20 μm after drying to obtain a resin film (semi-cured). Next, 500 mJ / cm was applied to the obtained resin film (semi-cured). ２The resin film was then irradiated with UV of 1000 kJ / s. Thereafter, the obtained resin film was heat-treated (thermally cured) in nitrogen at a temperature of 250°C for 60 minutes. Furthermore, the copper foil support was removed by physical peeling or etching to obtain a resin film (cured product) for evaluation. The dynamic viscoelasticity of the cured bismaleimide product prepared as described above was measured using a dynamic viscoelasticity measuring apparatus (DMA) (RSA-G2 manufactured by TA Instruments) (frequency 1 Hz, tensile mode, heating rate 3°C / min), and the temperature at which the loss factor (tan δ), which is the ratio M'' / M' of the loss modulus M'' to the storage modulus M', reached a maximum value was defined as the glass transition temperature Tg.

[0187] The resin compositions obtained in Examples 6 to 10 were applied to copper foil with an applicator so that the thickness after drying was 20 μm, and then dried to obtain a resin film (semi-cured). Next, 3000 mJ / cm ２ The cured product was irradiated with UV of 1000 kJ / s. The copper foil support was then removed by physical peeling or etching to obtain a cured product for evaluation. The dynamic viscoelasticity of the cured bismaleimide product prepared as described above was measured using a dynamic viscoelasticity analyzer (DMA) (RSA-G2, manufactured by TA Instruments) (frequency 10 Hz, tensile mode, heating rate 3°C / min), and the temperature at which the loss factor (tan δ), which is the ratio M'' / M' of the loss modulus M'' to the storage modulus M', reached a maximum value was defined as the glass transition temperature. The results are shown in Tables 1 and 2.

[0188] (Evaluation of Solder Heat Resistance) A commercially available double-sided copper-clad FR-4 substrate (MCL-E-67 manufactured by Resonac Inc., copper wiring thickness 18 μm) was used, and the photocurable resin composition shown in Table 1 was applied onto the substrate using a spin coater so that the film thickness after heat curing treatment would be 20 μm, and the composition was prebaked using a hot plate at 110° C. for 5 minutes to produce a cured film (coating film). Next, the composition was prebaked using a hot plate at an illuminance of 30 mW / cm at a wavelength of 365 nm. ２ 500mJ / cm ２The photosensitive portions were exposed to ultraviolet light of 1000 W at 288°C to cause a photo-curing reaction. The substrates were then post-baked at 250°C for 60 minutes using a hot air dryer to obtain test substrates for evaluating solder heat resistance in Examples 1 to 5 and Comparative Examples 1 and 2. The test substrates prepared under the above conditions were immersed in a solder bath at 288°C for 30 seconds in accordance with the test method of JIS C-6481, and a peeling test using cellophane tape was performed as one cycle. This cycle was repeated one to three times, after which the condition of the coating film was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ⊚: No change in the coating film even after three cycles. ◯: Slight change in the coating film after three cycles. △: Change in the coating film after two cycles. ×: Change in the coating film after one cycle.

[0189] As is clear from the results shown in Tables 1 and 2, the bismaleimide compounds obtained using the photosensitive resin compositions of the present invention have good compatibility with other resins, and photocuring of the maleimide groups proceeds sufficiently even with a low exposure dose, demonstrating that the bismaleimide compounds are excellent alkali-developable maleimide compounds having low dielectric properties and high heat resistance.

[0190] Synthesis Example X-1 Into a four-neck flask equipped with a thermometer, a condenser, and a stirrer, 695.1 g (1.0 mol) of dimer diamine maleimide (product name: BMI-689, manufactured by DMI Co., Ltd.) as a bismaleimide compound, 77.1 g (0.5 mol) of bis(aminomethyl)norbornane (NBDA, manufactured by Mitsui Chemicals, Inc.) as a diamine compound, and 870.3 g of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was heated to 80°C and dissolved uniformly. After dissolution, a Michael addition reaction was carried out at 80°C for 8 hours to obtain a reaction solution containing a Michael adduct of bismaleimide and diamine. 98.1 g (1.0 mol) of maleic anhydride (manufactured by Junsei Chemical Co., Ltd.) as a secondary amine protecting agent was added to the reaction solution containing the obtained Michael adduct, and the protection reaction was carried out for 6 hours to obtain the bismaleimide compound (A-1) of the present invention. GPC analysis of the obtained bismaleimide compound (A-1) revealed that the content of n=0 components was 14.7%, and the weight average molecular weight Mw calculated in terms of polystyrene was 9558 and the number average molecular weight Mn was 2651. In addition, the acid value of the solid content (A.V.) was 73.3 mgKOH / g.

