Resin composition and its cured product, semiconductor element, and dry film resist

Abstract

This resin composition contains: a bismaleimide compound (A) that contains a constituent unit represented by formula (1); and at least one maleimide compound (B) that is selected from the group consisting of compounds represented by formulas (2)-(8).

Description

Resin compositions and their cured products, semiconductor devices, and dry film resists

[0001] The present invention relates to a resin composition containing a bismaleimide compound, its cured product, a semiconductor device, and a dry film resist.

[0002] In recent years, electronic devices have become smaller and more high-performance, requiring finer and higher-density wiring in multilayer printed circuit boards. Furthermore, next-generation materials for high-frequency bands are needed, and reducing transmission loss is essential for noise countermeasures, thus requiring the development of insulating materials with excellent dielectric properties.

[0003] Conventionally, polyimide resins and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, have been widely used for surface protective films and interlayer insulating films of semiconductor devices (Patent Document 1). When polyimide resins and polybenzoxazole resins are used as surface protective films or interlayer insulating films, a method of forming through-holes etc. by etching using a positive-type photoresist containing these resins is known. However, a problem with this method is that it requires complicated processes such as coating and peeling off the photoresist. Therefore, in order to streamline the work process, heat-resistant materials with photosensitivity have been investigated (Patent Document 2).

[0004] Furthermore, in recent years, the required characteristics of laminates on which electrical and electronic components are mounted have become broader and more sophisticated due to the expansion of their application fields. For example, while semiconductor chips were traditionally mounted on metal lead frames, high-performance semiconductor chips such as CPUs are increasingly mounted on laminates made of polymer materials. As the speed of CPUs and other components increases and clock frequencies rise, signal propagation delay and transmission loss become problems, requiring low dielectric constant and low dielectric loss tangent in the wiring boards. At the same time, as the speed of the components increases, the heat generated by the chips also increases, creating a need for improved heat resistance. In addition, with the recent proliferation of mobile electronic devices such as cell phones, precision electronic devices are being used and carried in outdoor environments and in close proximity to the human body, requiring resistance to external environments (especially humid and hot environments). Moreover, in the automotive sector, electronification is progressing rapidly, and precision electronic devices are sometimes placed near the engine, requiring even higher levels of heat and humidity resistance.

[0005] Conventionally, polyimide cured products, such as those found in Patent Document 3, which are obtained by ring-closing a polyimide precursor resin through thermosetting, have been widely used as high-performance printed circuit boards due to their excellent heat resistance, chemical resistance, and electrical properties. However, as described above, improvements are needed in situations where even higher performance is required.

[0006] It has become clear that these materials do not meet the dielectric properties requirements for high-frequency applications such as fifth-generation mobile communication systems (5G). In contrast, Patent Document 4 reports that an epoxy resin composition containing epoxy resin, an active ester compound, and a triazine-containing cresol novolac resin is effective in reducing dielectric loss tangent. However, even with this material, further reduction in dielectric strength is necessary for high-frequency applications.

[0007] On the other hand, Patent Document 5 reports that a resin film made from a resin composition containing a bismaleimide resin having a long-chain alkyl group and a curing agent as a non-epoxy material exhibits excellent low dielectric properties.

[0008] Furthermore, Patent Documents 6 and 7 disclose polyimides made from aromatic tetracarboxylic acids and dimer amines and alicyclic diamines derived from dimer acids, which are dimers of unsaturated fatty acids such as oleic acid.

[0009] Furthermore, Patent Document 8 discloses a bismaleimide resin that possesses both long-chain fatty acid regions and alicyclic structural regions, exhibits a low dielectric loss tangent, and has a glass transition temperature (Tg) of 100°C or higher.

[0010] Japanese Patent Publication No. 11-199557, Japanese Patent Publication No. 11-24271, International Publication No. 2015 / 199220, Japanese Patent Publication No. 2011-132507, International Publication No. 2016 / 114287, Japanese Patent Publication No. 2017-119361, Japanese Patent Publication No. 2019-104843, Japanese Patent Publication No. 2021-123672

[0011] Recent studies have shown that low-molecular-weight aromatic maleimides achieve glass transition temperatures (Tg) above 200°C, but due to their rigid skeleton, they have low reaction site mobility, very low photoreactivity, and poor photopatterning properties. On the other hand, bismaleimide resins with long-chain alkyl groups have high reaction mobility and good photoreactivity due to the long-chain alkyl groups, and also achieve low dielectric loss tangent, but they have also been found to have low Tg.

[0012] As described in Patent Document 8 above, the bismaleimide compound having both long-chain alkyl groups and alicyclic structural moieties becomes very difficult to achieve a high Tg of 200°C or higher when the proportion of long-chain alkyl groups increases, and the toughness of the cured film decreases and crack resistance decreases when the proportion of alicyclic structural moieties increases. Therefore, it is very difficult to achieve low dielectric loss tangent and high Tg with maleimide resin alone.

[0013] The film described in Patent Document 5 is a combination of a bismaleimide resin having substantially long-chain alkyl groups and a hard, low-molecular-weight aromatic maleimide. However, it has poor compatibility, is prone to uneven properties and curing, and is extremely difficult to achieve the high glass transition temperature (Tg) of 200°C or higher required for semiconductor device applications. Furthermore, the polyimides described in Patent Documents 6 and 7 are difficult to use for single-layer curing and have poor compatibility with other resins. In addition, because the polyimide undergoes ring-closing dehydration during curing, voids may form and flatten the film depending on the usage conditions when laminating, for example, a redistribution layer.

[0014] Therefore, the present invention aims to provide a bismaleimide compound-containing resin composition that is photopatternable or thermocurable, has a glass transition temperature of 200°C or higher, and has a low dielectric loss tangent.

[0015] Furthermore, the present invention aims to provide a bismaleimide compound-containing resin composition having a glass transition temperature of 200°C or higher, and possessing excellent thermal decomposition resistance, low dielectric loss tangent, insulation reliability, and adhesion.

[0016] The inventors of this invention conducted extensive research to solve the above problems and, as a result, discovered that the following bismaleimide compound-containing resin composition can achieve the above objectives, thus completing the present invention.

[0017] In other words, the present invention relates to the following [1] to

[15] : [1] A resin composition comprising a bismaleimide compound (A) containing a structural unit represented by the following (1), and at least one maleimide compound (B) selected from the group consisting of compounds represented by the following formulas (2) to (8).

[0018]

[0019] A in general formula (1) １ This represents a tetravalent organic group containing a cyclic structure. B １ A is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. When multiple constituent units of general formula (1) are present in a bismaleimide compound, multiple A １ Each of them is independent, and they may be the same or different, and there may be multiple B １They may each be independent and may be the same or different.

[0020]

[0021] In formula (2), R １ , R ２ , and R ３ each independently represent a hydrogen atom, a hydroxy group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. n represents an integer of 1 to 10.

[0022]

[0023] In formula (3), R ４ each independently represent a hydrogen atom or a methyl group. n represents an integer of 1 to 10.

[0024]

[0025] In formula (4), R ５ , R ６ , and R ７ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent.

[0026]

[0027] In formula (5), R ８ each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R ９ each independently represent a hydrogen atom or a methyl group.

[0028]

[0029] In formula (6), R １０ each independently represent a hydrogen atom, a methyl group, or an ethyl group.

[0030]

[0031] In formula (7), R １１ each independently represent a hydrogen atom or a methyl group. n represents an integer of 1 to 10.

[0032]

[0033] In formula (8), multiple Rs １２Each of these independently represents an alkyl group with 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value n ａｖｅ is 1 < n ａｖｅ < 5. [2] A resin composition comprising a bismaleimide compound (A) containing a structural unit represented by the following formula (1), and at least one polymer (E) containing a structural unit represented by the following formula (12) and / or (13).

[0034] A in general formula (1) １ This represents a tetravalent organic group containing a cyclic structure. B １ A is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. When multiple constituent units of general formula (1) are present in a bismaleimide compound, multiple A １ Each of them is independent, and they may be the same or different, and there may be multiple B １ Each of them is independent and can be the same or different.

[0035] In formula (12), A ２ This indicates a tetravalent organic group, B ２ R indicates a divalent organic group. １３ and R １４ Each of these independently represents a hydrogen atom or a monovalent organic group. There may be multiple structural units represented by formula (12), and A in multiple structural units ２ , B ３、 R １３ and R １４ These may be the same or different. １３ and R １４ The combination of each element is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups.

[0036] In formula (13), A ２ is a tetravalent organic group, B ２ represents a divalent organic group. Furthermore, it may have multiple structural units represented by formula (13), and A in multiple structural units ２ and B ２ These may be the same or different.

[0037] [3] The resin composition according to [1] or [2], wherein the bismaleimide compound (A) further comprises a constituent unit represented by the following formula (9), and has a dielectric loss tangent of 0.010 or less and a weight-average molecular weight of 1,000 to 75,000 when cured.

[0038]

[0039] A in equation (9) ３ This independently represents a tetravalent organic group containing a cyclic structure. B ３ It has a cyclic structure and represents hydrocarbon groups other than the divalent hydrocarbon group derived from the dimer acid. When multiple constituent units of general formula (9) are present in a bismaleimide compound, multiple A ３ Each of them is independent, and they may be the same or different, and there may be multiple B ３ Each of these is independent and may be the same or different. Furthermore, the order of each repeating unit is not limited, and the combination method may be alternating, in blocks, or random. [4] A of the general formula (1) １ Or A in the general formula (9) above ３ The resin composition according to [3], wherein the organic group constituting the is selected from the group consisting of the following structural formulas.

[0040]

[0041] In the above structural formula, the bond marked with * is the A １ Or A ３ This shows the locations where the organic group and imide group that make up the compound are bonded.

[0042] [5] In the above general formula (1), the B １ The hydrocarbon group constituting is an alkylene group or alkenylene group having 14 to 30 carbon atoms, and is linear or has a branched chain of one or more alkyl groups and / or alkenyl groups having 1 to 4 carbon atoms, and in the general formula (9) B ３The resin composition according to [3] or [4], comprising a bismaleimide compound (A) in which the hydrocarbon group constituting is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure. [6] In the general formula (1), the B １ The hydrocarbon group constituting is a hydrocarbon group having 2n (where n is 7 to 14) carbon atoms of an alkylene group or an alkenylene group in the main chain portion, and is a hydrocarbon group having a branched chain composed of an ethyl group, and in the general formula (9) the B ３ The resin composition according to [3] or [4], comprising a bismaleimide compound (A) in which the hydrocarbon group constituting is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure. [7] In the general formula (1), the B １ The hydrocarbon group constituting is a hydrocarbon group obtained by removing the amine group from 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene, and in the general formula (9), the B ３ The resin composition according to [3] or [4], comprising a bismaleimide compound (A) in which the hydrocarbon group constituting is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure. [7] The B ３ The resin composition according to [3] or [4], wherein the hydrocarbon group constituting the is a hydrocarbon group having an aromatic ring structure represented by the following formula (10), or a hydrocarbon group having an aliphatic ring structure selected from the group represented by the following formula (11).

[0043]

[0044] R １５ Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. l represents an integer from 0 to 4. Bonds marked with an asterisk (*) in the structural formula represent bonding.

[0045]

[0046] R １６Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. p represents an integer from 0 to 4, p' represents an integer from 0 to 14, and p'' represents an integer from 0 to 7. In the structural formula, bonds marked with * represent bonds. [9] The resin composition according to any one of [1] to [8], further comprising a photopolymerization initiator (C).

[10] The resin composition according to any one of [1] to [8], further comprising a thermosetting initiator.

[11] The resin composition according to any one of [1] to [8], further comprising a curing accelerator (D).

[12] The resin composition according to

[11] , wherein the curing accelerator (D) comprises at least one selected from a thermal radical polymerization initiator and an imidazole compound.

[13] The resin composition according to any one of [1] to

[12] , further comprising a crosslinking agent (G).

[14] A cured product comprising the resin composition described in any one of [1] to

[13] .

[15] A semiconductor device comprising a surface protective film, an interlayer insulating film, or an insulating film of a redistribution layer comprising the resin composition described in any one of [1] to

[13] .

[16] A dry film resist comprising the resin composition described in any one of [1] to

[13] and a substrate sandwiching the resin composition.

[0047] According to the present invention, it is possible to provide a resin composition that has good photocurability or thermosetting properties, a high glass transition temperature (Tg) of 200°C or higher, an excellent thermal decomposition temperature, and a good dielectric loss tangent, and that can produce a good resin sheet, as well as a resin sheet using the same, a multilayer printed circuit board, and a semiconductor device.

