Bismaleimide compound, resin composition using same, cured product thereof, semiconductor element, and dry film resist

Abstract

The purpose of the present invention is to provide a bismaleimide compound which is capable of achieving a high glass transition point (Tg), and with which it is possible to provide a resin composition that satisfies: (1) the dielectric loss tangent is low; (2) the compatibility with organic solvent and resin material, especially with a resin material having a polar functional group is good; and (3) photolithography using an organic solvent or an alkaline aqueous solution is possible. Disclosed is a bismaleimide compound which includes a structural unit represented by general formula (1). In general formula (1), A represents a tetravalent organic group including a cyclic structure. B1 represents a divalent hydrocarbon group having 13 to 200 carbon atoms and no cyclic structure. In cases where a plurality of structural units of general formula (1) are present in the bismaleimide compound, a plurality of A's may be independent and may be the same as or different from each other, and a plurality of B1s may be independent and may be the same as or different from each other.

Description

Bismaleimide compound, resin composition using the same, cured product thereof, semiconductor device, and dry film resist

[0001] The present invention relates to a bismaleimide compound, a resin composition using the same, a cured product thereof, a semiconductor device, and a dry film resist. 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 will be essential as a noise countermeasure. Therefore, there is a demand for the development of insulating materials that can be formed into fine patterns and have 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 has the drawback of requiring 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 a lower dielectric loss tangent for high-frequency applications.

[0004] Therefore, 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 aromatic tetracarboxylic acids and dimer acids, which are dimers of unsaturated fatty acids such as oleic acid.

[0006] 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

[0007] However, the polyimides described in Patent Documents 5 and 6 are difficult to cure alone and have poor compatibility with other resins. Furthermore, because polyimides undergo ring-closing dehydration during curing, voids may form and flattening may be impossible, depending on the conditions of use, for example, when laminating a rewiring layer. The bismaleimide compound using dimer diamine described in Patent Document 4 has a low dielectric loss tangent and excellent dielectric properties, but the range of compatible resin skeletons is narrow, which limits the resins that can be incorporated into the composition. Furthermore, it has poor compatibility with alkaline aqueous solutions, particularly 1% sodium carbonate aqueous solutions. Therefore, when studying resin compositions that can be patterned by alkaline development, the range of resins with polar functional groups to be selected is narrow, making them less practical.

[0008] Therefore, an object of the present invention is to provide a bismaleimide compound with a high Tg (glass transition temperature) that 1) has a low dielectric dissipation factor, 2) has good compatibility with organic solvents and resin materials, particularly with resin materials having a polar functional group, and 3) is capable of providing a resin composition that can be photolithographed using an organic solvent or an alkaline aqueous solution.

[0009] As a result of extensive research to solve the above problems, the present inventors have found that the following bismaleimide compound can achieve the above object, and have thus completed the present invention.

[0010] That is, the present invention relates to the following:

[0011] [1] A bismaleimide compound containing a structural unit represented by the following general formula (1):

[0012]

[0013] In the general formula (1), A represents a tetravalent organic group containing a cyclic structure. １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. １ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. When a plurality of structural units of general formula (1) are present in a bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and each of the plurality of B's １ are each independent and may be the same or different. * denotes a bonding site to other structural units.

[0014] [2] The bismaleimide compound according to [1], further comprising a structural unit represented by the following general formula (2), which has a dielectric loss tangent of 0.010 or less when cured and a molecular weight of 2,000 to 50,000: In general formula (2), A's each independently represent a tetravalent organic group containing a cyclic structure. ２ represents a divalent hydrocarbon group having a cyclic structure. * represents a bonding site with another structural unit. However, B ２ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. When a plurality of structural units of the general formula (2) are present in the bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and each of the plurality of B's １ , B ２ are each independently and may be the same or different. The order of the repeating units is not limited, and the bonding pattern may be alternating, block, or random.

[0015] [3] The bismaleimide compound according to [1] or [2], further comprising a structural unit represented by the following general formula (3):

[0016] In formula (3), A independently represents a tetravalent organic group containing a cyclic structure. ３ Each independently represents a divalent hydrocarbon group derived from a dimer acid. * represents a bond to another structural unit.

[0017] [4] The bismaleimide compound according to any one of [1] to [3], wherein in the general formula (1), (2), or (3), the organic group constituting A is selected from the group consisting of the following structural formulas:

[0018]

[0019] In the above structural formula, the bond marked with a wavy line indicates the position where the organic group constituting A is bonded to the imide group in the general formula (1), (2) or (3).

[0020] [5] In the general formula (1), B １ The hydrocarbon group constituting the formula (2) is an alkylene group or alkenylene group having 14 to 30 carbon atoms, and is a linear or branched alkylene group or alkenylene group having one or more side chains of alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms, and in the formula (2), B ２ [5] The bismaleimide compound according to any one of [1] to [4], wherein the hydrocarbon group constituting the formula (I) represents a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

[0021] [6] In the general formula (1), B １ is a branched hydrocarbon group having 2n (n is an integer of 6≦n≦14) carbon atoms in the main chain portion and having a side chain composed of an ethyl group or a methyl group, and ２ The bismaleimide compound according to [2] or [3], wherein the hydrocarbon group constituting the formula (I) represents a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

[0022] [7] In the general formula (1), B １ is a hydrocarbon group obtained by removing an amine group from 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene, and in the general formula (2), B ２ The bismaleimide compound according to [2] or [3], wherein the hydrocarbon group constituting the formula (I) represents a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

[0023] [8] B ２ is a hydrocarbon group having an aromatic ring structure represented by the following formula (4-1), or a hydrocarbon group having an alicyclic structure selected from the group represented by the following formula (4-2):

[0024]

[0025] In formula (4-1), 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 a bonding site to N or another structural unit.

[0026]

[0027] In formula (4-2), 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 10, p' independently represents an integer of 1 to 14, and p'' independently represents an integer of 1 to 7. * represents a bonding site to N or another structural unit.

[0028] [9] A resin composition comprising the bismaleimide compound (X) according to any one of [1] to [8] and a compound or resin (Y) containing one or more carboxy groups.

[0029]

[10] The resin composition according to [9], further comprising one or more compounds or resins (Z) selected from the group consisting of maleimide compounds other than the bismaleimide compound (X), cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

[0030]

[11] The resin composition according to

[10] , further containing a photopolymerization initiator (W) or a curing catalyst.

[0031]

[12] A cured product of a resin composition containing the bismaleimide compound according to any one of [1] to [8].

[0032]

[13] 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 any one of [1] to [8].

[0033]

[14] A dry film resist comprising a composition containing the bismaleimide compound according to any one of [1] to [8] and a photopolymerization initiator.

[0034] The bismaleimide compound of the present invention has excellent compatibility. Therefore, the bismaleimide compound is compatible with a wide range of resin materials and can be formulated with various resins or compounds having a carboxy group. Therefore, the bismaleimide compound can provide a resin composition that can be photolithographed using an alkaline aqueous solution. Furthermore, the present invention makes it possible to provide a bismaleimide compound that can have a high Tg (glass transition temperature).

[0035] The present invention will be described in detail below. <Bismaleimide Compound> The bismaleimide compound according to the present invention is a bismaleimide compound containing two or more structural units represented by the following general formula (1).

[0036]

[0037] In the general formula (1), A represents a tetravalent organic group containing a cyclic structure. １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and no cyclic structure. When a plurality of structural units of general formula (1) are present in the bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and the plurality of B's １ are each independent and may be the same or different. * denotes a bonding site to another structural unit. The bismaleimide compound according to the present invention may further contain a structural unit represented by the following general formula (2):

[0038]

[0039] In general formula (2), A's each independently represent a tetravalent organic group containing a cyclic structure.２ represents a divalent hydrocarbon group having a cyclic structure. * represents a bonding site with another structural unit. However, B ２ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. When a plurality of structural units of general formula (1) and (2) are present in the bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and the plurality of B's １ , B ２ are each independently and may be the same or different. The order of the repeating units is not limited, and the bonding pattern may be alternating, block, or random.

[0040] The bismaleimide compound according to the present invention may further contain a structural unit represented by the following general formula (3).

[0041] In the general formula (3), A's each independently represent a tetravalent organic group containing a cyclic structure. ３ Each independently represents a divalent hydrocarbon group derived from a dimer acid. * represents a bond to another structural unit.

[0042] The above formula (1) can also be expressed as the following formula (1').

[0043] In formula (1'), n is 1 to 100, and A represents a tetravalent organic group containing a cyclic structure. １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and no cyclic structure. When a plurality of structural units of general formula (1) are present in the bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and the plurality of B's １ are each independent and may be the same or different. * denotes a bonding site to other structural units.

[0044] The above formula (2) can also be expressed as the following formula (2').

[0045] In formula (2'), A independently represents a tetravalent organic group containing a cyclic structure. ２ represents a divalent hydrocarbon group having a cyclic structure. * represents a bonding site with another structural unit. However, B２ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid, and m is 0 to 100. The order of the repeating units bracketed by m in formula (1') and n in formula (2') is not limited, and the bonding pattern may be alternating, block, or random.

[0046] The above formula (3) can also be expressed as the following formula (3').

[0047] In formula (3′), A independently represents a tetravalent organic group containing a cyclic structure. ３ Each independently represents a divalent hydrocarbon group derived from a dimer acid. * represents a bond to another structural unit.

[0048] The bismaleimide compound according to the present invention may be a bismaleimide compound containing three structural units represented by the following formula (5):

[0049] In formula (5), A independently represents a tetravalent organic group containing a cyclic structure. １ , B ２ are each independently, B １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure, and B ２ represents a divalent hydrocarbon group having a cyclic structure. ３ Each independently represents a divalent hydrocarbon group derived from a dimer acid. * represents a bond to another structural unit.

[0050] The above formula (5) can also be expressed as the following formula (5'): That is, the bismaleimide compound according to the present invention may be a bismaleimide compound containing three structural units represented by the following formula (5').

[0051] In formula (5'), A independently represents a tetravalent organic group containing a cyclic structure. １ , B ２ are each independently, B １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure, and B ２ represents a divalent hydrocarbon group having a cyclic structure. ３independently represent a divalent hydrocarbon group derived from a dimer acid. * represents a bonding site with another structural unit. m is 1 to 100, and n and o are 0 to 100. The order of the repeating units bracketed by m, n, and o is not limited, and the bonding pattern may be alternating, block, or random.