[0191] Synthesis Example X-2 A bismaleimide compound (A-2) of the present invention was obtained by the same procedure as in Synthesis Example X, except that 192.1 g (1.0 mol) of trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.) was used instead of 98.1 g of maleic anhydride. GPC analysis of the obtained bismaleimide compound (A-2) revealed that the n=0 component was 12.4%, and the weight average molecular weight Mw, calculated in terms of polystyrene, was 9362 and the number average molecular weight Mn was 2508. In addition, the acid value of the solid content (A.V.) was 120.0 mg KOH / g.

[0192] Synthesis Example X-3 A bismaleimide compound (A-3) of the present invention was obtained by the same procedure as in Synthesis Example X, except that 152.2 g (1.0 mol) of tetrahydrophthalic anhydride (manufactured by New Japan Chemical Co., Ltd.) was used instead of 98.1 g of maleic anhydride. GPC analysis of the obtained bismaleimide compound (A-3) revealed that the n=0 component was 14.8%, and the weight average molecular weight Mw, calculated in terms of polystyrene, was 8053 and the number average molecular weight Mn was 2247. The acid value of the solid content (A.V.) was 66.4 mg KOH / g.

[0193] Synthesis Example X-4 A bismaleimide compound (A-4) of the present invention was obtained by the same procedure as in Synthesis Example X, except that 148.1 g (1.0 mol) of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 98.1 g of maleic anhydride. GPC analysis of the obtained bismaleimide compound (A-4) revealed that the n=0 component was 13.9%, and the weight average molecular weight Mw calculated in terms of polystyrene was 8176 and the number average molecular weight Mn was 2305. In addition, the acid value of the solid content (A.V.) was 63.8 mg KOH / g.

[0194] Synthesis Example X-5: A bismaleimide compound (A-5) of the present invention was obtained by the same procedure as in Synthesis Example X, except that 168.2 g (1.0 mol) of Rikacid MH (manufactured by New Japan Chemical Co., Ltd.) was used instead of 98.1 g of maleic anhydride. GPC analysis of the obtained bismaleimide compound (A-5) revealed that the n=0 component was 14.7%, and the weight average molecular weight Mw, calculated in terms of polystyrene, was 8953 and the number average molecular weight Mn was 2069. The acid value of the solid content (A.V.) was 68.7 mg KOH / g.

[0195] Synthesis Example X-6: A bismaleimide compound (A-6) of the present invention was obtained by the same procedure as in Synthesis Example X, except that 178.2 g (1.0 mol) of Kayahard MCD (manufactured by Nippon Kayaku Co., Ltd.) was used instead of 98.1 g of maleic anhydride. GPC analysis of the obtained bismaleimide compound (A-6) revealed that the n=0 component was 14.3%, and the weight average molecular weight Mw, calculated in terms of polystyrene, was 7140 and the number average molecular weight Mn was 1337. The acid value of the solid content (A.V.) was 71.5 mg KOH / g.

[0196] Example X-1 50.0 parts by weight of the bismaleimide compound (A-1) obtained in Synthesis Example X-1, 50.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), and 1.5 parts by weight of ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02") were uniformly mixed to obtain a resin solution. The resin solution was coated on rolled copper foil (BHY-82F-HA-V2 (thickness 18 μm) manufactured by JX Metals Corporation) so that the thickness after drying was 20 μm, and the resulting resin film (semi-cured) was dried at 80 ° C. for 30 minutes to obtain a resin film. Next, the obtained resin film (semi-cured) was subjected to 3000 mJ / cm ２ A resin film was obtained by irradiating the cured film with UV of 1000 nm. Thereafter, the cured film was heated at 150°C for 60 minutes as a heating step to obtain a resin film that had undergone a heating step. Furthermore, the copper foil support was removed by physical peeling or etching to obtain a cured film for evaluation.

[0197] Example X-2 A cured film for evaluation was obtained in the same manner as in Example X, except that the bismaleimide compound (A-2) obtained in Synthesis Example X-2 was used instead of the bismaleimide compound (A-1).

[0198] Example X-3 A cured film for evaluation was obtained in the same manner as in Example X, except that the bismaleimide compound (A-3) obtained in Synthesis Example X-3 was used instead of the bismaleimide compound (A-1).

[0199] Example X-4 A cured film for evaluation was obtained in the same manner as in Example X, except that the bismaleimide compound (A-4) obtained in Synthesis Example X-4 was used instead of the bismaleimide compound (A-1).

[0200] Example X-5 A cured film for evaluation was obtained in the same manner as in Example X, except that the bismaleimide compound (A-5) obtained in Synthesis Example X-5 was used instead of the bismaleimide compound (A-1).