[0048] Furthermore, according to the present invention, it is possible to obtain a resin composition that has a high glass transition temperature (Tg) of 200°C or higher, high thermal decomposition resistance, good dielectric loss tangent, excellent insulation reliability, and excellent adhesion to a substrate, as well as a resin sheet using the same, a multilayer printed circuit board, and a semiconductor device.

[0049] Embodiments of the present invention will be described in detail below. This embodiment is a resin composition comprising a bismaleimide compound (A) and a maleimide compound (B).

[0050] <Bismaleimide compound (A)> The bismaleimide compound (A) according to this embodiment includes a constituent unit represented by the following formula (1).

[0051] A in general formula (1) １ This represents a tetravalent organic group containing a cyclic structure. B １ A is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. When multiple constituent units of general formula (1) are present in a bismaleimide compound, multiple A １ Each of them is independent, and they may be the same or different, and there may be multiple B １ Each of them is independent and can be the same or different.

[0052] The bismaleimide compound (A) may further contain a constituent unit represented by the following formula (9).

[0053]

[0054] A in equation (9) ３ This independently represents a tetravalent organic group containing a cyclic structure. B ３ It has a cyclic structure and represents hydrocarbon groups other than the divalent hydrocarbon group derived from the dimer acid. When multiple constituent units of general formula (9) are present in a bismaleimide compound, multiple A ３ Each of them is independent, and they may be the same or different, and there may be multiple B ３ Each of these units is independent and may be identical or different. Furthermore, the order of each repeating unit is not restricted, and the combination can be alternating, block-based, or random.

[0055] The bismaleimide compound (A) may have a structure represented by the following formula (1') consisting of the constituent units represented by formula (1), and a structure represented by the following formula (9') consisting of the constituent units represented by formula (9). In formulas (1') and (9'), m and n are between 1 and 100. Furthermore, the order of each repeating unit enclosed by m and n is not limited, and the bonding mode may be alternating, in blocks, or random.

[0056]

[0057] Furthermore, the bismaleimide compound (A) according to this embodiment may also contain three structural units represented by the following formulas (1), (9), and (12). The bismaleimide compound (A) may have a structure represented by the following formula (1') consisting of the structural unit represented by formula (1), a structure represented by the following formula (9') consisting of the structural unit represented by formula (9), and a structure represented by the following formula (12') consisting of the structural unit represented by formula (12).

[0058] In formulas (1), (9), (12) or (1'), (9'), (12'), A １ A ３ A ４ This independently represents a tetravalent organic group containing a cyclic structure. B １ B is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. ３ This represents a divalent hydrocarbon group consisting of a cyclic structure. B ４ represents a hydrocarbon group consisting of a diamine derived from a dimer acid. m, n, and o are between 1 and 100. Furthermore, the order of each repeating unit enclosed by m, n, and o is not limited, and the bonding pattern may be alternating, block-like, or random.

[0059] The bismaleimide compound (A) is not particularly limited, but from the viewpoint of good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, it is preferably 1,000 to 75,000, more preferably 1,500 to 50,000, and even more preferably 1,500 to 30,000. In this embodiment, "weight-average molecular weight" refers to the weight-average molecular weight on a polystyrene standard basis, calculated by gel permeation chromatography (GPC).

[0060] Normally, maleimide compounds have poor light transmittance. Therefore, when the resin composition described later contains a maleimide compound, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, making it difficult for the photocuring initiator to generate radicals. Consequently, photoradical reactions of maleimide compounds generally do not proceed easily, and even if radical polymerization or dimerization reactions of maleimide alone proceed, the reactivity is very low. However, the bismaleimide compound (A) has excellent light transmittance because the maleimide group is bonded to the aromatic ring via a methylene group, resulting in a short conjugation length. This allows sufficient light to reach the photocuring initiator, and the photoradical reaction of maleimide occurs efficiently. Furthermore, when a chloroform solution containing 1% by mass of the maleimide compound is prepared and its light transmittance is measured using light at a wavelength of 405 nm (h-line), the transmittance is 3% or more, indicating excellent light transmittance. Therefore, for example, when manufacturing printed circuit boards with high-density and high-definition wiring patterns using direct lithography, the photoradical reaction of maleimide occurs efficiently even when active energy rays including a wavelength of 405 nm (h-line) are used.

[0061] When using active energy rays including a wavelength of 405 nm (h-ray), polymerization will not proceed unless the photocuring initiator absorbs light at a wavelength of 405 nm (h-ray) and generates radicals. Therefore, in this case, it is preferable to use a photocuring initiator that exhibits excellent absorption of light at a wavelength of 405 nm (h-ray), with an absorbance of 0.1 or higher at a wavelength of 405 nm (h-ray), as described later.

[0062] As described above, the bismaleimide compound (A) has excellent light transmittance, so even when using light with a wavelength of 405 nm, for example, the light reaches the photocuring initiator sufficiently, and the radical reaction using radicals generated from the photocuring initiator proceeds, making photocuring possible even in resin compositions containing a large amount of maleimide compound. Furthermore, the cured product obtained containing the resin composition of this embodiment has excellent photocurability, heat resistance, and thermal stability, so a protective film and an insulating layer can be suitably formed.

[0063] In the above formulas (1), (1'), (9), (9'), (12) or (12'), A １ A ３ A ４ These independently represent a tetravalent organic group containing a cyclic structure, and it is preferable that it be one of the tetravalent organic groups shown in the following structural formula. In the following structural formula, the bond marked with * is A １ A ３ A ４ This shows the locations where the organic group and imide group that make up the compound are bonded.

[0064]

[0065] In the above formulas (1), (1'), (9), (9'), (12) or (12'), B １The group is a divalent hydrocarbon group having 13 to 200 carbon atoms that does not have a cyclic structure, preferably having 14 to 30 carbon atoms, more preferably 16 to 24 carbon atoms, and even more preferably 18 to 22 carbon atoms, and is an alkylene group or alkenylene group that is linear or has a branched chain of one or more alkyl groups and / or alkenyl groups having 1 to 4 carbon atoms. The term "alkylene group or alkenylene group having 14 to 30 carbon atoms" as used herein includes linear or branched alkylene groups having 14 to 30 carbon atoms and linear or branched alkenylene groups having 14 to 30 carbon atoms. Examples of alkylene or alkenylene groups having 14 to 30 carbon atoms include linear alkylene groups having 14 to 30 carbon atoms; alkylene groups having 14 to 30 carbon atoms and having a branched chain of one or more C1-C4 alkyl groups and / or alkenyl groups; linear alkenylene groups having 14 to 30 carbon atoms; and alkenylene groups having 14 to 30 carbon atoms and having a branched chain of one or more C1-C4 alkyl groups and / or alkenyl groups. Because these alkylene or alkenylene groups having 14 to 30 carbon atoms are linear or have a branched chain of one or more C1-C4 alkyl groups and / or alkenyl groups, they exhibit excellent compatibility with the maleimide compounds (B) or polymers (E) described later.

[0066] Examples of linear alkylene groups having 14 to 30 carbon atoms include n-tetradecanylene, n-pentadecanylene, n-hexadecanylene, n-heptadecanylene, n-octadecanylene, n-nonadecanylene, n-icosanylene, n-henicosanylene, n-docosaniylene, n-tricosaniylene, n-tetracosanylene, n-pentacosanylene, n-hexacosanylene, n-heptacosanylene, and n-octacosanylene. Examples of linear alkenylene groups having a total of 14 to 28 carbon atoms include tetradekenylene, pentadekenylene, hexadekenylene, heptadekenylene, octadekenylene, nonadekenylene, eicosenylene, henicosenylene, docosenylene, tricosenylene, tetracosenylene, pentacosenylene, hexacosenylene, heptacosenylene, and octacosenylene.

[0067] "An alkylene group having 14 to 30 carbon atoms and a branched chain of one or more C1 to C4 alkyl groups and / or alkenyl groups" refers to an alkylene group having 14 to 30 carbon atoms that includes at least one group selected from the group consisting of C1 to C4 alkyl groups and C1 to C4 alkenyl groups as a branched chain. "An alkenylene group having 14 to 30 carbon atoms and a branched chain of one or more C1 to C4 alkyl groups and / or alkenyl groups" refers to an alkenylene group having a total of 14 to 30 carbon atoms that includes at least one group selected from the group consisting of C1 to C4 alkyl groups and C1 to C4 alkenyl groups as a branched chain. Examples of C1 to C4 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. Examples of alkenyl groups having 1 to 4 carbon atoms include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, and 3-butenyl groups.

[0068] In the above formulas (1) and (1'), B １The hydrocarbon group constituting the above is preferably an alkylene group having 14 to 30 carbon atoms, which is linear or has a branched chain of one or more alkyl groups having 1 to 4 carbon atoms, in order to impart appropriate flexibility to the resulting resin composition when used as a component of the resin additive described later. More preferably, it is an alkylene group having 14 to 30 carbon atoms, which has a branched chain of one alkyl group having 1 to 4 carbon atoms, and even more preferably, it is an alkylene group having a total of 14 to 30 carbon atoms, which has a branched chain of one ethyl group or one or more methyl groups. Alternatively, B in formulas (1) and (1') above may be used. １ Since the hydrocarbon groups constituting the alkylene group or alkenylene group can be easily produced using commercially available dibasic acids or their derivatives, as described later, it is preferable that the main chain portion (i.e., the chain-like hydrocarbon portion excluding the branched chain) of the constituent alkylene group or alkenylene group has 2n carbon atoms (where n is an integer from 6 to 14).

[0069] Specific examples of such hydrocarbon groups include linear saturated diamines such as tetradecanediamine, hexadecanediamine, octadecanediamine, eicosadiamine, docosadiamine, tetracosadiamine, and octacosadiamine; tetradecanediamine-7-ene, hexadecanediamine-6-ene, hexadecanediamine-8-ene, octadecanediamine-8-ene, octadecanediamine-10-ene, eicosadiamine-6-ene, eicosadiamine-8-ene, eicosadiamine-12-ene, eicosa Linear unsaturated diamines such as diamine-8,12-diene, eicosadiamine-10,14-diene, docosadiamine-7,11,15-triene, docosadiamine-8,12,16-triene, 1,24-tetracosadiamine-8,12,16-triene, and tetracosadiamine-10,14,18-triene; 6,8-dimethyltetradecanediamine, 7-ethyltetradecanediamine, 7-propyltetradecanediamine, 7-ethylhexadecanediamine, 7-butylhexadecanediamine, and 7-isopropyl Branched saturated diamines such as pyr-10-methylhexadecanediamine, 8-ethyloctadecanediamine, 8-isopropyl-11-methyloctadecanediamine, 8,13-diethyloctadecanediamine, 8,13-dimethyleicosadiamine, 9,12-dimethyleicosadiamine, and 9,12-diethyleicosadiamine; 7-vinyltetradecanediamine, 7-vinylhexadecanediamine-8-ene, 7-isopropenyl-10-methylhexadecanediamine-9-ene, and 8-vinyl-octadecane Examples include branched unsaturated diamines such as diamine-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-dimethyleicosadiamine-8,12-diene, and 9,12-dimethyleicosadiamine-8,12-diene; and hydrocarbon groups obtained by removing the amine group from these diamines. One of these may be used, or two or more may be used.

[0070] In the above formula (1) or (1'), B １The hydrocarbon groups constituting the compound are preferably hydrocarbon groups obtained by removing the amine group from diamines such as 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene, from the viewpoint of achieving both flexibility and heat resistance. One of these may be used, or two or more may be used. B １ As a commercially available diamine having hydrocarbon groups that constitute the compound, it is preferable to use Diamine H2O (manufactured by Okamura Oil Co., Ltd.).

[0071] In the above formula (9) or (9'), B ３ This is independently a divalent hydrocarbon group having a cyclic structure. A divalent hydrocarbon group having a cyclic structure can be any compound having a cyclic structure, and it may have substituents attached. Examples of cyclic structures include aromatic rings and aliphatic rings. Examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, tetracene rings, chrysene rings, triphenylene rings, tetrafen rings, pyrene rings, pentacene rings, picene rings, and perylene rings. On the other hand, examples of aliphatic rings include monocycloalkane rings, bicycloalkane rings, tricycloalkane rings, tetracycloalkane rings, and dicyclopentadiene.

[0072] B ３ The hydrocarbon groups constituting the compound are hydrocarbon groups having an aromatic ring structure represented by the following formula (10), or hydrocarbon groups having an alicyclic structure selected from the group represented by the following formula (11).

[0073]

[0074] In formula (10), R １５ Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. l represents an integer from 0 to 4. Bonds marked with an asterisk (*) in the structural formula represent bonding.