[0052] By compounding the bismaleimide compound of the present invention with a compound or resin (Y) (also referred to as component (Y)) containing one or more carboxy groups, as described below, a resin composition suitable for photolithography (alkali development) using an alkaline aqueous solution can be obtained. The compound or resin (Y) containing one or more carboxy groups in the molecule has excellent alkaline developability due to the carboxy groups, but is prone to polarization and has a dielectric dissipation factor of approximately 0.02 to 0.03 when cured alone. Therefore, this material is difficult to use in the semiconductor field, where low dielectric properties such as a dielectric dissipation factor of 0.01 or less are required. To utilize such a resin in the semiconductor field, it is necessary to compound it with other resin materials to achieve low dielectric properties as a composition. Therefore, the resin material used in the compounding must have low dielectric properties. Therefore, it is desirable for the bismaleimide compound of the present invention to have a dielectric dissipation factor of 0.010 or less when cured.

[0053] Furthermore, in order to enable the composition to form a pattern by alkali development after i-line exposure, the molecular weight must be 100,000 or less. On the other hand, from the viewpoint of compatibility with resin materials having polar functional groups, the molecular weight is desirably 1,000 or more. Therefore, the molecular weight of the bismaleimide compound is desirably 1,000 to 100,000, more desirably 2,000 to 75,000, and even more desirably 2,000 to 50,000.

[0054] In the formula (1), (1'), (2), (2'), (3), (3'), (5) or (5'), each A independently represents a tetravalent organic group containing a cyclic structure, and is preferably any of the tetravalent organic groups represented by the following structural formulas: In the structural formulas, the bond marked with a wavy line indicates the position at which the organic group constituting A is bonded to the imide group in the general formula (1), (1'), (2), (2'), (3), (3'), (5) or (5').

[0055]

[0056] In the formula (1), (1'), (2), (2'), (3), (3'), (5) or (5'), A is more preferably any of the tetravalent organic groups represented by the following structural formulas:

[0057]

[0058] In the formula (1), (1′), (5) or (5′), B １ are independently divalent hydrocarbon groups having 13 to 200 carbon atoms and no cyclic structure, and are alkylene or alkenylene groups having preferably 14 to 30 carbon atoms, more preferably 16 to 24 carbon atoms, and even more preferably 18 to 22 carbon atoms, which are linear or branched alkylene or alkenylene groups having one or more side chains of alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms. １ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid.

[0059] The term "alkylene group or alkenylene group having 14 to 30 carbon atoms" used herein encompasses linear or branched alkylene groups having 14 to 30 carbon atoms and linear or branched alkenylene groups having 14 to 30 carbon atoms.

[0060] Examples of alkylene or alkenylene groups having 14 to 30 carbon atoms include linear alkylene groups having 14 to 30 carbon atoms; branched alkylene groups having 14 to 30 carbon atoms and having one or more alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms as side chains; linear alkenylene groups having 14 to 30 carbon atoms; and branched alkenylene groups having 14 to 30 carbon atoms and having one or more alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms as side chains. １ is an alkylene group or alkenylene group having 14 to 30 carbon atoms, and is either linear or branched having one or more alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms as side chains, whereby a bismaleimide compound having excellent compatibility with resin materials having a polar functional group, in particular a carboxy group, can be obtained.

[0061] Examples of linear alkylene groups having 14 to 30 carbon atoms include an n-tetradecanylene group, an n-pentadecanylene group, an n-hexadecanylene group, an n-heptadecanylene group, an n-octadecanylene group, an n-nonadecanylene group, an n-icosanylene group, an n-henicosanylene group, an n-docosanylene group, an n-tricosanylene group, an n-tetracosanylene group, an n-pentacosanylene group, an n-hexacosanylene group, an n-heptacosanylene group, and an n-octacosanylene group. Examples of linear alkenylene groups having 14 to 28 carbon atoms include tetradekenylene, pentadekenylene, hexadekenylene, heptadekenylene, octadekenylene, nonadekenylene, icosenylene, henicosenylene, docosenylene, tricosenylene, tetracosenylene, pentacosenylene, hexacosenylene, heptacosenylene, and octacosenylene groups.

[0062] A "branched alkylene group having 14 to 30 carbon atoms and having one or more side chains of alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms" refers to an alkylene group having 14 to 30 carbon atoms and having at least one group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms as a branched chain. An "alkenylene group having 14 to 30 carbon atoms and having one or more branched chains of alkyl groups having 1 to 4 carbon atoms and / or alkenyl groups having 2 to 4 carbon atoms" refers to an alkenylene group having a total of 14 to 30 carbon atoms and having at least one group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkenyl groups having 2 to 4 carbon atoms as a branched chain. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. Examples of the alkenyl group having 2 to 4 carbon atoms include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.

[0063] B of the bismaleimide compound of the present invention １ The hydrocarbon group constituting the above is preferably an alkylene group having 14 to 30 carbon atoms, which is linear or branched having one or more alkyl group(s) having 1 to 4 carbon atoms as a side chain, from the viewpoint that it can impart appropriate flexibility to the resulting resin composition when used as a component of a resin additive described later, more preferably an alkylene group having 14 to 30 carbon atoms, which is branched having one alkyl group having 1 to 4 carbon atoms as a side chain, and even more preferably an alkylene group having a total of 14 to 30 carbon atoms, which is branched having one ethyl group or one or more methyl group as a side chain. １The hydrocarbon group having 14 to 28 carbon atoms constituting the above group can be easily produced using a commercially available dibasic acid or a derivative thereof as described below, and therefore, it is preferred that the main chain portion (i.e., the chain hydrocarbon portion excluding branched chains) of the constituting alkylene group or alkenylene group has 2n carbon atoms (n is an integer of 7 to 14).

[0064] Examples of such hydrocarbon groups include divalent hydrocarbon groups obtained by removing two amino groups from a diamine having 14 to 200 carbon atoms. Specific examples of diamines having 14 to 200 carbon atoms include linear saturated diamines such as tetradecanediamine, hexadecanediamine, octadecanediamine, eicosanediamine, docosanediamine, tetracosanediamine, and octacosanediamine; tetradecanediamine-7-ene, hexadecanediamine-6-ene, hexadecanediamine-8-ene, octadecanediamine-8-ene, octadecanediamine-10-ene, eicosanediamine-6-ene, eicosanediamine-8-ene, and eicosanediamine-10-ene; Straight-chain unsaturated diamines such as 2-ene, eicosanediamine-8,12-diene, eicosanediamine-10,14-diene, docosanediamine-7,11,15-triene, docosanediamine-8,12,16-triene, 1,24-tetracosanediamine-8,12,16-triene, and tetracosanediamine-10,14,18-triene; 6,8-dimethyltetradecanediamine, 7-ethyltetradecanediamine, 7-propyltetradecanediamine, 7-ethylhexadecanediamine, and 7-butylhexadecanediamine. Branched saturated diamines such as decanediamine, 7-isopropyl-10-methylhexadecanediamine, 8-ethyloctadecanediamine, 8-isopropyl-11-methyloctadecanediamine, 8,13-diethyloctadecanediamine, 8,13-dimethyleicosanediamine, 9,12-dimethyleicosanediamine, and 9,12-diethyleicosanediamine; 7-vinyltetradecanediamine, 7-vinylhexadecanediamine-8-ene, 7-isopropenyl-10-methylhexadecanediamine-9-ene, and the like. branched unsaturated diamines such as octadecane, 8-vinyl-octadecanediamine-9-ene, 7,12-dimethyloctadecanediamine-7,11-diene, 7,12-diethyloctadecanediamine-7,11-diene, 8-isopropenyl-11-methyloctadecanediamine-10-ene, 8-ethyl-11-isopropenyloctadecanediamine-10-ene, 8,13-dimethyleicosanediamine-8,12-diene, and 9,12-dimethyleicosanediamine-8,12-diene; and the like.A specific example of a commercially available diamine is Diamine H20 (manufactured by Okamura Oil Mills, Ltd.).

[0065] B of the bismaleimide compound １ The divalent hydrocarbon group constituting the formula (I) is preferably a divalent hydrocarbon group obtained by removing the amine group from 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene.

[0066] In the formula (2), (2'), (5) or (5'), B ２ are independently divalent hydrocarbon groups having a cyclic structure. ２ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. The divalent hydrocarbon group having a cyclic structure may be a compound having a cyclic structure, and may have a substituent bonded thereto. The cyclic structure may be an aromatic ring or an aliphatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a chrysene ring, a triphenylene ring, a tetraphene ring, a pyrene ring, a pentacene ring, a picene ring, and a perylene ring. On the other hand, examples of the aliphatic ring include a monocycloalkane ring, a bicycloalkane ring, a tricycloalkane ring, a tetracycloalkane ring, and a dicyclopentadiene ring.

[0067] B ２ The hydrocarbon group constituting the formula (4-1) is preferably a hydrocarbon group having an aromatic ring structure represented by the following formula (4-1) or a hydrocarbon group having an alicyclic structure selected from the group represented by the following formula (4-2):

[0068]

[0069] In formula (4-1), 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 a bonding site to N or another structural unit.

[0070]

[0071] In formula (4-2), 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. * represents a bond to N or another structural unit.

[0072] R in the formula (4-1) １ and R in the formula (4-2) 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 1 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.

[0073] 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 ２As 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.

[0074] In the formula (4-1), l represents an integer of 1 to 4. In addition, in the formula (4-2), p represents an integer of 1 to 10, p' represents an integer of 1 to 14, and p'' represents an integer of 1 to 7. In addition to excellent adhesion to chips and substrates, etc., the compound exhibits good solubility in solvents, a low melting point, low water absorption, and good compatibility with other resins. １ and R ２ are preferably all hydrogen atoms, and therefore, l is preferably 4, p is preferably 8, p' is preferably 12, and p'' is preferably 6.

[0075] Specific examples of the hydrocarbon group having an aromatic ring represented by the formula (4-1) include hydrocarbon groups obtained by removing an amine group from metaxylenediamine (the following formula (6)), paraxylenediamine (the following formula (7)), and orthoxylenediamine (the following formula (8)). ２ is preferably a hydrocarbon group of the following formula (6): In the following formulas (6) to (8), * represents a bond to N or another structural unit.