[0201] Example X-6 A cured film for evaluation was obtained in the same manner as in Example X, except that the bismaleimide compound (A-6) obtained in Synthesis Example X-6 was used instead of the bismaleimide compound (A-1).

[0202] Example X-7 A cured film for evaluation was obtained in the same manner as in Example X-1, except that the temperature in the heating step was changed from 150°C to 120°C.

[0203] Example X-8 A cured film for evaluation was obtained in the same manner as in Example X-1, except that the temperature in the heating step was changed from 150° C. to 250° C. and the atmosphere in the heating step was changed from air to nitrogen.

[0204] Reference Example Y-1: A cured film was obtained in the same manner as in Example X-1, except that the heating step of heating at 150°C for 60 minutes was omitted. The obtained cured film was subjected to simultaneous thermogravimetry (TG) and differential thermal analysis (DTA) using a thermogravimetric mass spectrometer (TG-MS) with a differential thermal analysis (TG-DA) (TG-DTA measurement). The cured film was measured using a TG-MS (EVO ThermoMass 410 Photo, manufactured by Rigaku) ​​under a helium / oxygen atmosphere (helium:oxygen = 80:20) at a heating rate of 10°C / min. Mass analysis was performed using electron ionization (EI). The obtained TG / DTA curve is shown in Figure 1. Furthermore, the gas generated from the sample at 180° C. during the TG-DTA measurement was introduced into a gas chromatograph mass spectrometer (GC-MS). The resulting mass spectrum chart is shown in FIG.

[0205] Reference Example Y-2 A cured film was obtained in the same manner as in Example X-2, except that the heating step of heating at 150° C. for 60 minutes was omitted.

[0206] Reference Example Y-3 A cured film was obtained in the same manner as in Example X-3, except that the heating step of heating at 150° C. for 60 minutes was omitted.

[0207] Reference Example Y-4 A cured film was obtained in the same manner as in Example X-4, except that the heating step of heating at 150° C. for 60 minutes was omitted.

[0208] Reference Example Y-5 A cured film was obtained in the same manner as in Example X-5, except that the heating step of heating at 150° C. for 60 minutes was omitted.

[0209] Reference Example Y-6 A cured film was obtained in the same manner as in Example X-6, except that the heating step of heating at 150° C. for 60 minutes was omitted.

[0210] <Evaluation of Photosensitive Resin Composition> The cured films of Examples X-1 to X-7 and Reference Examples Y-1 to Y-7 were evaluated as follows.

[0211] (Evaluation of Dielectric Properties (Dielectric Loss Tangent: Df)) The cured film was cut into a length of 80 mm, a width of 3 mm, and a thickness of 0.02 mm, and the resulting test pieces were used to measure the dielectric properties by a cavity resonator perturbation method. The measuring instrument used was an AET vector network analyzer ADMSO10c1, and the cavity resonator was an AET 10 GHz band resonator. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C. The results are shown in Tables 3 and 4.

[0212] (5% Weight Loss Temperature (Td5)) The cured film was measured for 5% weight loss temperature using a thermogravimetric differential scanning calorimeter (TGA / DSC1 manufactured by Mettler Toledo) at a temperature range of 50 to 580°C (heating rate of 10°C / min). The results are shown in Tables 3 and 4.

[0213]

[0214]

[0215] As is clear from the results shown in Tables 3 and 4, the cured films obtained by subjecting the resin compositions containing the bismaleimide compounds (A-1 to A-6) to a heating step were shown to have low dielectric properties and high heat resistance.

[0216] As is clear from the results shown in Figure 1, compound (A-1) began to lose weight at around 150°C. Furthermore, Figure 2 suggests that the gas evolved from the sample during the heating step was maleic anhydride (molecular weight 98). Therefore, it is believed that the heating step caused the volatilization of carboxyl groups derived from the acid anhydride contained in the cured film, reducing the polarity of the cured film, thereby decreasing the dielectric tangent and increasing the 5% weight loss temperature.

[0217] As described above, the present invention is applicable to a photosensitive resin having a relatively low exposure dose (500 mJ / cm ２The present invention provides a bismaleimide compound and a photosensitive resin composition thereof that are capable of forming fine patterns on a substrate (such as a substrate for a semiconductor device) and have good compatibility with other resins, and that have a high Tg and are alkali-developable. Therefore, the bismaleimide compound and the photosensitive resin composition of the present invention are very useful as surface protection films, interlayer insulating films, insulating films for rewiring layers, and the like for semiconductor devices.

Claims

1. A bismaleimide compound represented by the following general formula (1): In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units and represents an integer of 1 to 100.