[0075]

[0076] In formula (11), R １６Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. p represents an integer from 0 to 10, p' represents an integer from 0 to 14, and p'' represents an integer from 0 to 7. Bonds marked with an asterisk (*) in the structural formula represent bonding.

[0077] The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples include methyl, ethyl, n-propyl, i-propyl, butyl, isobutyl, sec-butyl, and tert-butyl groups. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl, ethyl, n-propyl, and i-propyl groups are more preferred, as they exhibit excellent adhesion to chips and substrates, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0078] The linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, and tert-butoxy groups. Among these, alkoxy groups having 1 to 4 carbon atoms are preferred, and methoxy, ethoxy, n-propoxy, and iso-propoxy groups are more desirable, as they exhibit excellent adhesion to chips and substrates, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. In addition to excellent adhesion to chips and substrates, as well as good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, the aromatic ring structure represented by formula (10) is unsubstituted (l=0), or R １５ The functional group is preferably a methyl group, ethyl group, hydroxyl group, methoxy group, or ethoxy group, more preferably substituted with a functional group selected from methyl and hydroxyl groups, and even more preferably unsubstituted.

[0079] In addition to excellent adhesion to chips and substrates, etc., it exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Therefore, the alicyclic structure selected from the group shown in formula (11) is either unsubstituted (p=0, p'=0, p''=0), R １６ The functional group is preferably a methyl group, an ethyl group, a hydroxyl group, a methoxy group, or an ethoxy group, more preferably a functional group selected from a methyl group and a hydroxyl group, and even more preferably p=0, p'=0, and p''=0.

[0080] Specific examples of hydrocarbon groups having an aromatic ring represented by formula (10) include a hydrocarbon group obtained by removing the amine group from metaxylenediamine (formula (13) below), a hydrocarbon group obtained by removing the amine group from paraxylenediamine (formula (14) below), and a hydrocarbon group obtained by removing the amine group from orthoxylendiamine (formula (15) below). B represented by formulas (1) and (1') above. １ Preferably, it is a hydrocarbon group of the following formula (13). * represents a bond.

[0081]

[0082]

[0083]

[0084] Preferred hydrocarbon groups having an aliphatic ring represented by formula (11) include the hydrocarbon group obtained by removing the amine group from 1,3-bis(aminomethyl)cyclohexane (formula (16) below), the hydrocarbon group obtained by removing the amine group from norbornanediamine (formula (17) below), the hydrocarbon group obtained by removing the amine group from tricyclodecanedimethylamine (formula (18) below), and the hydrocarbon group obtained by removing the amine group from isophoronediamine (formula (19) below). (* indicates a bond.)

[0085]

[0086]

[0087]

[0088]

[0089] In the above formula (12) or (12'), B ４ The hydrocarbon groups constituting the molecule are independently divalent hydrocarbon groups having 6 to 200 carbon atoms, preferably 8 to 100, and more preferably 10 to 50 carbon atoms. In particular, it is preferable that the branched divalent hydrocarbon group is one in which one or more hydrogen atoms in the divalent hydrocarbon group are substituted with alkyl or alkenyl groups having 6 to 200 or more carbon atoms, preferably 8 to 100, and more preferably 10 to 50 carbon atoms. The branched divalent hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated hydrocarbon group, and may have an alicyclic or aromatic ring structure in the middle of the molecular chain. Specifically, examples of the branched divalent hydrocarbon group include hydrocarbon groups derived from diamines at both ends, called dimer amines. Dimer amines are obtained by substituting the two carboxyl groups of dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, with primary amino groups, as shown in formulas (20) to (25) below (see Japanese Patent Publication No. 9-12712, etc.). Specific examples of commercially available dimer amines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamin 551 (manufactured by Cognis Japan Co., Ltd.). These may be used individually or in combination of two or more. The following are non-restrictive general formulas for dimer amines. In formulas (20) to (25), m+n = 6 to 17 is preferred, and p+q = 8 to 19 is preferred. In formulas (20) to (23), the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0090]

[0091] The residues obtained by removing the amino group from the dimer amines represented by formulas (20) to (25) above are specifically divalent hydrocarbon groups represented by the following formulas (20') to (25'). In each of formulas (20') to (25'), m+n = 6 to 17 is preferred, and p+q = 8 to 19 is preferred. In formulas (20') to (23'), the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. * indicates a bond with N.

[0092] <Method for Producing Bismaleimide Compounds> There are no particular restrictions on the method for producing bismaleimide compound A, but it can be efficiently produced by, for example, the method shown below. A bismaleimide compound can be obtained by synthesizing an amic acid with a tetrabasic acid dianhydride and a diamine, undergoing ring-closing dehydration in step I, then reacting with maleic anhydride to synthesize maleamic acid, and finally undergoing ring-closing dehydration in step II to seal the molecular chain ends with maleimide groups.

[0093] In the above manufacturing method, each step can be broadly divided into two parts: the synthesis reaction of amic acid or maleamic acid and the ring-closing dehydration reaction, which will be described in detail below.

[0094] In step I, amic acid is first synthesized by reacting a specific tetrabasic dianhydride with a specific diamine. This reaction generally proceeds in an organic solvent (e.g., a nonpolar solvent or a high-boiling point aprotic polar solvent) at room temperature (25°C) to 100°C. The subsequent ring-closing dehydration reaction of amic acid proceeds under conditions of 90 to 130°C, while removing the by-product water from the system via a condensation reaction. Organic solvents (e.g., nonpolar solvents, high-boiling point aprotic polar solvents, etc.) or acid catalysts can be added to accelerate the ring-closing dehydration reaction.

[0095] Examples of organic solvents include toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). These may be used individually or in combination of two or more. Examples of acid catalysts include sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. These may be used individually 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. By blending in this ratio, a copolymer containing amino groups at both ends can be synthesized.

[0096] In Step II, maleamic acid is synthesized by reacting a diamine having amino groups at both ends obtained in Step I with maleic anhydride at room temperature (25°C) to 100°C. Finally, ring closure dehydration is carried out while removing water in the system as a by-product under the conditions of 95 to 130°C to block the molecular chain ends with maleimide groups, and the target bismaleimide compound can be obtained. When the blocking reaction with the maleimide groups at the molecular chain ends is carried out at 130°C or lower, side reactions and high molecular weight substances are less likely to occur, which is preferable, and it is more preferable to carry out the reaction at 120°C or lower. With such a production method, the obtained bismaleimide compound has a block copolymer structure, so that the compatibility of the synthesized resin can be made uniform and improved.

[0097] The purification method of the compound of the present embodiment may be a conventional method, and reprecipitation, liquid separation, etc. can be used.

[0098] As the mixing ratio of the raw materials in the reaction, (B １ the total number of moles of the organic diamine having a hydrocarbon group constituting it and B ３ the total number of moles of the organic diamine having a cyclic skeleton constituting it and B ４ the total number of moles of the organic diamine derived from the dimer acid constituting it): (A １ A ３ A ４ the total number of moles of the tetracarboxylic dianhydride constituting it and half of the number of moles of maleic anhydride) is preferably 1:1 to 1:1.4. Further, from the viewpoint of obtaining a composition capable of obtaining a cured product having a high Tg and low dielectric characteristics, (B １ the number of moles of the organic diamine having 13 to 200 carbon atoms constituting it): (B ３ the number of moles of the organic diamine having a cyclic structure constituting it) is preferably 0.1:10 to 10:10, and more preferably 0.5:10 to 5:10. Furthermore, when introducing the organic diamine derived from the dimer acid constituting B ４ ), (B １ the number of moles of the organic diamine having 13 to 200 carbon atoms constituting it and the number of moles of the organic diamine derived from the dimer acid constituting B ４ ): (B ３It is desirable that the ratio of moles of organic diamines having a cyclic structure constituting the compound be 0.5:10 to 5:10. That is, if the bismaleimide compound contains the three structures represented by formulas (1'), (9'), and (12'), it is desirable that m+o:n = 0.5:10 to 5:10. Furthermore, regarding m:o, from the viewpoint of compatibility with polar functional groups, as the ratio of o increases, the compounds become incompatible, so it is desirable that m:o = 10:0 to 5:5.

[0099] The resin composition of this embodiment contains at least one maleimide compound (B) selected from the group consisting of compounds represented by the following formulas (2) to (8). (Compound represented by formula (2)) The compound represented by formula (2) is the following compound.

[0100]

[0101] In formula (2), R １ , R ２ , and R ３ Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom, a hydroxyl group, or a substituent. n represents an integer from 1 to 10. From the viewpoint of achieving good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, methyl, ethyl, n-propyl, and isopropyl groups are preferred as the linear or branched alkyl group having 1 to 6 carbon atoms, and methyl groups are more preferred. １ , R ２ , and R ３ In this regard, from the viewpoint of exhibiting superior solubility in solvents, R １ and R ３ However, it is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ２ It is preferable that is a hydrogen atom. The preferred alkyl group is as described above. n is preferably an integer from 1 to 10, and more preferably an integer from 1 to 6, from the standpoint of excellent solubility in the solvent, obtaining a more suitable viscosity, and being able to better control the increase in the viscosity of the varnish.

[0102] The compound represented by formula (2) may be a commercially available product, for example, BCPH13 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd., represented by formula (26), BCPH01 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd., or BMCX426 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd., represented by formula (27).

[0103]

[0104] In equation (26), n is an integer between 1 and 5.

[0105]

[0106] In equation (27), n is an integer between 1 and 10.

[0107] (Compound represented by formula (3)) The compound represented by formula (3) is the following compound:

[0108]

[0109] In formula (3), R ４ Each of these independently represents either a hydrogen atom or a methyl group. n represents an integer from 1 to 10. As the maleimide compound represented by formula (3), a commercially available product may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd., represented by formula (28).

[0110]

[0111] In equation (28), n is an integer between 1 and 10.

[0112] (Compound represented by formula (4)) The compound represented by formula (4) is the following compound:

[0113]

[0114] In formula (4), R ５ , R ６ , and R ７Each of these independently represents a linear or branched alkyl group having 1 to 8 carbon atoms, which may have a hydrogen atom or a substituent. The linear or branched alkyl group having 1 to 8 carbon atoms, which may have a substituent, is not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, and heptyl group. The hydrogen atoms in these alkyl groups may be substituted with halogen atoms such as fluorine and chlorine atoms, and cyano groups, etc. Among these alkyl groups, methyl group, ethyl group, isopropyl group, and tert-butyl group are preferred, more preferably methyl group, ethyl group, and tert-butyl group, and even more preferably methyl group, from the viewpoint of superior photocurability, heat resistance, and thermal stability, as well as better solubility in solvents. The compound represented by formula (4) is more preferably the compound represented by formula (29) (also referred to as TMDM in this embodiment) because it has superior photocurability, heat resistance, and thermal stability, as well as better solubility in solvents.

[0115]

[0116] (Compound represented by formula (5)) The compound represented by formula (5) is the following compound:

[0117]

[0118] In formula (5), R ８ Each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ９ Each of these independently represents either a hydrogen atom or a methyl group. ８ From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, it is preferable that the group be a methyl group or an ethyl group. ９ From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, hydrogen atoms are preferred.

[0119] As the maleimide compound represented by formula (5), a commercially available product may be used, for example, BMI-70 (trade name) manufactured by K.I. Chemicals Co., Ltd., represented by formula (30).

[0120]

[0121] (Compound represented by formula (6)) The compound represented by formula (6) is the following compound:

[0122]

[0123] In formula (6), R １０ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group. １０ From the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins, a methyl group or an ethyl group is preferred. As the maleimide compound represented by formula (6), a commercially available product may be used, for example, BMI-80 (trade name) manufactured by K.I. Chemicals Co., Ltd., represented by formula (31).

[0124]

[0125] (Compound represented by formula (7)) The compound represented by formula (7) is the following compound:

[0126]

[0127] In formula (7), R １１ Each of these independently represents either a hydrogen atom or a methyl group. n represents an integer from 1 to 10. １１ As for n, it is preferable that it be a hydrogen atom, from the viewpoint of exhibiting good solubility in solvents, low boiling point, low water absorption, and good compatibility with other resins. As for n, it is more preferable that it be an integer from 1 to 5, from the viewpoint of having excellent solubility in solvents, obtaining a more suitable viscosity, and being able to better control the increase in the viscosity of the varnish.

[0128] As the maleimide compound represented by formula (7), a commercially available product may be used, for example, BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd., represented by formula (32).

[0129]

[0130] In equation (32), n is an integer between 1 and 5.