[0076]

[0077]

[0078]

[0079] The hydrocarbon group having an alicyclic structure represented by the formula (4-2) is preferably a hydrocarbon group obtained by removing an amine group from 1,3-bis(aminomethyl)cyclohexane (formula (9) below), norbornanediamine (formula (10) below), isophoronediamine (formula (11) below), or (formula (12) below). (* represents a bond to N or another structural unit.)

[0080]

[0081]

[0082]

[0083]

[0084] In the formula (3), (3'), (5) or (5'), B ３ The divalent hydrocarbon groups derived from dimer acid constituting the formula (I) are independently divalent hydrocarbon groups having 6 to 200, preferably 8 to 100, and more preferably 10 to 50 carbon atoms. Among these, branched divalent hydrocarbon groups in which one or more hydrogen atoms in the divalent hydrocarbon group are substituted with an alkyl or alkenyl group having 6 to 200 or more, preferably 8 to 100, and more preferably 10 to 50 carbon atoms, are 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 along the molecular chain. Specific examples of the branched divalent hydrocarbon group include divalent hydrocarbon groups obtained by removing two carboxy groups from a dimer of an unsaturated fatty acid and divalent hydrocarbon groups obtained by removing two amino groups from a diamine having amino groups at both ends, known as a dimer diamine. Dimer diamines are compounds in which two carboxy groups of a dimer acid, a dimer of an unsaturated fatty acid such as oleic acid, have been substituted with primary amino groups, as shown in the following formulas (13) to (18) (see, for example, Japanese Patent Application Laid-Open No. 9-12712). Specific examples of commercially available dimer diamines include PRIAMINE (registered trademark) 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. A non-limiting general formula for dimer diamines is shown below. In each of formulas (13) to (18), 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.

[0085]

[0086] B ３ The hydrocarbon group constituting the above is preferably a divalent hydrocarbon group obtained by removing two amino groups from a dimer diamine represented by the above formulas (13) to (18). Specifically, it is preferably a divalent hydrocarbon group represented by the following formulas (13') to (18'). In each of formulas (13') to (18'), m+n preferably represents 6 to 17, and p+q preferably represents 8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. * represents a bond to N or another structural unit.

[0087] <Method for Producing Bismaleimide Compound> The method for producing the bismaleimide compound is not particularly limited, but the compound can be efficiently produced, for example, by the method shown below. A bismaleimide compound can be obtained by synthesizing an amic acid from a tetrabasic acid dianhydride and a diamine, followed by ring-closing dehydration in Step I, then reacting with maleic anhydride to synthesize a maleamic acid, and finally by ring-closing dehydration to cap the molecular chain terminals with maleimide groups in Step II.

[0088] In the above production method, each step can be roughly divided into two steps: a synthesis reaction of amic acid or maleamic acid, and a ring-closing dehydration reaction, which will be described in detail below.

[0089] In step I, a specific tetrabasic acid dianhydride is first reacted with a specific diamine to synthesize an amic acid. This reaction generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling aprotic polar solvent) at room temperature (25°C) to 100°C. The subsequent ring-closing dehydration reaction of the amic acid is carried out at 90 to 120°C, and then the water by-produced by the condensation reaction is removed from the system. To promote the ring-closing dehydration reaction, an organic solvent (e.g., a nonpolar solvent, a high-boiling aprotic polar solvent, etc.) or an acid catalyst can be added.

[0090] Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). These may be used alone or in combination of two or more. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These may be used alone or in combination of two or more. The molar ratio of diamine to tetrabasic acid dianhydride is preferably diamine / tetrabasic acid dihydrate = 2.5 to 1.02 / 1.0, and more preferably diamine / tetrabasic acid dianhydride = 2.0 to 1.15 / 1.0. Blending at this ratio ultimately enables the synthesis of a copolymer containing amino groups at both ends.

[0091] In step II, the diamine having amino groups at both ends obtained in step I is reacted with maleic anhydride at room temperature (25°C) to 100°C to synthesize maleamic acid. Finally, the molecular chain ends are capped with maleimide groups by ring-closing dehydration while removing the water by-product in the system at 95 to 120°C, thereby obtaining the desired bismaleimide compound. Carrying out the capping reaction with maleimide groups at the molecular chain ends at 120°C or below is preferred because it reduces the likelihood of side reactions and high molecular weight products. This production method allows the resulting bismaleimide compound to have a block copolymer structure, thereby achieving uniform and improved compatibility with the synthesized resin.

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

[0093] The mixing ratio of the raw materials in the reaction is as follows: (B １ and an organic diamine having a divalent hydrocarbon group having 13 to 200 carbon atoms and no cyclic structure constituting B. ２ and an organic diamine having a divalent hydrocarbon group having a cyclic structure constituting B ３In addition, from the viewpoint of obtaining a composition that can achieve a high Tg and can provide a cured product having low dielectric properties, it is preferable that the ratio of (B) to (the total number of moles of the tetracarboxylic dianhydride constituting A and half the number of moles of maleic anhydride) is 1:1. １ the number of moles of an organic diamine having a divalent hydrocarbon group having 13 to 200 carbon atoms and no cyclic structure constituting (B) ２ The molar ratio of the organic diamine having a cyclic structure constituting B is preferably 10:0.1 to 10:10, and more preferably 10:0.1 to 10:5. ３ When a divalent hydrocarbon group derived from a dimer acid constituting the compound (B １ and the number of moles of an organic diamine having a divalent hydrocarbon group having 13 to 200 carbon atoms constituting B ３ the number of moles of the organic diamine having a divalent hydrocarbon group constituting the compound (B) ２ It is desirable that the ratio of m+o:n (the number of moles of an organic diamine having a divalent hydrocarbon group with a cyclic structure constituting the bismaleimide compound) is 10:0.1 to 10:5. That is, when the bismaleimide compound contains three structural units represented by formula (5'), it is desirable that m+o:n = 10:0.1 to 10:5. Furthermore, with regard to m:o, from the viewpoint of compatibility with polar functional groups, an increase in the ratio of o leads to incompatibility, so it is desirable that m:o = 10:0 to 5:5.

[0094] <Compound or resin (Y) containing one or more carboxy groups> The compound or resin (Y) containing one or more carboxy groups (also referred to as component (Y)) is not particularly limited as long as it contains one or more carboxy groups in the compound. The compound containing one or more carboxy groups may be a salt such as a sodium salt or a potassium salt, and when it contains two or more carboxy groups in the molecule, it may be an acid anhydride formed by linking them together. Component (Y) can be used alone or in an appropriate mixture of two or more types.

[0095] Examples of the component (Y) include formic acid, aliphatic compounds containing one or more carboxy groups, aromatic compounds containing one or more carboxy groups, and heterocyclic compounds containing one or more carboxy groups. These components (Y) can be used alone or in combination of two or more.

[0096] Examples of aliphatic compounds containing one or more carboxy groups include linear aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, linear aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may have a hydrogen atom and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxy group, an amino group, or a carboxyalkyl group in the molecule. Furthermore, when these compounds have two or more carboxy groups in the molecule, they may be acid anhydrides formed by linking them together. When these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by linking a carboxyalkyl group and a carboxy group together. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them together.

[0097] Examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy. Examples of aryloxy groups include phenoxy and p-tolyloxy. Examples of aryl groups include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthryl. Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminodimethyl group, an aminodiethyl group, an aminodipropyl group, an aminobutyl group, an aminohexyl group, and an aminononyl group. Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, a carboxyhexyl group, and a carboxynonyl group.

[0098] Examples of the chain aliphatic monocarboxylic acid include saturated fatty acids such as acetic acid, propionic acid, isobutyric acid, butyric acid, isovaleric acid, valeric acid, caproic acid, lactic acid, succinic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid; and unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

[0099] Examples of alicyclic monocarboxylic acids include monocyclic carboxylic acids such as cyclopropanecarboxylic acid, cyclopropenecarboxylic acid, cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, cycloheptenecarboxylic acid, cyclooctanecarboxylic acid, and cyclooctenecarboxylic acid; and polycyclic or bridged alicyclic carboxylic acids such as norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid, ethyladamantanecarboxylic acid, and butyladamantanecarboxylic acid.

[0100] Examples of the linear aliphatic polycarboxylic acid include carboxylic acids in which one or more carboxy groups are further added to a linear aliphatic monocarboxylic acid, such as propionedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

[0101] Examples of the alicyclic polycarboxylic acid include carboxylic acids in which one or more carboxy groups are further added to an alicyclic monocarboxylic acid. Examples of the carboxylic acid include monocyclic carboxylic acids such as cyclopropane dicarboxylic acid, cyclopropene dicarboxylic acid, cyclopropane tricarboxylic acid, cyclopropene tricarboxylic acid, cyclobutane dicarboxylic acid, cyclobutene dicarboxylic acid, cyclobutane tricarboxylic acid, cyclobutene tricarboxylic acid, cyclobutane tetracarboxylic acid, cyclobutene tetracarboxylic acid, cyclopentane dicarboxylic acid, cyclopentene dicarboxylic acid, cyclopentane tricarboxylic acid, cyclopentene tricarboxylic acid, cyclopentane tetracarboxylic acid, cyclopentene pentacarboxylic acid, cyclopentene pentacarboxylic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, cyclohexane tricarboxylic acid, cyclohexene tricarboxylic acid, cyclohexane tetracarboxylic acid, cyclohexene tetracarboxylic acid, cyclohexane pentacarboxylic acid, cyclohexene pentacarboxylic acid, cyclohexane hexacarboxylic acid, cyclohexene hexacarboxylic acid, cycloheptane dicarboxylic acid, cycloheptene dicarboxylic acid, cyclooctane dicarboxylic acid, and cyclooctene dicarboxylic acid; and polycyclic or bridged alicyclic dicarboxylic acids such as norbornane dicarboxylic acid and adamantane dicarboxylic acid.

[0102] (Aromatic Compounds Containing One or More Carboxy Groups) Examples of the parent skeleton of an aromatic compound containing one or more carboxy groups include benzoic acid, phenylene acetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalene carboxylic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, anthracene carboxylic acid, anthracene dicarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, and anthracene pentacarboxylic acid. The aromatic compounds may have, on the aromatic ring of the parent skeleton, a hydrogen atom, and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxy group, an amino group, or a carboxyalkyl group. Furthermore, when these compounds have two or more carboxy groups in the molecule, they may be acid anhydrides formed by linking them to each other. When these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by linking a carboxyalkyl group and a carboxy group to each other. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. For details of these substituents, see the above.