2. The bismaleimide compound according to claim 1, wherein X in formula (1) is one or more divalent hydrocarbon groups represented by the following formulae (2-1) to (4): In formulas (2-1) to (4), n1 and n2 each represent a number from 5 to 30 and may be the same or different. R independently represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 4 to 40 carbon atoms. * represents the bond to the maleimide group.

3. The bismaleimide compound according to claim 1 or 2, wherein the weight average molecular weight of the bismaleimide compound of formula (1) is 1,000 to 50,000, and the dielectric loss tangent of a cured product obtained by addition polymerization of the bismaleimide compound of formula (1) is 0.010 or less.

4. The bismaleimide compound according to claim 1 or 2, wherein in general formula (1), the hydrocarbon group constituting Y is a hydrocarbon group having an aromatic ring structure represented by the following formula (5), or a hydrocarbon group having an aliphatic ring structure selected from the group represented by the following formula (6): In formula (5), R １ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each 1 independently represents an integer of 1 to 4. * represents the bond to N. In formula (6), R ２ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, a halogen atom, a hydroxy group, or a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 3 to 6 carbon atoms. Each p independently represents an integer of 1 to 4. * represents the bond to N.

5. The bismaleimide compound according to claim 1 or 2, wherein in general formula (1), the carboxyl group-containing organic group constituting Z is derived from maleic anhydride, trimellitic anhydride, phthalic anhydride, 4-methylhexahydrophthalic anhydride, methyl-endomethylenetetrahydrophthalic anhydride, or tetrahydrophthalic anhydride.

6. The bismaleimide compound according to claim 1 or 2, wherein in the general formula (1), the carboxyl group-containing organic group constituting Z has any one of the following structures: In the formula, the wavy line represents the bond to the N.

7. The bismaleimide compound according to claim 1 or 2, wherein in the general formula (1), the ethylenically unsaturated group-containing organic group constituting Z has a partial structure represented by the following formula (7): In formula (7), R ３ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents the bond to N.

8. A method for producing a bismaleimide compound represented by the following general formula (1), comprising the steps of: reacting a bismaleimide compound (A) represented by the following general formula (8) with a diamino compound (B) represented by the following general formula (9) to obtain a bismaleimide compound (C) represented by the following general formula (10); and reacting the bismaleimide compound (C) represented by the general formula (10) with a protecting agent (D) selected from an acid anhydride or an ethylenically unsaturated group-containing compound. In formula (8), X represents a divalent hydrocarbon group having 6 to 200 carbon atoms. In formula (9), Y represents a divalent hydrocarbon group having 6 to 50 carbon atoms. In formula (10), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, and each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms. n is the average number of repeating units and represents an integer of 1 to 100. In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group, provided that at least one Z is a carboxyl group-containing organic group or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units and represents an integer of 1 to 100.

9. A resin composition comprising a bismaleimide compound represented by the following general formula (1) and a bismaleimide compound represented by the following general formula (8), wherein the content of the bismaleimide compound represented by the following general formula (8) is 50% or less when the total of the maleimide compound represented by the following general formula (1) and the bismaleimide compound represented by the following general formula (8) is taken as 100%. In formula (1), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms, each Y independently represents a divalent hydrocarbon group having 6 to 50 carbon atoms, and each Z independently represents a monovalent group which is a hydrogen atom, a carboxyl group-containing organic group, or an ethylenically unsaturated group-containing organic group. n is the average number of repeating units and is an integer of 1 to 100. In formula (8), each X independently represents a divalent hydrocarbon group having 6 to 200 carbon atoms.

10. A resin composition containing the bismaleimide compound according to claim 1 or 2 and a compound capable of reacting with a maleimide group.

11. A resin composition comprising the bismaleimide compound according to claim 1 or 2 and one or more compounds selected from the group consisting of maleimide compounds other than the bismaleimide compound, cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

12. A resin composition containing the bismaleimide compound according to claim 1 or 2 and a photopolymerization initiator or a curing catalyst.

13. The resin composition according to claim 9, further comprising a filler.

14. A resin composition comprising the bismaleimide compound according to claim 1 or 2 and at least one selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, an anionic curing accelerator, and a cationic curing accelerator.

15. A cured product of a resin composition containing the bismaleimide compound according to claim 1 or 2.

16. A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film of a rewiring layer, which contains the bismaleimide compound according to claim 1 or 2.

17. A dry film resist comprising a composition containing the bismaleimide compound (1) according to claim 1 or 2 and a photopolymerization initiator.

18. A cured film obtained by subjecting a resin composition containing the bismaleimide compound according to claim 1 or 2 to a heating process.

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