[0131] The compound represented by formula (8) is the following compound:

[0132] In equation (8), there are multiple R １２ Each of these independently represents an alkyl group with 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value n ａｖｅ is 1 < n ａｖｅ < 5. The mean value of n is n ａｖｅ This can be calculated from the number-average molecular weight of the compound and the molecular weight of the repeating units. The number-average molecular weight of the compound represented by formula (8) can be calculated based on the analysis results using a differential refractive index detector in GPC (gel permeation chromatography) analysis.

[0133] In formula (8), m is usually 0 to 3, preferably 0 to 2, and more preferably 0. １２ is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group. When m is greater than 3 or R １２ If the alkyl group has six or more carbon atoms, the electrical properties may deteriorate due to molecular vibrations when the alkyl group is exposed to high frequencies.

[0134] Compound (8) more preferably has a structure represented by the following formula (33). In formula (8), R １２ This is because, in the case of an alkyl group having 1 to 5 carbon atoms, the crystallinity decreases compared to when the propyl group is substituted at the para position on the benzene ring that is not bonded to the maleimide group.

[0135]

[0136] In equation (33), there are multiple R １５ Each of these independently represents an alkyl group with 1 to 5 carbon atoms. m represents an integer from 0 to 3. n is the number of repetitions, and its average value n ａｖｅ is 1 < n ａｖｅ < 5

[0137] R in equation (33) １５The preferred ranges for , m, and n are the same as in equation (8).

[0138] In the resin composition, the content of bismaleimide compound (A) is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, and even more preferably 30 to 80 parts by mass, based on 100 parts by mass of the total of bismaleimide compound (A) and maleimide compound (B), in order to obtain a resin composition with better compatibility with maleimide compound (B), better heat resistance and thermal stability, and furthermore, good photocurability and crack resistance.

[0139] Bismaleimide resin (A) and maleimide resin (B) are characterized by their excellent compatibility. In this application, "compatible" means that when a resin composition is formed by uniformly mixing two or more resins, the haze of the solution is less than 50 in the case of a liquid, and when a cured product is formed, only one glass transition temperature (Tg) is measured for the resin composition. In other words, when the resins are "not compatible," the haze is 50 or more in the case of a liquid, and in the case of a cured product, even if the resins are uniformly mixed, multiple Tg values ​​are measured.

[0140] The compatibility and haze of the resin composition of this embodiment were measured as follows: [Compatibility] When the resin composition was observed visually, those that did not contain precipitates, etc., and could be applied to a substrate were considered to have good compatibility, while those that contained precipitates, etc., and were difficult to apply to a substrate were considered to have poor compatibility. [Haze Value] In accordance with JIS K7136, the resin composition was placed in a square cell with an optical path length of 10 mm, and light was irradiated onto the resin composition using a color and turbidity simultaneous meter (Nippon Denshoku, COH400) at a temperature of 25°C. The haze value was calculated using the following formula (1) as the ratio of the total light transmittance (Tt), which represents the total amount of light transmitted, and the diffuse light transmittance (Td) transmitted after being diffused by the sheet. The total light transmittance (Tt) is the sum of the parallel light transmittance (Tp) transmitted while remaining coaxial with the incident light and the diffuse light transmittance (Td). Haze (H) = Td / Tt × 100 ... (1)

[0141] The resin composition of this embodiment may contain the following polymer (E) instead of the maleimide resin (B). Alternatively, the resin composition of this embodiment may contain the following polymer (E) together with the maleimide resin (B). (Polymer (E)) Polymer (E) has structural units represented by the following formulas (12) and / or (13). (Structural units represented by formula (12))

[0142] In formula (12), A ２ This indicates a tetravalent organic group. B ２ R indicates a divalent organic group. １３ and R １４ Each of these independently represents a hydrogen atom or a monovalent organic group. There may be multiple structural units represented by formula (12), and A in multiple structural units ２ , B ２、 R １３ and R １４ These may be the same or different. １３ and R １４ The combination of each element is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups.

[0143] A ２ When the tetravalent organic group represented by contains an aromatic ring, each aromatic ring may have a substituent or be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, amino groups, etc. ２ When a tetravalent organic group represented by contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)). Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ -; Two R's ＢEach of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2. The rings may be linked by linking groups such as ( ), or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0144] In equation (12), A ２ When the tetravalent organic group represented by contains an aromatic ring or alicyclic structure, -COOR １３ Preferably, the group and the -CO- group are located at the positions of adjacent carbon atoms (ortho position in the case of a benzene ring), and -COOR １４ Preferably, the group and the -CONH- group are located at the positions of adjacent carbon atoms (ortho positions in the case of a benzene ring).

[0145] In equation (12), A ２ The tetravalent organic group represented by is preferably one of the tetravalent organic groups shown in the following structural formula. In the following structural formula, the bonds marked with * are -COOR １３ group, -CO- group, -COOR １４ This indicates the site where the group is bonded to the -CONH- group.

[0146]

[0147] In equation (12), B ２ The divalent organic group represented by may be a divalent aliphatic group, a divalent aromatic group, or a combination of multiple divalent organic groups. For example, as a divalent aliphatic group, B １ Or B ４Examples of structures that make up the compound include: As divalent aromatic groups, for example, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3 '-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylthioether, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimeth Rubentidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis(3-aminophenoxyphenyl)propane, 2,2'-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxyphenyl)benzene, 1,3'-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane (no-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane, bis(4-amino-3,5-dipropylphenyl)methane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,Examples include 2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene, etc. From the viewpoint of heat resistance, B, ３ The divalent organic group represented is preferably a divalent aromatic group.

[0148] Furthermore, B ２ When a divalent organic group represented by contains a phenolic hydroxyl group in its structure, it may also be a reaction product with a compound having a functional group that can react with that phenolic hydroxyl group. Examples of functional groups that can react with a phenolic hydroxyl group include isocyanate groups, carboxylic acid chloride groups, acid anhydride groups, epoxy groups, silyl chloride groups, alkyl halogenated groups, ester groups, sulfonyl chloride groups, and carboxyl groups.

[0149] R １３ and R １４ Each of these independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following formula (21), an ethyl group, an isobutyl group, or a t-butyl group, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following formula (21). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (21), the transmittance of the h-ray is high, and good cured products tend to be formed even when curing at low temperatures of 350°C or below.

[0150]

[0151] In formula (21), R １６ This indicates a divalent linking group, R １７ Each of these independently represents a hydrogen atom and an aliphatic hydrocarbon group having 1 to 3 carbon atoms. * represents the bond with O in formula (12). (Structural unit represented by formula (13))

[0152]

[0153] In formula (13), A ２ This indicates a tetravalent organic group, B ２ This indicates a divalent organic group. A ２ and B ２ This is equivalent to formula (12) above. Furthermore, there may be multiple structural units represented by formula (13), and A in multiple structural units ２ and B ２ These may be the same or different.

[0154] In the resin composition, the content of maleimide compound (A) is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, and even more preferably 30 to 80 parts by mass, per 100 parts by mass of bismaleimide compound (A), from the viewpoint of obtaining a resin composition with better compatibility with at least one polymer (E) containing structural units represented by formula (12) and / or (13), better heat resistance and thermal stability, and furthermore, good photocurability and crack resistance.

[0155] <Photopolymerization Initiator (C)> The resin composition of the present invention may optionally contain a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited, and conventionally used ones can be used as appropriate, for example, acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyldimethyl ketal, thioxatone, 2-chlorothioxatone, 2-methylthioxatone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl- Examples of photopolymerization initiators include 1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-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-benzoyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), and 2,4-dimethylthioxanthone. Such photopolymerization initiators (C) may be used individually or in combination of two or more types.

[0156] Among these, as the photopolymerization initiator (C), it is preferable to use one that efficiently generates radicals at exposure wavelengths of 310 to 436 nm, more preferably 405 nm, from the viewpoint that fine patterns can be formed using a reduction projection exposure machine (stepper; light source wavelength: 365 nm, 436 nm) which is standardly used in the manufacturing process of semiconductor protective films, etc. Furthermore, maleimide groups generally do not undergo homopolymerization by radicals, and instead, a dimerization reaction of the bismaleimide compound proceeds mainly through reaction with radicals generated from the photopolymerization initiator, forming a crosslinked structure. For this reason, the inventors surmise that bismaleimide compounds are generally less reactive than acrylic compounds and the like that are commonly used as photopolymerizable compounds. Therefore, from the viewpoint that radicals can be generated more efficiently and reactivity is higher at exposure wavelengths of 310 to 436 nm, more preferably 405 nm, it is even more preferable that the photopolymerization initiator in this embodiment is a compound having an oxime structure or a thioxanthone structure.

[0157] Examples of such photopolymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] having an oxime structure (BASF Japan, "IRGACURE OXE-01"), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (BASF Japan, "IRGACURE OXE-02"), and 2,4-dimethylthioxanthone having a thioxanthone structure (Nippon Kayaku Co., Ltd., "DETX-S"). While such photopolymerization initiators with high radical generation ability by light tend to be too reactive and difficult to control when used in the photopolymerization of ordinary acrylic compounds, they can be suitably used in this embodiment.

[0158] In the resin composition, the content of the photopolymerization initiator (C) 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, based on 100 parts by mass of the total of the bismaleimide compound (A) and the maleimide compound (B) or polymer (E), in order to obtain a resin sheet that has better compatibility with the bismaleimide compound (A) and the maleimide compound (B) or polymer (E), which allows for sufficient photocuring of these compounds, sufficiently insolubilizes the exposed areas in terms of developability with organic solvents, and further suppresses cracking.

[0159] <Curing accelerator (D)> The resin composition may further contain a curing accelerator (D). For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine. Examples include amines such as triphenylphosphine, tributylphosphine, and trioctylphosphine; organometallic 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; thermal radical polymerization initiators; 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. Curing accelerator (D) can also be used as a thermosetting initiator. Among these, thermal radical polymerization initiators are preferred.

[0160] Examples of thermal radical polymerization initiators include organic peroxide-based polymerization initiators such as di-tert-butyl peroxide and dicumyl peroxide, and azo-based polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile.

[0161] Specific examples of curing accelerators (D) are shown below. Examples of organic peroxide polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butyl peroxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexyl peroxy)cyclohexane, 1,1-bis(t-hexyl peroxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butyl peroxy)cyclohexane, and 2,2-bis(4,4-di- t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl4,4-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-dimeth Lu-2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3,-Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl Examples include peroxymalic acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, t-butyl peroxyallyl monocarbonate, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0162] 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-carbonitride), 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)dihydrochloride. 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 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-diazepine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidine-2-yl)propane]dihydrochloride, 2,2'-Azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidine-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].

[0163] Furthermore, examples of curing accelerators (D) include phosphine compounds, compounds containing phosphonium salts, and imidazole compounds, and one or more of these can be used in combination. Imidazole compounds are particularly preferred. Imidazole compounds have excellent catalytic properties and can more reliably accelerate the polymerization reaction of maleimide resins (A) and (B).

[0164] Examples of imidazole compounds include, but are not limited to, 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-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole. In particular, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferred. Using these compounds further accelerates the reaction of maleimide resins (A) and (B), resulting in the advantage of improved heat resistance of the resulting cured product. These can be used individually or in combination of two or more.

[0165] The phosphine compounds are not particularly limited, but examples include primary phosphines such as alkyl phosphines like ethylphosphine and propylphosphine, and phenylphosphine; secondary phosphines such as dialkylphosphines like dimethylphosphine and diethylphosphine, diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; trialkylphosphines such as trimethylphosphine, triethylphosphine, tributylphosphine, and trioctylphosphine; tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tripenzylphosphine, tritlylphosphine, tri-p-styrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, and tri-2-cyanoethylphosphine. Among these, tertiary phosphines are preferred. These can be used individually or in combination of two or more.

[0166] Compounds containing phosphonium salts include compounds containing tetraphenylphosphonium salts, alkyltriphenylphosphonium salts, and tetraalkylphosphonium. More specifically, examples include tetraphenylphosphonium-thiocyanate, tetraphenylphosphonium-tetra-p-methylphenylborate, butyltriphenylphosphonium-thiocyanate, tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid.

[0167] The curing accelerator (D) can be used alone or in combination of two or more types. The content of the curing accelerator (D) is not particularly limited, but is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of reactive resin components.

[0168] <Compound (F) containing one or more carboxyl groups> The resin composition may contain a compound (F) (also referred to as component (F) or compound (F)) containing one or more carboxyl groups. Compound (F) is not particularly limited as long as it contains one or more carboxyl groups. The carboxyl groups may be salts such as sodium salts and potassium salts, and if the molecule contains two or more carboxyl groups, it may be an acid anhydride formed by the linkage of these groups. Compound (F) can be used alone or by mixing two or more as appropriate.