[0103] (Heterocyclic Compounds Containing One or More Carboxy Groups) Examples of the parent skeleton of a heterocyclic compound containing one or more carboxy groups include compounds containing one or more carboxy groups in a heterocycle such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole. The heterocyclic compounds may have, on the parent skeleton, for example, a hydrogen atom, and a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an aryl group, an aminoalkyl group, a hydroxy group, an amino group, or a carboxyalkyl group. Furthermore, when these compounds have two or more carboxy groups in the molecule, they may be acid anhydrides formed by linking them together. When these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by linking a carboxyalkyl group and a carboxy group together. When these compounds have two or more carboxyalkyl groups in the molecule, they may be acid anhydrides formed by linking them to each other. For details of these substituents, see the above.

[0104] As the component (Y), from the viewpoint of imparting superior alkaline developability to the resin composition, a compound represented by formula (19), a compound represented by formula (20), a compound represented by formula (21), or a compound represented by formula (22) is preferred. From the viewpoint of alkaline developability, a compound represented by formula (20), a compound represented by formula (21), or a compound represented by formula (22), or a resin having a structure in which one or more hydrogen atoms have been removed from the structures represented by formulas (19) to (22), is more preferred. From the viewpoint of the crosslink density of the cured product obtained by photocuring, the resin having the structure is desirably a resin having an ethylenically unsaturated group.

[0105] The compound represented by formula (19) is as follows:

[0106]

[0107] In formula (19), R ３ R each independently represents a hydrogen atom, a hydroxy group, a carboxy group, an amino group, or an aminomethyl group. When the compound represented by formula (19) has two or more carboxy groups, they may be bonded to each other to form an acid anhydride. In formula (19), the upper limit of the number of carboxy groups is 6. ３ are preferably each independently a hydrogen atom, a hydroxy group, a carboxy group, or an amino group from the viewpoint of alkaline developability, and more preferably contain a carboxy group from the viewpoint of obtaining better alkaline developability.

[0108] The compound represented by formula (19) is preferably a compound represented by formula (23) in that it provides better alkaline developability.

[0109]

[0110] In formula (23), R ３ R each independently represents a hydrogen atom, a hydroxy group, an amino group, or an aminomethyl group. ３ is preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkaline developability. Each q' independently represents an integer of 0 to 4. The number of carboxyl groups, r, represents an integer of 5-q'. From the viewpoint of exhibiting better alkaline developability, the number of carboxyl groups, r, is preferably an integer of 1 to 3. In this case, R ３ The number q' is 5-r and is an integer of 2 to 4. The compound represented by formula (23) may contain two or more carboxy groups and may be an acid anhydride formed by linking them to each other.

[0111] Examples of the compound represented by formula (23) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and anhydrides thereof. Examples of the anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. As the compound represented by formula (23), phthalic acid, trimellitic acid, pyromellitic acid, and anhydrides thereof are preferred, since they provide better alkaline developability.

[0112] The compound represented by formula (20) is as follows:

[0113]

[0114] In formula (20), R ４ R each independently represents a hydrogen atom, a hydroxy group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. When the compound represented by formula (20) has two or more carboxy groups, they may be an acid anhydride formed by linking them to each other. In formula (20), the upper limit of the number of carboxy groups is 10. When the compound represented by formula (20) has a carboxymethyl group, they may be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other. ４ are preferably each independently a hydrogen atom, a hydroxy group, a carboxy group, or an amino group from the viewpoint of alkaline developability, and more preferably contain a carboxy group from the viewpoint of obtaining better alkaline developability. Each s independently represents an integer of 1 to 9. In addition, in formula (20), R ４ Compounds containing one or more other carboxy groups tend to have better alkaline developability than piperidine carboxylic acid in which R is hydrogen.

[0115] From the viewpoint of alkali developability, the number of carboxy groups in the compound represented by formula (20) is preferably 1 to 3. ４ 0 to 2 of R are carboxy groups, and the other 7 to 9 R ４ is other than a carboxy group, R ４is preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom. When the compound represented by formula (20) contains 1 to 3 carboxy groups, R other than the carboxy groups ４ The number is 7 to 9.

[0116] Examples of the compound represented by formula (20) include piperidine carboxylic acid, piperidine-2,4-dicarboxylic acid, piperidine-3,4-dicarboxylic acid, and piperidine dicarboxylic acid anhydride.

[0117] The compound represented by formula (21) is as follows:

[0118]

[0119] In formula (21), R ５ R each independently represents a hydrogen atom, a hydroxy group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. When the compound represented by formula (21) has two or more carboxy groups, they may be an acid anhydride formed by linking them to each other. In formula (21), the upper limit of the number of carboxy groups is 10. When the compound represented by formula (21) has a carboxymethyl group, they may be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other. ５ are preferably each independently a hydrogen atom, a hydroxy group, a carboxy group, or an amino group from the viewpoint of alkaline developability, and more preferably contain a carboxy group from the viewpoint of obtaining better alkaline developability.

[0120] The compound represented by formula (21) is preferably a compound represented by formula (24) in that better alkaline developability can be obtained.

[0121]

[0122] In formula (24), R ５ R each independently represents a hydrogen atom, a hydroxy group, a carboxymethyl group, an amino group, or an aminomethyl group. ５is preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkaline developability. Each t' independently represents an integer of 0 to 8. u represents the number of carboxy groups further bonded to the cyclohexene ring of 3-cyclohexene-1-carboxylic acid (the number of carboxy groups, u), and represents an integer of 9 - t'. The number of carboxy groups, u, is preferably an integer of 1 to 3 from the viewpoint of exhibiting better alkaline developability. In this case, R ５ The number t' is 9-u, which is an integer of 6 to 8. The compound represented by formula (24) may contain two or more carboxy groups and may be an acid anhydride formed by linking them to each other. Furthermore, when the compound represented by formula (24) has a carboxymethyl group, the carboxymethyl group and the carboxy group may be linked to each other to form an acid anhydride.

[0123] Examples of the compound represented by formula (24) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. As the compound represented by formula (23), cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride are preferred, as they provide better alkaline developability.

[0124] The compound represented by formula (22) is as follows:

[0125]

[0126] In formula (22), R ６R each independently represent a hydrogen atom, a hydroxy group, a carboxy group, a carboxymethyl group, an amino group, or an aminomethyl group. Furthermore, when the compound represented by formula (22) has one or more carboxy groups, it may be an acid anhydride formed by linking a carboxymethyl group and a carboxy group to each other. Furthermore, when formula (22) has two or more carboxy groups, it may be an acid anhydride formed by linking them to each other. In formula (22), the upper limit of the number of carboxy groups is 5. In formula (22), when formula (22) has two or more carboxymethyl groups, it may be an acid anhydride formed by linking them to each other. In formula (22), the upper limit of the number of carboxymethyl groups is 6. ６ are each independently preferably a hydrogen atom, a hydroxy group, a carboxy group, or an amino group from the viewpoint of alkaline developability, and more preferably contain a carboxy group from the viewpoint of obtaining better alkaline developability.

[0127] The compound represented by formula (22) is preferably a compound represented by formula (25) in that better alkaline developability can be obtained.

[0128]

[0129] In formula (25), R ６ R each independently represents a hydrogen atom, a hydroxy group, a carboxymethyl group, an amino group, or an aminomethyl group. ６ is preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom, from the viewpoint of exhibiting better alkaline developability. Each w' independently represents an integer of 0 to 4. x represents the number of carboxy groups bonded to the phenyl group of phenylacetic acid (the number of carboxy groups x), and represents an integer of 5-w'. The number of carboxy groups x is preferably an integer of 1 to 3 from the viewpoint of exhibiting better alkaline developability. In this case, R ６The number w' is 5-x, which is an integer of 2 to 4. In formula (25), the carboxymethyl group and the carboxy group may be bonded to each other to form an acid anhydride. When the compound represented by formula (25) has two or more carboxy groups, they may be bonded to each other to form an acid anhydride. In formula (25), the upper limit of the number of carboxy groups bonded to the phenyl group is 5. When the compound represented by formula (25) has two or more carboxymethyl groups, they may be bonded to each other to form an acid anhydride. In formula (25), the upper limit of the number of carboxymethyl groups is 6.

[0130] Examples of compounds represented by formula (25) include phenylacetic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, and anhydrides thereof. Examples of these anhydrides include 1,2-phenylenediacetic anhydride. As the compound represented by formula (25), 1,2-phenylenediacetic acid is preferred because it provides better alkaline developability. These compounds (Y) containing one or more carboxy groups can be used alone or in appropriate mixtures of two or more.

[0131] In the resin composition, the content of the compound containing one or more carboxy groups or the resin containing one or more carboxy groups (component Y) is preferably 0.01 to 50 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the resin solid content in the composition of this embodiment.

[0132] <Maleimide Compound (Z) Other Than the Bismaleimide Compound> The other maleimide compound is not particularly limited as long as it is a compound other than the bismaleimide compound of the present embodiment and has 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 the maleimide compounds include maleimide compounds represented by the following formula (26), such as bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethane maleimide, and polyphenylmethane maleimide; maleimide compounds represented by the following formula (27); 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.

[0133] As the other maleimide compound represented by the following formula (26), 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 the following formula (27), 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 the following formula (28), commercially available products may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0134]

[0135]

[0136]

[0137] 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.

[0138] <Cyanate Ester Compound (Z)> 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 a phenol-dicyclopentadiene co-condensate in which a hydroxyl group has been converted to a cyanate group, 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.

[0139] 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.

[0140] <Phenol Resin (Z)> As the phenol resin, any known phenol resin having two or more hydroxy groups per molecule can be used. Examples thereof include, but are not limited to, bisphenol A phenol resin, bisphenol E phenol resin, bisphenol F phenol resin, bisphenol S phenol resin, phenol novolac resin, bisphenol A novolac phenol resin, glycidyl ester phenol resin, aralkyl novolac phenol resin, biphenyl aralkyl phenol resin, cresol novolac phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene phenol resin, naphthalene skeleton-modified novolac phenol resin, phenol aralkyl phenol resin, naphthol aralkyl phenol resin, dicyclopentadiene phenol resin, biphenyl phenol resin, alicyclic phenol resin, polyol phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, and hydroxyl group-containing silicone resin. These phenolic resins may be used singly or in a suitable mixture of two or more.