[0169] Compound (F) can be photocured with the bismaleimide compound (A) and maleimide compound (B), and optionally with a photocuring initiator (C), using various active energy rays to obtain a cured product. A resin composition containing compound (F) can also be obtained in the unexposed areas. When an N-methylpyrrolidone solution containing compound (F) at a concentration of 1% by mass is prepared and the transmittance of the N-methylpyrrolidone solution containing compound (F) at a concentration of 1% by mass is measured using active energy rays including a wavelength of 405 nm (h-ray), the transmittance is preferably 5% or higher, and even in this case, it exhibits excellent light transmittance. When such compound (F) is used, for example, when manufacturing a printed circuit board with high density and high-definition wiring formation (pattern) using a direct writing exposure method, the photoradical reaction of maleimide occurs efficiently even when using active energy rays including a wavelength of 405 nm (h-ray). The transmittance at a wavelength of 405 nm (h-ray) is preferably in the following order: 5% or more, 8% or more, 10% or more, 20% or more, and 30% or more, in order to obtain a resin composition with superior photocurability. The upper limit for the transmittance at a wavelength of 405 nm (h-ray) is, for example, 99.9% or less.

[0170] In this embodiment, it is preferable that the molecule of compound (F) contains an integer number of carboxyl groups from 2 to 4, in order to obtain better alkali developability.

[0171] The molecular weight of compound (F) is preferably 50 to 1000, and more preferably 100 to 800, from the viewpoint of improving developability.

[0172] Examples of compound (F) include formic acid, aliphatic compounds containing one or more carboxyl groups, aromatic compounds containing one or more carboxyl groups, and heterocompounds containing one or more carboxyl groups. These compounds (F) can be used individually or in appropriate mixtures of two or more.

[0173] (Aliphatic compounds containing one or more carboxyl groups) Examples of aliphatic compounds containing one or more carboxyl groups include linear aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, linear aliphatic polycarboxylic acids, and alicyclic polycarboxylic acids. These compounds may have substituents such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups in their molecules. Furthermore, if these compounds have two or more carboxyl groups in their molecules, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in their molecules, they may be acid anhydrides formed by the linkage of a carboxyalkyl group and a carboxyl group. If these compounds have two or more carboxyalkyl groups in their molecules, they may be acid anhydrides formed by the linkage of these groups.

[0174] 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 groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy groups. Examples of aryloxy groups include phenoxy and p-tolyloxy groups. Examples of aryl groups include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthryl groups. Examples of aminoalkyl groups include aminomethyl, aminoethyl, aminopropyl, aminodimethyl, aminodiethyl, aminodipropyl, aminobutyl, aminohexyl, and aminononyl groups. Examples of carboxyalkyl groups include carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxyhexyl, and carboxynonyl groups.

[0175] Examples of chain-like aliphatic monocarboxylic acids 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, as well as unsaturated fatty acids such as oleic acid, elaidic acid, erucic acid, nervonic acid, linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, and linolenic acid.

[0176] 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, as well as polycyclic or bridged alicyclic carboxylic acids such as norbornanecarboxylic acid, tricyclodecanecarboxylic acid, tetracyclododecanecarboxylic acid, adamantanecarboxylic acid, methyladamantanecarboxylic acid, ethyladamantanecarboxylic acid, and butyladamantanecarboxylic acid.

[0177] Examples of linear aliphatic polycarboxylic acids include carboxylic acids in which one or more carboxyl groups are further added to a linear aliphatic monocarboxylic acid. Examples include propionidioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, and octadecanedioic acid.

[0178] Examples of alicyclic polycarboxylic acids include carboxylic acids in which one or more carboxyl groups are further added to an alicyclic monocarboxylic acid. Examples include monocyclic carboxylic acids such as cyclopropanedicarboxylic acid, cyclopropenedicarboxylic acid, cyclopropanetricarboxylic acid, cyclopropentricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutenedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutentricarboxylic acid, cyclobutanetetracarboxylic acid, cyclobutenetetracarboxylic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclopentanetricarboxylic acid, cyclopententricarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclopentenepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexenetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexenetetracarboxylic acid, cyclohexenepentacarboxylic acid, cyclohexanehexacarboxylic acid, cyclohexenehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptenedicarboxylic acid, cyclooctanedicarboxylic acid, and cyclooctenedicarboxylic acid, as well as polycyclic or bridged alicyclic dicarboxylic acids such as norbornanedicarboxylic acid and adamantanedicarboxylic acid.

[0179] (Aromatic compounds containing one or more carboxyl groups) Examples of the parent skeleton of aromatic compounds containing one or more carboxyl groups include benzoic acid, phenyleneacetic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, pentacarboxybenzene, hexacarboxybenzene, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, naphthalentetracarboxylic acid, anthracenecarboxylic acid, anthracenedicarboxylic acid, anthracenetricarboxylic acid, anthracenetetracarboxylic acid, and anthracenepentacarboxylic acid. Aromatic compounds may have substituents on the aromatic ring of these parent skeletons, such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups. Furthermore, if these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by the linkage of a carboxyalkyl group and a carboxyl group. These compounds may also be acid anhydrides formed by the linkage of two or more carboxyalkyl groups within the molecule. Refer to the above for details regarding these substituents.

[0180] (Heterocompounds containing one or more carboxyl groups) Examples of parent skeletons of heterocompounds containing one or more carboxyl groups include compounds containing one or more carboxyl groups in a heterocycle such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole. Heterocompounds may have substituents on these parent skeletons, such as alkyl groups, alkoxy groups, aryloxy groups, aryl groups, aminoalkyl groups, hydroxyl groups, amino groups, and carboxyalkyl groups. Furthermore, if these compounds have two or more carboxyl groups in the molecule, they may be acid anhydrides formed by the linkage of these groups. If these compounds have a carboxyalkyl group in the molecule, they may be acid anhydrides formed by the linkage of a carboxyalkyl group and a carboxyl group. These compounds may also be acid anhydrides formed by the linkage of two or more carboxyalkyl groups within the molecule. Refer to the above for details regarding these substituents.

[0181] The compound (F) is preferably the compound represented by formula (34), the compound represented by formula (35), the compound represented by formula (36), and the compound represented by formula (37) in order to impart excellent alkali developability to the resin composition, and is more preferably the compound represented by formula (36) in order to impart even better alkali developability to the resin composition.

[0182] The compound represented by formula (34) is as follows:

[0183]

[0184] In formula (34), R １８Each of these independently represents a hydroxyl group, a carboxyl group, an amino group, or an aminomethyl group. Furthermore, if the compound represented by formula (34) has two or more carboxyl groups, it may be an acid anhydride formed by the linkage of these groups. In formula (34), the upper limit of the number of carboxyl groups is 6. R １８ From the viewpoint of alkali developability, each is preferably independently a hydroxyl group, a carboxyl group, or an amino group, and it is more preferable to include a carboxyl group in order to obtain better alkali developability. Note that benzoic acid tends to have inferior alkali developability compared to compounds (F) that contain one or more other carboxyl groups. Also, each independently represents an integer from 0 to 5.

[0185] The compound represented by formula (34) is preferably the compound represented by formula (38) because it provides better alkali developability.

[0186]

[0187] In formula (38), R １８ Each of these independently represents a hydroxyl group, an amino group, or an aminomethyl group. １８ It is preferable that R is a hydroxyl group from the viewpoint of exhibiting superior alkali developability. Also, r' independently represents an integer from 0 to 4. It is preferable that r' is 0. The number of carboxyl groups s represents an integer from 1 to 5. It is preferable that the number of carboxyl groups s be an integer from 1 to 3 from the viewpoint of exhibiting superior alkali developability. In this case, R １８ The number r' is an integer less than or equal to 5-s. The compound represented by formula (38) may be an acid anhydride containing two or more carboxyl groups linked together.

[0188] Examples of compounds represented by formula (34) include 4-aminobenzoic acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid, 4-aminomethylbenzoic acid, and their anhydrides. Examples of these anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Phthalic acid, trimellitic acid, pyromellitic acid, and their anhydrides are preferred as compounds represented by formula (34) because they provide better alkali developability.

[0189] The compound represented by formula (35) is as follows:

[0190]

[0191] In formula (35), R １９ Each of these independently represents a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. Furthermore, if the compound represented by formula (35) has two or more carboxyl groups, it may be an acid anhydride formed by the linkage of these groups. In formula (35), the upper limit of the number of carboxyl groups is 10. If the compound represented by formula (35) has a carboxymethyl group, it may be an acid anhydride formed by the linkage of a carboxymethyl group and a carboxyl group. R １９ From the viewpoint of alkali developability, each of these is preferably a hydroxyl group, a carboxyl group, or an amino group, and it is more preferable to include a carboxyl group in order to obtain better alkali developability. Also, each of these independently represents an integer from 0 to 9. It is preferable that t is 0.

[0192] R １９ When a carboxyl group is present, from the viewpoint of alkali developability, the number of carboxyl groups p is preferably 1 to 3. １９ A hydroxyl group is preferred, and R other than a carboxyl group. １９ It is more preferable that there be no R other than the carboxyl group. When the compound represented by formula (35) contains 1 to 3 carboxyl groups, １９ The number is less than or equal to 10 - p.

[0193] Examples of compounds represented by formula (35) include piperidinecarboxylic acid, 1,2-piperidinedicarboxylic acid, and piperidinedicarboxylic acid anhydride.

[0194] The compound represented by formula (36) is as follows:

[0195]

[0196] In formula (36), R ２０ Each of these independently represents a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. Furthermore, if the compound represented by formula (36) has two or more carboxyl groups, it may be an acid anhydride formed by the linkage of these groups. In formula (36), the upper limit of the number of carboxyl groups is 10. If the compound represented by formula (36) has a carboxymethyl group, it may be an acid anhydride formed by the linkage of a carboxymethyl group and a carboxyl group. ２０ From the viewpoint of alkali developability, each of these is preferably a hydroxyl group, a carboxyl group, or an amino group, and it is more preferable to include a carboxyl group in order to obtain better alkali developability. Also, each of these independently represents an integer from 0 to 9.

[0197] The compound represented by formula (36) is preferably the compound represented by formula (39) because it provides better alkali developability.

[0198]

[0199] In formula (39), R ２１ Each of these independently represents a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. ２１ It is preferable that R is a hydroxyl group from the viewpoint of exhibiting superior alkali developability. Also, u' independently represents an integer from 0 to 8. It is preferable that u' is 0. The number of carboxyl groups v represents an integer from 1 to 9. It is preferable that the number of carboxyl groups v is an integer from 1 to 3 from the viewpoint of exhibiting superior alkali developability. In this case, R １９The number u' is an integer less than or equal to 9 - v. The compound represented by formula (39) may be an acid anhydride containing two or more carboxyl groups linked together. Furthermore, if the compound represented by formula (39) has a carboxymethyl group, the carboxymethyl group and the carboxyl group may be an acid anhydride formed by them linked together.

[0200] Examples of compounds represented by formula (36) include 3-cyclohexene-1-carboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride. As for the compound represented by formula (23), cis-4-cyclohexene-1,2-dicarboxylic acid and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride are preferred because they provide better alkali developability.

[0201] The compound represented by formula (37) is as follows:

[0202]

[0203] In formula (37), R ２２ Each of these independently represents a hydroxyl group, a carboxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. Furthermore, if the compound represented by formula (37) has one or more carboxyl groups, it may be an acid anhydride formed by the linkage of a carboxymethyl group and a carboxyl group. Also, if formula (37) has two or more carboxyl groups, it may be an acid anhydride formed by the linkage of those groups. In formula (37), the upper limit of the number of carboxyl groups is 5. In formula (37), if there are two or more carboxymethyl groups, it may be an acid anhydride formed by the linkage of those groups. In formula (37), the upper limit of the number of carboxymethyl groups is 6. R ２２ From the viewpoint of alkali developability, each of these is preferably a hydroxyl group, a carboxyl group, or an amino group, and it is more preferable to include a carboxyl group in order to obtain better alkali developability. Also, each of these independently represents an integer from 0 to 5.

[0204] The compound represented by formula (37) is preferably the compound represented by formula (40) because it provides better alkali developability.

[0205]

[0206] In formula (40), R ２３ Each of these independently represents a hydroxyl group, a carboxymethyl group, an amino group, or an aminomethyl group. ２３ It is preferable that the group is a hydroxyl group because it exhibits superior alkali developability. Also, each w' independently represents an integer from 0 to 4. It is preferable that w' is 0. The number of carboxyl groups x represents an integer from 1 to 5. It is preferable that the number of carboxyl groups x is an integer from 1 to 3 because it exhibits superior alkali developability. In this case, R ２３ The number w' is an integer less than or equal to 5 - x. In formula (40), the carboxymethyl group and the carboxyl group may be acid anhydrides formed by them being linked together. If the compound represented by formula (40) has two or more carboxyl groups, it may be an acid anhydride formed by them being linked together. In formula (40), the upper limit of the number of carboxyl groups is 5. If the compound represented by formula (40) has two or more carboxymethyl groups, it may be an acid anhydride formed by them being linked together. In formula (40), the upper limit of the number of carboxymethyl groups is 6.