[0141] 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.

[0142] <Epoxy Resin (Z)> 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, tetraglyceride ... 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.

[0143] 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.

[0144] <Oxetane Compound (Z)> As the oxetane resin, generally known compounds 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 (trade name, manufactured by Toagosei Co., Ltd.), and OXT-121 (trade name, manufactured by Toagosei Co., Ltd.), but are not particularly limited thereto. These oxetane resins can be used alone or in appropriate mixtures of two or more.

[0145] 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.

[0146] <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.

[0147] 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.

[0148] <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 carbodiimides, 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 appropriate mixtures of two or more.

[0149] 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.

[0150] <Compound (Z) 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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, of 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 tetraols, pentaols, or hexaols.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] The compound having an ethylenically unsaturated group can be a commercially available product, and examples thereof include KAYARAD (registered trademark) ZXR-1801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), KAYARAD (registered trademark) ZXR-1807H (trade name, manufactured by Nippon Kayaku Co., Ltd.), KAYARAD (registered trademark) ZXR-1810H (trade name), KAYARAD (registered trademark) ZXR-1889H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZXR-8001H (trade name), KAYARAD (registered trademark) ZFR-1401H (trade name), KAYARAD (registered trademark) ZAR-2000 (trade name), etc. These compounds having an ethylenically unsaturated group can be used alone or in appropriate mixtures of two or more types.

[0159] 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.

[0160] <Photopolymerization Initiator (W)> The photopolymerization initiator (W) is not particularly limited, and a conventionally used photopolymerization initiator can be appropriately adopted. For example, 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-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), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), photopolymerization initiators such as 2,4-dimethylthioxanthone, etc. Such photopolymerization initiators (W) may be used singly or in combination of two or more.

[0161] Among these, the photopolymerization initiator (W) is preferably one that efficiently generates radicals at an exposure wavelength of 310 to 436 nm (more preferably 365 nm) from the viewpoint of enabling fine pattern formation using a reduction projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm) that is standardly used in the production process of semiconductor protective films, etc. Furthermore, maleimide groups generally do not undergo homopolymerization by radicals, but rather undergo a dimerization reaction of the bismaleimide compound primarily by reaction with radicals generated from the photopolymerization initiator to form a crosslinked structure. For this reason, the inventors infer that bismaleimide compounds appear to have poorer reactivity than acrylic compounds and the like that are commonly used as photopolymerizable compounds. Therefore, from the viewpoint of more efficient radical generation and higher reactivity at an exposure wavelength of 310 to 436 nm (more preferably 365 nm), the photopolymerization initiator of the present invention is more preferably a compound having an oxime structure or a thioxanthone structure.

[0162] Examples of such photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) having an oxime structure ("IRGACURE (registered trademark) OXE-01" manufactured by BASF Japan), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ("IRGACURE OXE-02" manufactured by BASF Japan), and 2,4-dimethylthioxanthone having a thioxanthone structure ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.). Such photopolymerization initiators with high photoradical generation ability tend to be too reactive and difficult to control the reaction when used in the photopolymerization of ordinary acrylic compounds and the like, but can be suitably used in the present invention.

[0163] In the resin composition, the content of the photocuring initiator (W) is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the resin solids in the composition of this embodiment, from the viewpoint of obtaining a resin sheet that sufficiently promotes photocuring of the bismaleimide compound (X), the compound or resin (Y) containing one or more carboxy groups, the maleimide compound other than the bismaleimide compound, the cyanate ester compound, the phenolic resin, the epoxy resin, the oxetane resin, the benzoxazine compound, the carbodiimide compound, and the one or more compounds or resins (Z) selected from the group consisting of compounds having an ethylenically unsaturated group.

[0164] <Curing Accelerator (E)> The resin composition may further contain a curing accelerator (E). Examples of the curing accelerator 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, and triisopropyl methylisopropyl ether. Examples of the organic solvent include phosphines such as octylphosphine, organic metal salts 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.

[0165] Specific examples of the curing accelerator (E) are shown below. Examples of organic peroxide-based polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di- t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl 2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3,-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butyl Examples of the peroxymaleic acid include peroxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0166] Examples of azo polymerization initiators include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine)dihydrochloride, and 2,2'-azobis(2-methyl-N-phenylpropionamidine)dihydroxide. 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydridochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine]dihydrochloride, 2,2 '-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane ] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,Examples include 2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis[2-(hydroxymethyl)propionitrile].

[0167] Further, examples of the curing accelerator (E) include phosphine compounds, compounds containing phosphonium salts, and imidazole-based compounds, and these can be used alone or in combination of two or more. Among these, imidazole-based compounds are preferred. Imidazole-based compounds have particularly excellent catalytic properties, and can more reliably promote the polymerization reaction of the maleimide resin.

[0168] The imidazole compound is not particularly limited, but examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole. Among these, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferred. The use of these compounds further accelerates the reaction of the maleimide resins (A) and (B), resulting in an advantage of improved heat resistance of the resulting cured product. These compounds can be used alone or in combination of two or more.

[0169] The phosphine compound is not particularly limited, but examples thereof include primary phosphines such as alkyl phosphines (e.g., ethylphosphine and propylphosphine) and phenylphosphine; secondary phosphines such as dialkyl phosphines (e.g., dimethylphosphine and diethylphosphine), diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; and tertiary phosphines such as trialkyl phosphines (e.g., trimethylphosphine, triethylphosphine, tributylphosphine, and trioctylphosphine), tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tritolylphosphine, tri-p-styrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, and tri-2-cyanoethylphosphine. Among these, tertiary phosphines are preferably used. These compounds may be used alone or in combination of two or more.

[0170] Examples of the compound having a phosphonium salt include a tetraphenylphosphonium salt, an alkyltriphenylphosphonium salt, a compound having a tetraalkylphosphonium, and the like, and more specific examples include tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra-p-methylphenylborate, butyltriphenylphosphonium thiocyanate, tetraphenylphosphonium phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid.

[0171] The curing accelerator (E) may be used alone or in combination of two or more. The content of the curing accelerator (E) is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of the reactive resin components.

[0172] The resin composition may contain, as a component (E) other than the essential components, for example, an inorganic filler, a mold release agent, a flame retardant, an ion trapping agent, an antioxidant, an adhesion promoter, a stress reducing agent, a colorant, or a coupling agent, within a range that does not impair the effects of the present invention.

[0173] (Filler) The curable resin composition of the present invention 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.

[0174] 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.

[0175] 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 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.

[0176] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, preferably 0.01 to 50 μm.

[0177] In the resin composition, 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, relative to 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 relative to 100 parts by mass of the resin solid content in the resin composition.

[0178] (Silane coupling agent and wetting dispersant) In order to improve the dispersibility of the filler and the adhesive strength between the polymer and / or resin and the filler, the resin composition can also be used in combination with a silane coupling agent and / or a wetting dispersant. These silane coupling agents are not particularly limited as long as they are silane coupling agents that are generally used for the surface treatment of inorganic materials. Specific examples include aminosilane-based compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N-dimethylamino)-propyl]trimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethylsilane, epoxysilane-based compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; vinylsilane-based compounds such as vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, and trimethoxy(4-vinylphenyl)silane; methacrylsilane-based compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, and 3-methacryloxypropyldiethoxymethylsilane; acrylic silane-based compounds such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane;Isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane; isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyldimethoxymethylsilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane cationic silanes such as N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride; acid anhydride compounds such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenyl silanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; and aryl silanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used alone or in combination of two or more.

[0179] The content of the silane coupling agent in the resin composition is not particularly limited, but is typically 0.1 to 10 parts by mass per 100 parts by mass of resin solids in the resin composition. The wetting and dispersing agent is not particularly limited, as long as it is a dispersion stabilizer used in paints. Specific examples include wetting and dispersing agents such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903, manufactured by BYK Japan Co., Ltd. These wetting and dispersing agents can be used alone or in appropriate mixtures of two or more types. The content of the wetting and dispersing agent in the resin composition is not particularly limited, but is typically 0.1 to 10 parts by mass per 100 parts by mass of resin solids in the resin composition.

[0180] <Organic Solvent> The resin composition may contain an organic solvent as needed. The use of an organic solvent can adjust the viscosity of the resin composition during preparation. The type of organic solvent is not particularly limited as long as it can dissolve part or all of the resin in the resin composition. Examples of such organic solvents include halogenated solvents such as dichloromethane, chloroform, dichloroethane, and chlorobenzene; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; cellosolve solvents such as 2-ethoxyethanol and propylene glycol monomethyl ether; aliphatic alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; aromatic group-containing phenol solvents such as phenol and cresol; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; and aromatic hydrocarbon solvents such as toluene and xylene.

[0181] Among these, cyclopentanone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred because they can exhibit excellent solubility in the bismaleimide compound (X), the compound or resin (Y) having one or more carboxy groups, the one or more resins or compounds (Z) selected from the group consisting of maleimide compounds other than the bismaleimide compounds, cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group, and also the photopolymerization initiator (W), and because they facilitate the preparation of a varnish having good solubility. These organic solvents can be used alone or in combination of two or more.

[0182] [Method for Producing Resin Composition] The resin composition is prepared by appropriately mixing a bismaleimide compound (X), a compound or resin (Y) having one or more carboxy groups, one or more maleimide compounds other than the bismaleimide compound, a cyanate ester compound, a phenolic resin, an epoxy resin, an oxetane resin, a benzoxazine compound, a carbodiimide compound, and one or more resins or compounds (Z) selected from the group consisting of compounds having an ethylenically unsaturated group, a photopolymerization initiator (W), a filler, other resins, other compounds, and additives in an organic solvent. The resin composition can be suitably used as a varnish when producing the resin sheet of this embodiment described below. The organic solvent used to prepare the varnish is not particularly limited, and specific examples are as described above.

[0183] The resin composition can be produced, for example, by sequentially blending the above-described components in a solvent and thoroughly stirring the mixture. The resin composition has excellent photocurability, and the cured product obtained from the resin composition has excellent heat resistance, thermal stability, and insulation reliability.

[0184] When producing the resin composition, known processes (such as stirring, mixing, and kneading) can be performed as needed to uniformly dissolve or disperse each component. Specifically, the dispersibility of each component in the resin composition can be improved by performing a stirring and dispersion process using a stirring tank equipped with a stirrer having appropriate stirring capabilities. The stirring, mixing, and kneading processes can be appropriately performed using known devices such as a stirring device for dispersion purposes such as an ultrasonic homogenizer, a mixing device for mixing purposes such as a three-roll mill, a ball mill, a bead mill, and a sand mill, and a revolution or rotation type mixer. Furthermore, when preparing the resin composition, an organic solvent can be used as needed. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples are as described above.

[0185] The resin composition can be suitably used as a varnish for producing the resin sheet of the present embodiment, which will be described later. The varnish can be obtained by a known method. For example, the varnish can be obtained by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components excluding the organic solvent in the resin composition of the present embodiment, and then performing the known mixing treatment (stirring, kneading, etc.) described above.

[0186] [Applications] The resin composition can be preferably used in applications requiring a resin composition with high insulating reliability. Examples of applications include photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component embedding resins. Among these, the resin composition has excellent photocurability, heat resistance, and thermal stability, and can therefore be suitably used as an insulating layer for multilayer printed wiring boards or as a solder resist.

[0187] [Cured Product] The cured product is obtained by curing the resin composition. For example, the resin composition can be melted or dissolved in a solvent, poured into a mold, and cured under normal conditions using heat or light. 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 light wavelength range is preferably in the range of 100 to 500 nm, which allows efficient curing by a photopolymerization initiator or the like.

[0188] [Resin Sheet] The resin sheet of this embodiment is a resin sheet with a support, which has a support and a resin layer disposed on one or both sides of the support, and the resin layer contains a resin composition. The resin sheet can be produced by applying the resin composition to the support and drying it. The resin layer in the resin sheet has excellent heat resistance, thermal stability, and insulation reliability.

[0189] Although known supports can be used, a resin film is preferred. Examples of resin films include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, polyethylene naphthalate films, polyvinyl alcohol films, and triacetyl acetate films. Among these, PET films are preferred.

[0190] The resin film preferably has a surface coated with a release agent to facilitate peeling from the resin layer. The thickness of the resin film is preferably in the range of 5 to 100 μm, more preferably in the range of 10 to 50 μm. If the thickness is less than 5 μm, the support tends to be easily torn when peeled off before development, while if the thickness exceeds 100 μm, the resolution tends to decrease when exposing from above the support.

[0191] In order to reduce scattering of light during exposure, the resin film is preferably one having excellent transparency.

[0192] Furthermore, in the resin sheet, the resin layer may be protected by a protective film. Protecting the resin layer side with a protective film can prevent the adhesion of dust and the like to the surface of the resin layer and scratches. The protective film can be made of the same material as the resin film. The thickness of the protective film is preferably in the range of 1 to 50 μm, and more preferably in the range of 5 to 40 μm. If the thickness is less than 1 μm, the handleability of the protective film tends to decrease, and if it exceeds 50 μm, the cost efficiency tends to decrease. It is preferable that the adhesive strength between the resin layer and the protective film is smaller than the adhesive strength between the resin layer and the support.

[0193] Examples of methods for producing the resin sheet include a method of applying the resin composition of this embodiment to a support such as a PET film and drying it to remove the organic solvent, thereby producing a resin sheet. The application method can be a known method using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, squeeze coater, or the like. Drying can be performed, for example, by heating in a dryer at 60 to 200°C for 1 to 60 minutes.

[0194] The amount of organic solvent remaining in the resin layer is preferably 5% by mass or less relative to the total mass of the resin layer from the viewpoint of preventing the organic solvent from diffusing in subsequent steps, and the thickness of the resin layer is preferably 1 to 50 μm from the viewpoint of improving handleability.

[0195] The resin sheet can be preferably used for producing an insulating layer of a multilayer printed wiring board.

[0196] [Multilayer Printed Wiring Board] The multilayer printed wiring board of this embodiment has an insulating layer and a conductor layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition. The insulating layer can be obtained, for example, by stacking one or more resin sheets and curing them. The number of insulating layers and conductor layers is not particularly limited, and can be appropriately determined depending on the intended application. The order of the insulating layers and conductor layers is also not particularly limited. The conductor layer may be a metal foil used in various printed wiring board materials, such as copper or aluminum foil. Examples of copper foil include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is usually 1 to 100 μm. Specifically, it can be produced by the following method.

[0197] (Laminating Process) In the laminating process, the resin layer side of the resin sheet is laminated to one or both sides of a circuit board using a vacuum laminator. Examples of circuit boards include glass epoxy substrates, metal substrates, ceramic substrates, silicone substrates, semiconductor encapsulation resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The term "circuit board" refers to a substrate on which a patterned conductor layer (circuit) is formed on one or both sides of the substrate. Also included in multilayer printed wiring boards formed by alternately stacking conductor layers and insulating layers is a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). The insulating layer laminated on this multilayer printed wiring board may be an insulating layer obtained by stacking and curing one or more resin sheets of the present embodiment, or may be an insulating layer obtained by stacking one or more resin sheets of the present embodiment and one or more known resin sheets different from the resin sheet of the present embodiment. The method of stacking the resin sheet of this embodiment and a known resin sheet different from the resin sheet of this embodiment is not particularly limited. The surface of the conductor layer may be roughened in advance by blackening and / or copper etching, etc. In the lamination process, if the resin sheet has a protective film, the protective film is peeled off and then the resin sheet and circuit board are preheated as necessary, and the resin layer of the resin sheet is pressure-bonded to the circuit board while being pressurized and heated. In this embodiment, a method of laminating the resin layer of the resin sheet to the circuit board under reduced pressure by vacuum lamination is preferably used.

[0198] The conditions for the lamination process are, for example, a pressure bonding temperature (lamination temperature) of 50 to 140°C and a pressure bonding pressure of 1 to 15 kgf / cm ２ It is preferable to perform lamination under reduced pressure with a pressure bonding time of 5 to 300 seconds and an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Two-Stage Build-Up Laminator (trade name) manufactured by Nikko Materials Co., Ltd.

[0199] (Exposure Process) In the exposure process, after the resin layer is provided on the circuit board in the lamination process, a predetermined portion of the resin layer is irradiated with active energy rays from a light source to cure the resin layer in the irradiated portion. The irradiation may be through a mask pattern, or a direct writing method may be used in which the radiation is directly irradiated. Examples of active energy rays include ultraviolet rays, visible light, electron beams, and X-rays. The wavelength of the active energy rays is, for example, in the range of 200 to 600 nm. When ultraviolet rays are used, the radiation dose is generally 10 to 1000 mJ / cm. ２ In addition, when a printed wiring board having a high-density, high-definition wiring pattern is manufactured using a stepper exposure method, it is preferable to use, for example, an active energy ray containing a wavelength of 365 nm (i-line). When an active energy ray containing a wavelength of 365 nm (i-line) is used, the exposure dose is approximately 10 to 10,000 mJ / cm. ２ When a printed wiring board having a high-density, high-definition wiring pattern is manufactured using a direct writing exposure method, it is preferable to use, for example, an active energy ray having a wavelength of 405 nm (h-ray). When an active energy ray having a wavelength of 405 nm (h-ray) is used, the exposure dose is generally 10 to 10,000 mJ / cm. ２ The exposure method using a mask pattern includes a contact exposure method in which the mask pattern is brought into close contact with the multilayer printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without contact, but either method can be used. Furthermore, if a support is present on the resin layer, exposure may be performed from above the support, or after peeling off the support.

[0200] (Developing Step) In this embodiment, a developing step may be included as necessary. That is, when no support is present on the resin layer, after the exposure step, the non-photocured portion (unexposed portion) is removed by wet development, followed by development, to form a pattern of the insulating layer. Furthermore, when a support is present on the resin layer, after the exposure step, the support is removed, and then the non-photocured portion (unexposed portion) is removed by wet development, followed by development, to form a pattern of the insulating layer.

[0201] In the case of wet development, the developer is not particularly limited as long as it selectively dissolves the unexposed portion. For example, organic solvents such as cyclohexanone, cyclopentanone, and γ-butyrolactone; and alkaline developers such as aqueous tetramethylammonium hydroxide solutions, aqueous sodium carbonate solutions, aqueous potassium carbonate solutions, aqueous sodium hydroxide solutions, and aqueous potassium hydroxide solutions can be used. These developers can be used alone or in combination of two or more.

[0202] The development method can be a known method such as dipping, puddling, spraying, swing immersion, brushing, or scraping. In forming a pattern, these development methods may be used in combination as needed. The use of high-pressure spraying is preferred as a development method, as it further improves resolution. When using a spray method, the spray pressure is preferably 0.02 to 0.5 MPa.

[0203] (Post-baking step) After the exposure step or the development step, a post-baking step is performed to form an insulating layer (cured product). Examples of post-baking steps include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven, and these steps can be used in combination. When irradiating with ultraviolet light, the irradiation amount can be adjusted as needed, and irradiation can be performed at an irradiation amount of, for example, about 50 to 10,000 mJ / cm2. The heating conditions can be selected as needed, but are preferably selected in the range of 150 to 300°C for 20 to 180 minutes, and more preferably 200 to 300°C for 30 to 60 minutes.

[0204] (Conductor Layer Forming Process) After forming an insulating layer (cured product), a conductor layer is formed on the surface of the insulating layer by dry plating. Known methods such as vapor deposition, sputtering, and ion plating can be used as dry plating. Vapor deposition (vacuum vapor deposition) involves, for example, placing a multilayer printed wiring board in a vacuum chamber and heating and evaporating metal to form a metal film on the insulating layer. Sputtering also involves, for example, placing a multilayer printed wiring board in a vacuum chamber, introducing an inert gas such as argon, applying a DC voltage, causing the ionized inert gas to collide with a target metal, and using the knocked-out metal to form a metal film on the insulating layer.

[0205] Next, a conductor layer is formed by electroless plating, electrolytic plating, etc. The subsequent pattern formation method may be, for example, a subtractive method, a semi-additive method, or the like.