[0207] Examples of compounds represented by formula (37) include phenyleneacetic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, and their anhydrides. An example of these anhydrides is 1,2-phenylenediacetic acid anhydride. As for the compound represented by formula (24), 1,2-phenylenediacetic acid is preferred because it provides better alkali developability.

[0208] Compounds (F) containing one or more of these carboxyl groups can be used individually or in appropriate mixtures of two or more.

[0209] In the resin composition, the content of compound (F) containing one or more carboxyl groups is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, based on 100 parts by mass of the total of bismaleimide compound (A) and maleimide compound (B), in order to improve compatibility with the bismaleimide compound (A) and maleimide compound (B) or polymer (E), reduce the amount of liquid components in the varnish, and provide better developability.

[0210] (Maleimide compounds other than bismaleimide compound (A) and maleimide compound (B)) The resin composition of this embodiment may contain maleimide compounds other than bismaleimide compound (A) and maleimide compound (B). The other maleimide compounds are not particularly limited as long as they are compounds other than bismaleimide compound (A) and maleimide compound (B) and have one or more maleimide groups in their molecule. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimoidhexanoic acid, 4-maleimoidbutyric acid, bis(4-maleimoidphenyl)methane, 2,2-bis{4-(4-maleimoidphenoxy)-phenyl}propane, 4,4-diph Phenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebismaleimide Phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1,5-bismaleimidepentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimidehexane, 1,6- Bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,Examples include 3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane, polyphenylmethanemaleimide, fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used individually or in appropriate mixtures of two or more.

[0211] In the aforementioned resin composition, the total content of other maleimide compounds is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0212] <Crosslinking agent (G)> The resin composition of this embodiment may contain a crosslinking agent (G) as needed. The crosslinking agent (G) is not particularly limited as long as it is a compound that can react with the bismaleimide compound (A) and the maleimide compound (B) or polymer (E). Examples of crosslinking agents (G) include cyanate ester compounds, phenol resins, epoxy resins, oxetane resins, benzoxazine compounds, carbodiimide compounds, and compounds having ethylenically unsaturated groups.

[0213] (Cyanate ester compounds) Cyanate ester compounds are obtained by reacting phenol resin with cyanide halide. Specific examples include, but are not limited to, dicyanatebenzene, tricyanatebenzene, dicyanatenaphthalene, dicyanatebiphenyl, 2,2'-bis(4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis(4-cyanatephenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene cocondensates in which the hydroxyl groups have been converted to cyanate groups. Furthermore, the cyanate ester compounds whose synthesis method is described in Japanese Patent Publication No. 2005-264154 are particularly preferred as cyanate ester compounds because they have excellent low hygroscopicity, flame retardancy, and dielectric properties. The cyanate ester compounds may also contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, and dibutyltin maleate in order to trimerize the cyanate group and form a sym-triazine ring as needed. The catalyst is usually 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 mass of the composition.

[0214] In the above composition, the total content of the cyanate ester compound is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0215] (Phenol Resins) As for phenol resins, any phenol resin having two or more hydroxyl groups in one molecule can be used, as long as it is generally known. Examples include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton-modified novolac type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, polymerizable unsaturated hydrocarbon group-containing phenol resin, and hydroxyl group-containing silicone resins, but are not particularly limited. These phenolic resins can be used individually or in appropriate mixtures of two or more types.

[0216] In the above composition, the total content of phenolic resin is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0217] (Epoxy resin) The epoxy resin is not particularly limited and generally known ones can be used. For example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglyceride Examples include diyl isocyanurates, 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, compounds in which double bonds of glycidylamine, butadiene, etc. are epoxidized, compounds obtained by the reaction of hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof. These epoxy resins can be used individually or in appropriate mixtures of two or more types.

[0218] In the above composition, the total content of epoxy resin is not particularly limited, but is preferably 0.01 to 50 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0219] (Oxetane Resin) Generally known oxetane resins can be used. Examples include oxetane, alkyl oxetanes such as 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-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd., trade name), and OXT-121 (manufactured by Toagosei Co., Ltd., trade name), and are not particularly limited. These oxetane resins can be used individually or in appropriate mixtures of two or more types.

[0220] In the above composition, the total content of oxetane resin is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0221] (Benzoxazine Compounds) As benzooxazine compounds, any compound having two or more dihydrobenzoxazine rings in one molecule can be used, and any generally known compound can be used. For example, bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein type benzoxazine, etc. are examples, but there are no particular limitations. These benzooxazine compounds can be used individually or in appropriate mixtures of two or more.

[0222] In the above composition, the total content of the benzoxazine compound is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0223] (Carbodiimide Compounds) Carbodiimide compounds are not particularly limited as long as they have at least one carbodiimide group in their 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, cycliccarbodiimide, Carbodilite (registered trademark: manufactured by Nisshinbo Chemical Co., Ltd.), and polycarbodiimides such as Stavaxol (registered trademark: manufactured by LANXESS Deutschland GmbH). These carbodiimide compounds can be used individually or in appropriate mixtures of two or more.

[0224] In the above composition, the total content of the carbodiimide compound is not particularly limited, but is preferably 0.01 to 40 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0225] (Compounds containing ethylenically unsaturated groups) Compounds containing ethylenically unsaturated groups are not particularly limited as long as they contain ethylenically unsaturated groups in one molecule. Specific examples of compounds 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, tricyclodecanedimethanol di(meth)acrylate, diethylenedi(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentanyl acrylate, tris(meth)acryloyloxyethyl isocyanurate, poly Examples include propylene glycol di(meth)acrylate, adipate 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 neopene 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 their ethylene oxide adducts; pentaerythritol tri(meth)acrylate and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and their ethylene oxide adducts.

[0226] In addition, other specific examples of compounds having ethylenically unsaturated groups include urethane (meth)acrylates that have both a (meth)acryloyl group and a urethane bond within the same molecule; polyester (meth)acrylates that have both a (meth)acryloyl group and an ester bond within the same molecule; epoxy (meth)acrylates derived from epoxy resins that also have a (meth)acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0227] Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates with polyisocyanates and other alcohols used as needed. For example, 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, and dipentaerythritol hexa ( Examples of urethane (meth)acrylates include those obtained by reacting sugar alcohols (meth)acrylates such as meth)acrylate with toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and polyisocyanates such as their isocyanurates and biuret reaction products.

[0228] Polyester (meth)acrylates include, for example, 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 hydroxypivalate ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalate 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.

[0229] Furthermore, 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; and 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; and mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols, or hexaols.

[0230] Furthermore, examples include (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, sebatic acid, azelaic acid, and 5-sodium sulfoisophthalic acid, and their anhydrides; and polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols consisting of diol components, polybasic acids, and their anhydrides with ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc.

[0231] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. Examples include phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadienephenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, and acid anhydride-modified epoxy (meth)acrylates thereof.

[0232] For example, 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, trimaallyl isocyanurate, and bisarylnadiimide are also specific examples of compounds having an ethylenically unsaturated group.

[0233] As compounds having an ethylenically unsaturated group, commercially available products can be used, for example, KAYARAD® ZXR-1801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), and propylene glycol monomethyl ether acetate of dicyclopentadiene type epoxy acrylate compounds (manufactured by Nippon Kayaku Co., Ltd., such as KAYARAD® ZXR-1806H (trade name), KAYARAD® ZXR-1810H (trade name), and KAYARAD® ZXR-1889H (trade name)). These compounds having an ethylenically unsaturated group can be used individually or in appropriate mixtures of two or more.

[0234] In the above composition, the total content of compounds having ethylenically unsaturated groups is not particularly limited, but is preferably 0.01 to 60 parts by mass per 100 parts by mass of resin solids in the composition of this embodiment.

[0235] The resin composition may also contain, in addition to the components (A) to (G) above, for example, fillers, mold release agents, flame retardants, ion trapping agents, antioxidants, adhesion promoters, stress reducers, colorants, and coupling agents, to the extent that they do not impair the effects of the present invention.

[0236] (Filler) The resin composition of this embodiment may further contain a filler in order to improve various properties such as coating properties and heat resistance. The filler is preferably an insulating material that does not hinder transmission to a wavelength of 405 nm (h-ray). The fillers are not particularly limited, but examples include inorganic fillers such as 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, fine powdered glass (e.g., E glass, T glass, D glass, etc.)), silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers can be used individually or in appropriate mixtures of two or more types.

[0237] Among these, it is preferable that one or more are selected from the group consisting of silica, boehmite, barium sulfate, silicone powder, fluororesin-based fillers, urethane resin-based fillers, (meth)acrylic resin-based fillers, polyethylene-based fillers, styrene-butadiene rubber, and silicone rubber. These fillers may be surface-treated with silane coupling agents or the like, as described later.

[0238] From the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition and obtaining good coating properties, silica is preferred, and fused silica is more preferred. Specific examples of silica include SFP-130MC from Denka Co., Ltd., and SC2050-MB, SC1050-MLE, YA010C-MFN, and YA050C-MJA from Admatex Co., Ltd.

[0239] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, and preferably 0.01 to 50 μm.

[0240] In the aforementioned 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 preferable to have 1,000 parts by mass or less, more preferably 500 parts by mass or less, and most preferably 300 parts by mass or less, per 100 parts by mass of resin solids in the resin composition. When a filler is included, the lower limit is not particularly limited, but from the viewpoint of obtaining the effect of improving various properties such as coating properties and heat resistance, it is usually 1 part by mass per 100 parts by mass of resin solids in the resin composition.

[0241] (Silane Coupling Agents and Wetting Dispersants) In addition to the resin composition, silane coupling agents and / or wetting dispersants may be used in combination to improve the dispersibility of the filler and the adhesion strength between the polymer and / or resin and the filler. These silane coupling agents are not particularly limited as long as they are silane coupling agents that are generally used for surface treatment of inorganic materials. Specific examples include, for example, 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, Aminosilanes such as N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, and [3-(N,N-dimethylamino)-propyl]trimethoxysilane; epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and [8-(glycidyloxy)-n-octyl]trimethoxysilane; Vinylsilanes such as nitris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trimethoxy(7-octen-1-yl)silane, and trimethoxy(4-vinylphenyl)silane; methacrylsilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, and 3-methacryloxypropyldiethoxymethylsilane; acrylicsilanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane;Isocyanate silanes such as 3-isocyanatetopropyltrimethoxysilane and 3-isocyanatetopropyltriethoxysilane; 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 Examples of silane coupling agents include: cationic silanes such as N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride; acid anhydrides such as [3-(trimethoxysilyl)propyl]succinic anhydride; phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, and p-tolyltrimethoxysilane; and arylsilanes such as trimethoxy(1-naphthyl)silane. These silane coupling agents can be used individually or in appropriate mixtures of two or more.

[0242] In the aforementioned resin composition, the content of the silane coupling agent is not particularly limited, but is usually 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 for paints. Specific examples include wetting and dispersing agents such as DISPERBYK®-110, 111, 118, 180, 161, BYK®-W996, W9010, and W903 manufactured by Big Chemie Japan Co., Ltd. These wetting and dispersing agents can be used individually or in appropriate mixtures of two or more. In the aforementioned resin composition, the content of the wetting and dispersing agent is not particularly limited, but is usually 0.1 to 10 parts by mass per 100 parts by mass of resin solids in the resin composition.

[0243] <Organic Solvent (H)> The resin composition may contain an organic solvent as needed. Using an organic solvent allows for adjustment of the viscosity during the preparation of the resin composition. The type of organic solvent is not particularly limited, as long as it is capable of dissolving part or all of the resin in the resin composition. Examples of such organic solvents include halogen 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.

[0244] Among these, cyclopentanone, propylene glycol monomethyl ether acetate, and dimethylacetamide are preferred because they exhibit excellent solubility with bismaleimide compounds (A) and maleimide compounds (B) or polymers (E), as well as with other resins and compounds such as photopolymerization initiators (C) and compounds containing one or more carboxyl groups (F), and crosslinking agents (G), making it easy to prepare varnishes with good solubility. These organic solvents can be used individually or in appropriate mixtures of two or more.

[0245] [Method for Producing Resin Composition] The resin composition is prepared by appropriately mixing a bismaleimide compound (A), a maleimide compound (B) or polymer (E), a photocuring initiator (C), and, if necessary, a curing accelerator (D), a compound containing one or more carboxyl groups (F), a crosslinking agent (G), a filler, other resins, other compounds, and additives. The resin composition can be suitably used as a varnish when producing the resin sheet of this embodiment, which will be described later. The organic solvent used in preparing the varnish is not particularly limited, and specific examples are as described above.

[0246] One method for producing the resin composition is to sequentially blend each of the aforementioned components into a solvent and stir thoroughly. The resin composition exhibits excellent photocurability, and the cured product obtained from the resin composition exhibits excellent heat resistance, thermal stability, and insulation reliability.

[0247] During the production of the resin composition, known treatments (stirring, mixing, kneading, etc.) 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 treatment using a stirring tank equipped with a stirrer having appropriate stirring capacity. Stirring, mixing, and kneading treatments can be appropriately performed using known devices such as stirring devices for dispersion, such as ultrasonic homogenizers, mixing devices such as three-roll mills, ball mills, bead mills, and sand mills, and orbital or rotational mixing devices. Furthermore, organic solvents can be used as needed during the preparation of the resin composition. 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.

[0248] The resin composition can be suitably used as a varnish when producing the resin sheet of this embodiment, which will be described later. The varnish can be obtained by known methods. 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 of the resin composition of this embodiment excluding the organic solvent, and then performing the known mixing treatment (stirring, kneading, etc.) described above.

[0249] [Applications] The resin composition can be preferably used in applications where a resin composition with high insulating reliability is required. For example, it can be used in photosensitive films, photosensitive films with supports, prepregs, resin sheets, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component embedding resins. Among these, the resin composition is particularly suitable for use as an insulating layer in multilayer printed wiring boards or as a solder resist due to its excellent photocurability, heat resistance, and thermal stability.

[0250] [Cured product] The cured product is obtained by curing the resin composition. For example, it can be obtained by melting or dissolving the resin composition in a solvent, pouring it into a mold, and curing it under normal conditions using light. The wavelength range of the light is preferably 100 to 500 nm, which allows for efficient curing by a photopolymerization initiator or the like.

[0251] [Resin Sheet] The resin sheet of this embodiment is a resin sheet with a support, comprising a support and a resin layer disposed on one or both sides of the support, wherein the resin layer contains a resin composition. The resin sheet can be manufactured by coating the resin composition onto the support and drying it. The resin layer in the resin sheet has excellent heat resistance, thermal stability and insulation reliability.

[0252] While known materials can be used as the support, a resin film is preferred. Examples of resin films include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetyl acetate film. Among these, PET film is preferred.

[0253] The resin film is preferably coated with a release agent on its surface to facilitate peeling from the resin layer. The thickness of the resin film is preferably in the range of 5 to 100 μm, and more preferably in the range of 10 to 50 μm. If the thickness is less than 5 μm, the support tends to tear easily when peeling it off before development, and if the thickness exceeds 100 μm, the resolution when exposing the support tends to decrease.

[0254] Furthermore, to reduce light scattering during exposure, the resin film should preferably have excellent transparency.

[0255] Furthermore, in the resin sheet, the resin layer may be protected by a protective film. Protecting the resin layer with a protective film prevents the adhesion of dust and other debris to the surface of the resin layer and prevents scratches. As the protective film, a film made of the same material as the resin film can be used. 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 handling of the protective film tends to decrease, and if it exceeds 50 μm, it tends to be less cost-effective. It is preferable that the adhesive strength between the resin layer and the protective film is less than the adhesive strength between the resin layer and the support.

[0256] The method for manufacturing the resin sheet can be, for example, a method of manufacturing a resin sheet by applying the resin composition of this embodiment to a support such as a PET film and removing the organic solvent by drying. The application method can be carried out by known methods using, for example, a roll coater, comma coater, gravure coater, die coater, bar coater, lip coater, knife coater, and squeeze coater. Drying can be carried out by, for example, heating in a dryer at 60 to 200°C for 1 to 60 minutes.

[0257] From the viewpoint of preventing the diffusion of organic solvent in subsequent processes, the amount of organic solvent remaining in the resin layer is preferably 5% by mass or less of the total mass of the resin layer. From the viewpoint of improving handling, the thickness of the resin layer is preferably 1 to 50 μm.

[0258] The resin sheet can be preferably used for manufacturing the insulating layer of a multilayer printed circuit board.

[0259] [Multilayer Printed Wiring Board] The multilayer printed wiring board of this embodiment has an insulating layer and a conductive layer formed on one or both sides of the insulating layer, and the insulating layer contains a resin composition. The insulating layer can also be obtained, for example, by stacking and curing one or more resin sheets. The number of layers of the insulating layer and the conductive layer is not particularly limited and can be set appropriately according to the intended application. The order of the insulating layer and the conductive layer is also not particularly limited. The conductive layer may be a metal foil used in various printed wiring board materials, for example, metal foils such as copper and aluminum. Examples of copper metal foils include rolled copper foil and electrolytic copper foil. The thickness of the conductive layer is usually 1 to 100 μm. Specifically, it can be manufactured by the following method.

[0260] (Laminating Process) In the laminating process, the resin layer side of the resin sheet is laminated to one or both sides of the circuit board using a vacuum laminator. Examples of circuit boards include glass epoxy substrates, metal substrates, ceramic substrates, silicon substrates, semiconductor encapsulating resin substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. A circuit board is defined as a substrate on which a patterned conductive layer (circuit) is formed on one or both sides of the substrate. In addition, a circuit board is also defined as a multilayer printed wiring board in which conductive layers and insulating layers are alternately laminated, and on which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductive 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 of the resin sheets of this embodiment, or it may be an insulating layer obtained by stacking one or more of the resin sheets of this embodiment and one or more of a known resin sheet different from the resin sheets of this embodiment. The method of layering the resin sheet of this embodiment with a known resin sheet different from the resin sheet of this embodiment is not particularly limited. The surface of the conductive layer may be pre-treated with a roughening treatment such as blackening and / or copper etching. In the lamination process, if the resin sheet has a protective film, after peeling off the protective film, the resin sheet and circuit board are preheated as necessary, and the resin layer of the resin sheet is pressed onto the circuit board while applying pressure and heating. In this embodiment, a method of laminating the resin layer of the resin sheet onto the circuit board under reduced pressure using a vacuum lamination method is preferably used.

[0261] The conditions for the lamination process include, for example, a bonding temperature (lamination temperature) of 50 to 140°C and a bonding pressure of 1 to 15 kgf / cm². ２ Preferably, lamination is performed under reduced pressure, with a pressing time of 5 to 300 seconds and an air pressure of 20 mmHg or less. The lamination process may be batch-type or continuous-type using rolls. Vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the 2-stage build-up laminator (product name) manufactured by Nikko Materials Co., Ltd.

[0262] (Exposure Process) In the exposure process, after a resin layer is formed on the circuit board by the lamination process, an active energy ray is irradiated as a light source to a predetermined portion of the resin layer, and the resin layer in the irradiated area is cured. Irradiation may be done through a mask pattern, or a direct writing method may be used for direct irradiation. Examples of active energy rays include ultraviolet light, visible light, electron beams, and X-rays. The wavelength of the active energy ray is, for example, in the range of 200 to 600 nm. When using ultraviolet light, the irradiation dose is generally 10 to 1000 mJ / cm². ２ Furthermore, when manufacturing printed circuit boards with high-density and high-resolution wiring patterns using the stepper exposure method, it is preferable to use active energy rays that include, for example, a wavelength of 365 nm (i-line). When using active energy rays that include a wavelength of 365 nm (i-line), the irradiation dose is approximately 10 to 10,000 mJ / cm². ２ Therefore, when manufacturing printed circuit boards with high-density and high-resolution wiring patterns using direct lithography, it is preferable to use active energy rays that include, for example, a wavelength of 405 nm (h-ray) as the active energy ray. When using active energy rays that include a wavelength of 405 nm (h-ray), the irradiation dose is approximately 10 to 10,000 mJ / cm². ２ There are two methods for exposure using a mask pattern: contact exposure, in which the mask pattern is in close contact with the multilayer printed circuit board, and non-contact exposure, in which the mask pattern is exposed using parallel light without contact. 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 the support has been removed.

[0263] (Development Process) In this embodiment, a development process may be included as needed. That is, if no support is present on the resin layer, after the exposure process, the un-photocured portion (unexposed portion) can be removed by wet development and then developed to form the insulating layer pattern. If a support is present on the resin layer, after the exposure process, the support can be removed, and then the un-photocured portion (unexposed portion) can be removed by wet development and then developed to form the insulating layer pattern.

[0264] In wet development, the developer is not particularly limited as long as it selectively dissolves the unexposed areas. For example, organic solvents such as cyclohexanone, cyclopentanone, and γ-butyrolactone; alkaline developers such as aqueous solutions of tetramethylammonium hydroxide, aqueous solution of sodium carbonate, aqueous solution of potassium carbonate, aqueous solution of sodium hydroxide, and aqueous solution of potassium hydroxide can be used. These developers can be used individually or in appropriate mixtures of two or more.

[0265] Furthermore, development can be carried out using known methods such as dipping, paddle work, spraying, oscillating immersion, brushing, and scraping. In pattern formation, these development methods may be used in combination as needed. In addition, using high-pressure spraying as a development method is preferable because it further improves resolution. When using the spraying method, the spray pressure is preferably 0.02 to 0.5 MPa.

[0266] (Post-baking process) After the exposure process or development process is completed, a post-baking process is performed to form an insulating layer (cured material). Examples of post-baking processes include ultraviolet irradiation using a high-pressure mercury lamp and heating using a clean oven, and these can be used in combination. When irradiating with ultraviolet light, the irradiation amount can be adjusted as needed, for example, 50 to 10,000 mJ / cm². ２Irradiation can be performed with a moderate irradiation dose. The heating conditions can be selected as needed, but preferably in the range of 150 to 300°C for 20 to 180 minutes, and more preferably in the range of 200 to 300°C for 30 to 60 minutes.

[0267] (Conductor layer formation process) After forming the 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. In the vapor deposition method (vacuum vapor deposition), for example, a metal film can be formed on the insulating layer by placing a multilayer printed circuit board in a vacuum chamber and heating and evaporating the metal. In the sputtering method, for example, a metal film can be formed on the insulating layer by placing a multilayer printed circuit 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 then hammering out the metal.

[0268] Next, a conductive layer is formed by electroless plating or electrolytic plating. Subsequent pattern formation methods include, for example, subtractive and semi-additive methods.

[0269] [Sealing Material] The sealing material of this embodiment includes the resin composition of this embodiment. The method for manufacturing the sealing material is not particularly limited and can be any method that is generally known. For example, the sealing material can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents commonly used in sealing material applications using a known mixer. The method for adding the maleimide compound, various additives, and solvent of this embodiment during mixing is not particularly limited and can be any method that is generally known.

[0270] [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, and chopped fibers. Furthermore, preforms (laminated woven base fabrics made of reinforcing fibers, or these sewn together with stitching threads, or fiber structures such as three-dimensional woven fabrics and braids) can also be applied as the form of the reinforcing fibers.

[0271] The manufacturing method for these fiber-reinforced composite materials is not particularly limited and can be any method that is generally known. Examples include liquid composite molding, resin film infusion, filament winding, hand layup, and pultrusion. Among these, resin transfer molding, a type of liquid composite molding, is preferable for mass production of relatively complex composite materials in a short time because it allows materials other than preforms, such as metal plates, foam cores, and honeycomb cores, to be pre-set in the mold, making it suitable for various applications.

[0272] [Adhesive] The adhesive of this embodiment includes the resin composition of this embodiment. The method for manufacturing the adhesive is not particularly limited and can be any method that is generally known. For example, the adhesive can be manufactured by mixing the resin composition of this embodiment with various known additives or solvents commonly used in adhesive applications using a known mixer. The method for adding the maleimide compound, various additives, and solvent of this embodiment during mixing is not particularly limited and can be any method that is generally known.

[0273] [Semiconductor Devices] The heat-resistant resin coating formed by the resin composition of this embodiment can be used in semiconductor devices, electronic components such as multilayer wiring boards, and organic EL display devices. Specifically, it is suitably used as a passivation film for semiconductors, a surface protective film for semiconductor devices, an interlayer insulating film, an insulating film for redistribution layers, an interlayer insulating film for multilayer wiring for high-density mounting, an interlayer insulating film for electronic components such as inductors and SAW filters, and an insulating film or flat layer for organic electroluminescent devices, but is not limited to these applications and can take various structures.