[0206] [Encapsulating Material] The encapsulating material of this embodiment includes the resin composition of this embodiment. A generally known method can be appropriately applied as a manufacturing method for the encapsulating material, and is not particularly limited. For example, the encapsulating material can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents that are generally used in encapsulating material applications using a known mixer. During mixing, the maleimide compound of this embodiment, various additives, and solvents can be added by generally known methods, and are not particularly limited.

[0207] [Fiber-Reinforced Composite Material] The fiber-reinforced composite material of this embodiment includes the resin composition of this embodiment and reinforcing fibers. Generally known reinforcing fibers can be used, and are not particularly limited. Examples include glass fibers such as E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, and spherical glass; carbon fibers; aramid fibers; boron fibers; PBO fibers; high-strength polyethylene fibers; alumina fibers; and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from woven fabrics, nonwoven fabrics, mats, knits, braids, unidirectional strands, rovings, chopped fibers, and the like. Furthermore, the reinforcing fibers can also be in the form of preforms (layers of woven fabric base fabrics made of reinforcing fibers, or fabrics sewn together with stitching threads, or fiber structures such as three-dimensional woven fabrics and braided fabrics).

[0208] As a method for producing these fiber-reinforced composite materials, a generally known method can be appropriately applied and is not particularly limited. Examples include the liquid composite molding method, the resin film infusion method, the filament winding method, the hand lay-up method, and the pultrusion method. Among these, the resin transfer molding method, which is one of the liquid composite molding methods, allows materials other than the preform, such as a metal plate, a foam core, or a honeycomb core, to be set in the mold in advance, making it suitable for a variety of applications. Therefore, it is preferably used when mass-producing composite materials with relatively complex shapes in a short period of time.

[0209] [Adhesive] The adhesive of this embodiment includes the resin composition of this embodiment. A generally known method can be appropriately applied as a manufacturing method for the adhesive, and is not particularly limited. For example, the adhesive can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents that are generally used in adhesive applications using a known mixer. Note that the method for adding the maleimide compound of this embodiment, various additives, and solvents during mixing can be appropriately applied as a generally known method, and is not particularly limited.

[0210] [Semiconductor Device] The heat-resistant resin coating film 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 a passivation film for semiconductors, a surface protection film for semiconductor elements, an interlayer insulating film, an insulating film for rewiring layers, an interlayer insulating film for multilayer wiring for high-density packaging, an interlayer insulating film for electronic components such as inductors and SAW filters, and an insulating film or flattening layer for organic electroluminescent devices, but is not limited thereto, and can have a variety of structures.

[0211] 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.

[0212] 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 example and comparative example, the compatibility, 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

[0213] Bismaleimide Compound (A) Synthesis Example 1 (A-1) 84 g of toluene and 28 g of N-methylpyrrolidone were placed in a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 65.5 g (0.20 mol) of diamine (trade name Diamine H20, manufactured by Okamura Oil Mills) was added, followed by the slow addition of 19.4 g (0.20 mol) of methanesulfonic acid to form a salt. After approximately 10 minutes of stirring, 22.4 g (0.10 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation reaction was reached by this time. The reaction mixture was cooled below room temperature, and 23.7 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water. After cooling to room temperature, an additional 50 ml of toluene was added to the flask. The diluted organic layer was then washed with water (100 ml x 5) to remove salts and unreacted raw materials. The solvent was then removed under vacuum, yielding 97 g of the desired bismaleimide compound (A-1) as a light brown liquid (yield 97%, Mw = 2,200).

[0214] Synthesis Example 2 (A-2) The same synthesis method as in A-1 was performed, except that 22.4 g (0.10 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was changed to 52.0 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanoic dianhydride (BPADA), to obtain 98 g (yield 98%, Mw = 2,400) of the target bismaleimide compound as a light brown solid (A-2).

[0215] Synthesis Example 3 (A-3) 84 g of toluene and 28 g of N-methylpyrrolidone were placed in a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 32.9 g (0.10 mol) of Diamine H20 (Okamura Oil Mills, Ltd.) and 54.0 g (0.10 mol) of dimer diamine (PRIAMINE 1075, Croda Japan Co., Ltd.) were added, followed by the slow addition of 19.4 g (0.20 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes, and then 22.4 g (0.10 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time. The reaction mixture was cooled to below room temperature, and 23.7 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml x 5 times) to remove salts and unreacted raw materials, yielding a bismaleimide compound varnish. The solvent was then removed under vacuum, yielding 97 g of the desired bismaleimide compound (97% yield, Mw = 2,300) as a light brown liquid (A-3).

[0216] Synthesis Example 4 (A-4) 160 g of toluene and 160 g of N-methylpyrrolidone were placed in a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 24.5 g (0.18 mol) of metaxylenediamine (Mitsubishi Gas Chemical Company, Inc.) and 6.6 g (0.02 mol) of Diamine H20 (Okamura Oil Mills, Ltd.) were added, followed by the slow addition of 19.4 g (0.20 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (44.4 g, 0.10 mol) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time. The reaction mixture was cooled to below room temperature, and 23.7 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml x 3 times) to remove salts and unreacted raw materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol for a reprecipitation step. The solvent was removed and the mixture was dried, yielding 86 g of the desired bismaleimide compound as a white solid (yield 86%, Mw = 2,500) (A-4).

[0217] Synthesis Example 5 (A-5) Synthesis was performed in the same manner as in A-4, except that 24.5 g (0.18 mol) of metaxylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) was changed to 25.6 g (0.18 mol) of 1,3-bisaminomethylcyclohexane (1,3-BAC) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (44.4 g, 0.10 mol) was changed to 52.0 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanoic dianhydride (BPADA), to obtain 82 g (yield 82%, Mw=2,400) of the target bismaleimide compound as a white solid (A-5).

[0218] Synthesis Example 6 (A-6) Synthesis was performed in the same manner as in A-4, except that 24.5 g (0.18 mol) of meta-xylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.) was changed to 27.8 g (0.18 mol) of norbornanediamine (NBDA) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (44.4 g, 0.10 mol) was changed to 57.2 g (0.11 mol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanoic dianhydride (BPADA), to obtain 81 g (yield 81%, Mw=2,100) of the target bismaleimide compound (A-6) as a light brown solid.

[0219] Synthesis Example 7 (A-7) 160 g of toluene and 160 g of N-methylpyrrolidone were placed in a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 21.8 g (0.16 mol) of metaxylenediamine (Mitsubishi Gas Chemical Company, Inc.) and 13.2 g (0.04 mol) of Diamine H20 (Okamura Oil Mills, Ltd.) were added, followed by the slow addition of 19.4 g (0.20 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (44.4 g, 0.10 mol) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time. The reaction mixture was cooled to below room temperature, and 23.7 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml x 3 times) to remove salts and unreacted raw materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol for reprecipitation, and the solvent was removed and dried to yield 68 g of the desired bismaleimide compound as a white solid (yield 68%, Mw = 2,500) (A-7).

[0220] Synthesis Example 8 (A-8) 160 g of toluene and 160 g of N-methylpyrrolidone were placed in a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 19.1 g (0.14 mol) of metaxylenediamine (Mitsubishi Gas Chemical Company, Inc.) and 19.8 g (0.06 mol) of Diamine H20 (Okamura Oil Mills, Ltd.) were added, followed by the slow addition of 19.4 g (0.20 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes, and then 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (44.4 g, 0.10 mol) was slowly added to the stirred mixture. The mixture was heated to reflux for 6 hours to form the amine-terminated diimide. The theoretical amount of water produced from this condensation had been reached by this time. The reaction mixture was cooled to below room temperature, and 23.7 g (0.24 mol) of maleic anhydride was added to the flask. The mixture was refluxed for an additional 8 hours, yielding the expected amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml x 3 times) to remove salts and unreacted raw materials, yielding a varnish of a bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol for a reprecipitation step. The solvent was removed and the mixture was dried, yielding 64 g of the desired bismaleimide compound as a white solid (yield 64%, Mw = 2,800) (A-8).

[0221] Synthesis Example 9 (A-9) A similar method to that of A-1 was performed, except that 65.5 g (0.20 mol) of Diamine H20 (manufactured by Okamura Oil Mills, Ltd.) was changed to 34.5 g (0.20 mol) of 1,12-diaminododecane (DAD), to obtain 95 g (yield 95%, Mw = 1,500) of the target bismaleimide compound as a pale brown liquid (A-9).

[0222] Synthesis Example 10 (A-10) A similar method to that of A-9 was used, except that 22.4 g (0.10 mol) of hydrogenated pyromellitic acid (H-PMDA) was changed to 52.0 g (0.10 mol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanoic dianhydride (BPADA), to obtain 96 g (yield 96%, Mw = 3,000) of the target bismaleimide compound as a light brown liquid (A-10).

[0223] <Compound or Resin (Y) Containing One or More Carboxy Groups> The following four compounds or resins (Y) containing one or more carboxy groups were prepared: (C-1) Propylene glycol monomethyl ether monoacetate solution of TrisP-PA type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD (registered trademark) ZCR-6001H")

[0224] (C-2) Propylene glycol monomethyl ether monoacetate solution of dicyclopentadiene-type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD (registered trademark) ZXR-1807H").

[0225] (C-3) Propylene glycol monomethyl ether monoacetate solution of bisphenol A type acid-modified epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD (registered trademark) ZAR-2000").

[0226] (C-4) 6-maleimidohexanoic acid (MCA) (Tokyo Chemical Industry Co., Ltd.)

[0227] [Component D; 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")

[0228] (Examples 1 to 8 and Comparative Examples 1 and 2) The component (A), the photopolymerization initiator (II), and 50 parts by mass of cyclopentanone as a solvent were blended in the amounts (parts by mass) shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2, and their cured physical properties were measured.

[0229] <Evaluation of Resin Compositions> Cured products were prepared from the resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2, and the following evaluations were carried out. The results are summarized in Table 1.

[0230] (Evaluation of Dielectric Properties (Dielectric Constant: Dk, Dielectric Loss Tangent: Df)) For the evaluation of dielectric properties, the resin compositions of Examples 1 to 8 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, 3000 mJ / cm was applied to the obtained resin film (semi-cured). ２ The resin film was then irradiated with UV light of 1000 kJ / cm². The 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. The resin film was 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 and Development Co., Ltd. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C. The results are shown in Table 1.

[0231] (Heat Resistance) (Evaluation of Glass Transition Temperature (Tg)) To evaluate the glass transition temperature, the resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were coated and dried on copper foil using a desktop coater to a thickness of 20 μm after drying to obtain a resin film (semi-cured). Next, the obtained resin film (semi-cured) was irradiated with 3000 mJ / cm ２ The 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. 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 1 Hz, tensile mode, heating rate 3°C / min). 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 was defined as the glass transition temperature Tg. The results are shown in Table 1.

[0232] (Evaluation of 5% Weight Loss Temperature (Td5)) To evaluate the weight loss temperature, the resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2 were coated and dried on copper foil using a desktop coater so that the thickness after drying was 20 μm, to obtain a resin film (semi-cured). Next, the obtained resin film (semi-cured) was irradiated with 3000 mJ / cm ２ The resin film was then irradiated with UV light of 1000 kJ / s. The 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. The cured resin film was cut into 4 mm square pieces, and 1.0 to 5.0 mg was weighed and placed in a measuring pan. The 5% weight loss rate (Td5) was measured under conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. A TGA / DSC1 (manufactured by METTLER TOLEDO) was used as the measuring device. The results are shown in Table 1.

[0233] As is clear from the results shown in Table 1, the bismaleimide compound of the present invention is a bismaleimide compound suitable for the field of semiconductor materials, having low dielectric properties, with a dielectric dissipation factor of 0.01 or less, and high heat resistance when cured alone.

[0234] Examples 9 to 16 and Comparative Examples 3 to 7 The components (A) and (C) were blended in the amounts (parts by mass) shown in Table 2, and 100 parts by mass of cyclopentanone was used as a solvent to prepare resin compositions of Examples 9 to 16 and Comparative Examples 3 to 7, and the developability was evaluated.

[0235] <Evaluation of Patterning Ability of Resin Composition> The patterning ability of the resin compositions of Examples 9 to 16 and Comparative Examples 3 to 7 was evaluated using an organic solvent / alkaline aqueous solution after photocuring. The results are summarized in Table 2.

[0236] <Evaluation Method> The resin compositions obtained in Examples 9 to 16 and Comparative Examples 3 to 7 were spin-coated onto silicon substrates and heated at 100°C for 2 minutes to form coating films with thicknesses of 10 to 15 μm. Next, reduction projection exposure was performed with i-line (365 nm) using a USHIO "ultra-high pressure mercury lamp 500W multilight" and a quartz photomask on which lines / spaces with widths of 50 to 200 μm were printed. For Examples 9 to 11, 13 to 16 and Comparative Examples 3, 4, and 7, exposure was performed at 500 mJ / cm. ２ For Example 12 and Comparative Examples 5 and 6, the exposure was 2000 mJ / cm ２ The specimens were exposed to light at 1000 K and heated at 150°C for 15 minutes to prepare test pieces for evaluating patterning properties. Cyclopentanone, a 1% aqueous solution of sodium carbonate, and a 2.38% aqueous solution of tetramethylammonium hydroxide were used as the developers, and the patterning properties in each developer were evaluated. Each test piece was immersed in a specified petri dish containing the developer and shaken at 40-50 rpm, and the pattern shape and residue remaining on the test piece were observed. (Criteria for determining patterning properties) ◯: A pattern remains after development. ×: Nothing remains after development, or uncured areas remain.

[0237] As is clear from the results shown in Table 2, it was shown that the resin composition containing the bismaleimide compound of the present invention and the carboxy group-containing compound or curable resin can be subjected to photolithography using an organic solvent and an alkaline aqueous solution.

[0238] <Evaluation of physical properties of resin compositions when thermally cured> (Example 17 and Comparative Examples 8 to 9) Resin compositions were prepared in the amounts (parts by mass) shown in Table 3, and the physical properties when thermally cured were evaluated. The following two compounds were prepared as comparative examples. (Comparative Example 8) Maleimide compound: Manufactured by Nippon Kayaku Co., Ltd., trade name "MIZ-001" (Comparative Example 9) Manufactured by SABIC, trade name "SA-9000"

[0239] (Method of Preparing Thermosetting Film) 100 parts by mass of the bismaleimide compound obtained in Synthesis Example 2 was dissolved in 100 parts by mass of toluene as a solvent and 1 part by mass of DCP (dicumyl peroxide, manufactured by Nouryon Chemical Co., Ltd.) as a thermal polymerization initiator to prepare a resin composition. The mixture was then dried in a vacuum dryer at 80°C for 30 minutes and then at 100°C for 30 minutes to remove the solvent, and the resulting solid was pulverized in an agate mortar. The resulting powder was sandwiched between copper foils from above and below to a thickness of approximately 250 μm, and cured under vacuum at 1 MPa and 220°C for 2 hours. The copper foil was then removed by etching to obtain a thermosetting film.

[0240] (Evaluation of dielectric properties (dielectric constant: Dk, dielectric loss tangent: Df)) The resin film was cut into a length of 50 mm and a width of 2.5 mm and used as a test piece to measure the dielectric properties by a cavity resonator perturbation method. The measuring instrument used was a vector network analyzer ADMSO10c1 manufactured by AET Corporation, and the cavity resonator used was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Application and Development Co., Ltd. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C. The results are shown in Table 3.

[0241] (Heat Resistance) (Evaluation of Glass Transition Temperature (Tg)) The dynamic viscoelasticity of the cured bismaleimide products prepared as described above was measured using a dynamic viscoelasticity measuring apparatus (DMA) (DMAQ800 manufactured by TA Instruments) (frequency 10 Hz, tensile mode, heating rate 2°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. The results are shown in Table 3.

[0242] As is clear from the results shown in Table 3, the bismaleimide compound of the present invention exhibits a low dielectric loss tangent when cured alone, even when cured by heat, and has high heat resistance, demonstrating that it is a bismaleimide compound suitable for the field of semiconductor materials.

[0243]

[0244]

[0245]

[0246] As described above, the present invention can provide a bismaleimide compound that has good compatibility with resins having polar functional groups, is excellent in low dielectric properties, and can achieve a high Tg. Therefore, such a bismaleimide compound and photosensitive resin composition of the present invention are highly useful as surface protection films, interlayer insulating films, insulating films for redistribution layers, and the like for semiconductor elements.

Claims

1. A bismaleimide compound containing a structural unit represented by the following general formula (1): In the general formula (1), A represents a tetravalent organic group containing a cyclic structure. １ is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. １ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. When a plurality of structural units of general formula (1) are present in a bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and each of the plurality of B's １ are each independent and may be the same or different. * denotes a bonding site to other structural units.

2. The bismaleimide compound according to claim 1, which further contains a structural unit represented by the following general formula (2), has a dielectric loss tangent of 0.010 or less when cured, and has a molecular weight of 2,000 to 50,000: In general formula (2), A's each independently represent a tetravalent organic group containing a cyclic structure. ２ represents a divalent hydrocarbon group having a cyclic structure. * represents a bonding site with another structural unit. However, B ２ represents a hydrocarbon group other than a divalent hydrocarbon group derived from a dimer acid. When a plurality of structural units of general formula (1) and (2) are present in the bismaleimide compound, each of the plurality of A's is independent and may be the same or different, and the plurality of B's ２ are each independently and may be the same or different. The order of the repeating units is not limited, and the bonding pattern may be alternating, block, or random.

3. The bismaleimide compound according to claim 1 or 2, further comprising a structural unit represented by the following general formula (3): In formula (3), A independently represents a tetravalent organic group containing a cyclic structure. ３ Each independently represents a divalent hydrocarbon group derived from a dimer acid. * represents a bond to another structural unit.

4. The bismaleimide compound according to any one of claims 1 to 3, wherein in general formula (1), (2), or (3), the organic group constituting A is selected from the group consisting of the following structural formulas: In the above structural formula, the bond marked with a wavy line indicates the position where the organic group constituting A is bonded to the imide group in the general formula (1), (2) or (3).

5. In the general formula (1), B １ is an alkylene group or alkenylene group having 14 to 30 carbon atoms, which is a linear or branched alkylene group or alkenylene group having one or more side chains of alkyl and / or alkenyl groups having 1 to 4 carbon atoms, ２ The bismaleimide compound according to any one of claims 1 to 4, wherein the hydrocarbon group constituting the formula (I) is a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

6. In the general formula (1), B １ is an alkylene or alkenylene group having 2n (n is an integer of 6≦n≦14) carbon atoms in the main chain portion and having a side chain composed of an ethyl group or a methyl group, ２ 4. The bismaleimide compound according to claim 2, wherein the hydrocarbon group constituting the formula (I) is a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

7. In the general formula (1), B １ is a hydrocarbon group obtained by removing an amino group from 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene, and ２ 4. The bismaleimide compound according to claim 2, wherein the hydrocarbon group constituting the formula (I) is a divalent hydrocarbon group having an aromatic ring structure or an alicyclic structure.

8. B above ２ The bismaleimide compound according to claim 7, wherein the hydrocarbon group constituting the formula (4-1) is a hydrocarbon group having an aromatic ring structure represented by the following formula (4-1), or a hydrocarbon group having an alicyclic structure selected from the group represented by the following formula (4-2): In formula (4-1), 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. 1 represents an integer of 1 to 4. * represents a bonding site to N or another structural unit. In formula (4-2), 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 10, p' represents an integer of 1 to 14, and p'' represents an integer of 1 to 7. * represents a bonding site to N or another structural unit.

9. A resin composition comprising the bismaleimide compound (X) according to any one of claims 1 to 8 and a compound or resin (Y) containing one or more carboxy groups.

10. The resin composition according to claim 9, further comprising one or more compounds or resins (Z) selected from the group consisting of maleimide compounds other than the bismaleimide compound (X), cyanate ester compounds, phenolic resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having an ethylenically unsaturated group.

11. The resin composition according to claim 10, further comprising a photopolymerization initiator (W) or a curing catalyst.

12. A cured product of a resin composition containing the bismaleimide compound according to any one of claims 1 to 8.

13. 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 any one of claims 1 to 8.

14. A dry film resist comprising a composition containing the bismaleimide compound according to any one of claims 1 to 8 and a photopolymerization initiator.

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