[0274] The compounds and compositions of this embodiment can also be used in the form of dry film resists. That is, the compounds and compositions of this embodiment can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then dried in a drying oven set at 45 to 140°C to remove a predetermined amount of solvent, and a cover film or the like can be laminated as needed 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. For the base film and cover film, for example, films such as polyester, polypropylene, polyethylene, TAC, and polyimide can be used. These films may be treated with a silicone-based release agent or a non-silicone-based release agent as needed. By supplying the resist as a dry film resist, the steps of application to a support and drying can be omitted, and the photosensitive resin composition of this embodiment can be used more simply.

[0275] The present invention will be described more specifically below based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" in the examples are based on mass. The compatibility, photocurability, crack resistance, heat resistance (glass transition temperature (Tg)), thermal stability (5% weight loss temperature (Td5)), and dielectric properties of each example and comparative example were evaluated as follows. The molecular weight measurement conditions are as follows: Instrument: 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

[0276] <Bismaleimide Compound (A)> Synthesis Example 1 (A-1) 504.3 g of toluene and 504.3 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 132.5 g (0.40 mol) of diamine H2O (manufactured by Okamura Oil Co., Ltd.) and 217.9 g (1.60 mol) of metaxylenediamine were added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for 10 minutes, and then 728.2 g (1.40 mol) of BISDA-1000 (4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, manufactured by SABIC) was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, yielding the amine-terminated diimide. The reaction mixture was cooled to below room temperature, and 141.2 g (1.44 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of water produced. After cooling to room temperature, toluene was added to a 500 ml flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. Subsequently, the varnish was reprecipitation by dropwise addition of 5,000 g of methanol, and after removing the solvent and drying, 1090 g of the desired white solid bismaleimide compound (yield 97%, Mw = 3,300) was obtained (A-1).

[0277] Synthesis Example 2 (A-2) 466.0 g of toluene and 466.0 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 66.2 g (0.20 mol) of diamine H2O and 284.9 g (1.80 mol) of norbornanediamine were added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for 10 minutes, and then 624.1 g (1.20 mol) of BISDA-1000 was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the amine-terminated diimide was obtained. The reaction mixture was cooled to below room temperature, and 188.3 g (1.92 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of product water. After cooling to room temperature, toluene was added to a 500 ml flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. The varnish was then reprecipitation by adding it dropwise to 5,000 g of methanol, and the solvent was removed and the mixture was dried to obtain 960 g of the desired white solid bismaleimide compound (yield 91%, Mw = 2,100) (A-2).

[0278] Synthesis Example 3 (A-3) 519.6 g of toluene and 519.6 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 99.3 g (0.30 mol) of diamine H2O and 262.2 g (1.70 mol) of trimethylhexamethylenediamine were added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for 10 minutes, and then 310.2 g (1.40 mol) of ODPA (4,4'-oxydiphthalic anhydride, manufactured by Manac Co., Ltd.) was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the amine-terminated diimide was obtained. The reaction mixture was cooled to below room temperature, and 141.2 g (1.44 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of product water. After cooling to room temperature, 500 ml of toluene was added to the flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. The varnish was then reprecipitation by adding it dropwise to 5,000 g of methanol, and the solvent was removed and the mixture was dried to obtain 810 g of the target white solid bismaleimide compound (yield 96%, Mw = 2,900) (A-2).

[0279] Synthesis Example 4 (A-4) 315.9 g of toluene and 315.9 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 99.3 g (0.30 mol) of diamine H2O (manufactured by Okamura Oil Co., Ltd.) and 231.5 g (1.70 mol) of metaxyldiamine were added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for 10 minutes, and then 358.7 g (1.60 mol) of H-PMDA (hydrogenated pyromellitic dianhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the amine-terminated diimide was obtained. The reaction mixture was cooled to below room temperature, and 94.1 g (0.96 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of product water. After cooling to room temperature, 500 ml of toluene was added to the flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. The varnish was then reprecipitation by adding it dropwise to 5,000 g of methanol, and the solvent was removed and the mixture was dried to obtain 660 g of the desired white solid bismaleimide compound (yield 95%, Mw = 4,300) (A-4).

[0280] Synthesis Example 5 (A-5) 504.7 g of toluene and 504.7 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 113.8 g (0.40 mol) of 1,18-octadecanediamine and 217.9 g (1.60 mol) of metaxylenediamine were added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes, and then 728.2 g (1.40 mol) of BISDA-1000 was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the amine-terminated diimide was obtained. The reaction mixture was cooled to below room temperature, and 141.2 g (1.44 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of product water. After cooling to room temperature, 500 ml of toluene was added to the flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. Subsequently, the varnish was reprecipitation by adding it dropwise to 5,000 g of methanol, and after removing the solvent and drying, 1030 g of the desired white solid bismaleimide compound (yield 93%, Mw = 3,300) was obtained (A-5).

[0281] <Comparative Bismaleimide Compound (A')> Synthesis Example 6 (Comparative Bismaleimide Compound (A'-1)) 475.1 g of toluene and 475.1 g of N-methylpyrrolidone were added to a 1 L round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer. Next, 272.4 g (2.00 mol) of metaxylenediamine was added, followed by the slow addition of 192.2 g (2.0 mol) of methanesulfonic acid to form a salt. The mixture was stirred for 10 minutes, and then 728.2 g (1.40 mol) of BISDA-1000 was slowly added to the stirred mixture. The mixture was refluxed at 140°C for 6 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the amine-terminated diimide was obtained. The reaction mixture was cooled to below room temperature, and 141.2 g (1.44 mol) of maleic anhydride was added. The mixture was further refluxed at 140°C for 8 hours to obtain the expected amount of product water. After cooling to room temperature, 500 ml of toluene was added to the flask, and the diluted organic layer was washed with water (500 ml x 5) to remove salts and unreacted starting materials to obtain a varnish of the bismaleimide compound. The varnish was then reprecipitation by adding it dropwise to 5,000 g of methanol, and the solvent was removed and the mixture was dried to obtain 940 g of the desired white solid bismaleimide compound (yield 90%, Mw = 2,700) (A'-1).

[0282] (A'-2) Bismaleimide (manufactured by DMI, trade name "BMI-689")

[0283] <Maleimide Compounds (B)> The following four compounds were prepared as maleimide compounds (B): (B-1) Maleimide compound manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000" (B-2) Maleimide compound manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-5000" (B-3) Maleimide compound manufactured by Kei-I Kasei, trade name "BMI-70"

[0284] <Photopolymerization Initiator (C)> Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (BASF Japan, "IRGACURE OXE-02")

[0285] <Curing Accelerator (D)> (D-1) Permil D (Dicumyl Peroxide (manufactured by Nippon Oil & Fats Co., Ltd.)) (D-2) 2-Ethyl-4-Methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

[0286] <Polymer (E)> Synthesis Example 7 (E-1) A 500 ml round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring device contained 5.40 g (0.015 mol) of DABPAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd.), 54.2 g (0.101 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 41.4 g (0.119 mol) of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation), and 171.58 g of anisole, and was heated to 70°C. Next, 65.00 g (0.210 mol) of ODPA, 2.00 g of triethylamine, and 25.77 g of toluene were added. The mixture was refluxed at 130°C for 8 hours to confirm that the theoretical amount of water produced from this condensation had been removed, and the reaction was carried out to obtain a polyimide resin solution. Subsequently, 9.80 g (0.063 mol) of 2-methacryloyloxyethyl isocyanate (Karens MOI, manufactured by Showa Denko K.K.) and 0.3 g of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and the mixture was reacted at 130°C for 4 hours. After that, the remaining triethylamine and toluene were removed at 130°C to obtain polymer (E-1) (Mw = 47,700).

[0287] Synthesis Example 8 (E-2) A 500 ml round-bottom flask equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet, and stirrer was placed in a flask containing 62.0 g of ODPA, 23.0 g of DABPAF, 5.40 g of 1,3-phenylenediamine, and 111 g of N-methylpyrrolidone. The mixture was stirred at 30°C for 8 hours to obtain a polyamic acid solution. 73.6 g of trifluoroacetic anhydride and 52.0 g of 2-hydroxyethyl methacrylate (HEMA) were added at room temperature, and the mixture was stirred at 60°C for 12 hours. Subsequently, the varnish was reprecipitation by dropwise adding it to 3,500 g of methanol, and the solvent was removed and the mixture dried to obtain a white solid polymer (E-2) (Mw = 32,500).

[0288] <Crosslinking agent (G)> Tricyclodecanedimethanol diacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD R-684")

[0289] (Examples 1-11 and Comparative Examples 1-4) The photosensitive resin compositions of Examples 1-11 and Comparative Examples 1-4 were prepared by blending components (A) to (C) in the amounts (parts by mass) shown in Tables 1 and 2, and 103 parts by mass of cyclopentanone as the organic solvent (H).

[0290] <Characteristic Evaluation> The following characteristics were measured for the prepared photosensitive resin composition and cured film. The results are shown in Tables 1 and 2.

[0291] [Compatibility] Visual compatibility refers to the state of the photosensitive resin composition after mixing components (A) to (C) and the organic solvent (H) and stirring, as observed visually. Good compatibility means that there are no precipitates, etc., and it is possible to apply it to a substrate, etc. Poor compatibility means that there are precipitates, etc., and it is difficult to apply it to a substrate, etc. (Evaluation criteria) ○: No precipitates ×: Precipitates etc. present

[0292] [Photopatterning Evaluation] The photosensitive resin compositions obtained in Examples 1-11 and Comparative Examples 1-4 were spin-coated onto silicon substrates and heated at 100°C for 2 minutes to form coatings with a thickness of 10-15 μm. Next, reduction projection exposure was performed using a USHIO "500W Multi-Light Ultra-High Pressure Mercury Lamp" with h-line (405 nm) light through a via (100 μm diameter) mask. The exposure dose was 2000 mJ / cm². ２ The following criteria were used. After exposure, the material was heated at 150°C for 15 minutes and developed using propylene glycol monomethyl ether glycol. Photocurability was determined by whether a pattern remained in the areas not covered by the mask after development. (Photocurability determination criteria (in the table: Photocurability)) ○: Pattern remains after development ×: Nothing remains after development Crack resistance was determined by observing the pattern under a microscope after development and determining whether cracks occurred on the pattern. (Crack resistance determination criteria (in the table: Crack resistance)) ○: No cracks ×: Cracks present Developability was also determined by observing the via areas under an optical microscope after development and determining whether there were residuals. (Developability determination criteria (in the table: Developability)) ○: No residuals ×: Residuals present The evaluation results for photocurability, crack resistance, and developability are shown in Tables 1 and 2.

[0293] [Glass Transition Temperature Evaluation (Tg in the table)] The photosensitive resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. This film-like photosensitive resin composition was exposed to an active energy ray including a wavelength of 405 nm (h-ray) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at an exposure dose of 3000 mJ / cm². ２The copper foil was removed by etching after exposure, and then heated at 250°C for 60 minutes under a nitrogen atmosphere to cure it, thereby obtaining a cured film. The dynamic viscoelasticity of the cured bismaleimide prepared as described above was measured using a dynamic viscoelasticity analyzer (DMA) (RSA-G2, T.A. Instruments, Inc.) (frequency 1 Hz, tensile mode, heating rate 5°C / min), and the glass transition temperature was determined by the maximum value of the loss tangent (tanδ). Furthermore, the tanδ peak waveform was examined from the viewpoint of compatibility, and the number of peaks was counted. The results are shown in Tables 1 and 2.

[0294] [Thermal Decomposition Resistance (Table: Td5)] The photosensitive resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. This film-like photosensitive resin composition was exposed to an active energy ray including a wavelength of 405 nm (h-ray) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at an exposure dose of 3000 mJ / cm². ２ The material was exposed to light, then heated at 250°C for 60 minutes under a nitrogen atmosphere to cure it, and finally the copper foil was removed by etching to obtain a cured film. The cured material was cut into 4 mm squares, and 1.0 to 5.0 mg was weighed into a measuring pan. The temperature at which the weight decreased by 5% (Td5) was measured by thermogravimetric analysis (TGA) under conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. The measuring apparatus used was a TGA / DSC1 (manufactured by METTLER TOLEDO).

[0295] [Dielectric Properties (Table: Dk, Df)] First, the photosensitive resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. This film-like photosensitive resin composition was exposed to an active energy ray including a wavelength of 405 nm (h-ray) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at an exposure dose of 3000 mJ / cm². ２ The resin film was exposed to light, then heated at 250°C for 60 minutes under a nitrogen atmosphere to cure it, and finally the copper foil was removed by etching to obtain a cured film. The cured resin film was cut to prepare 80 x 3 mm test pieces. The obtained test pieces were left in an environment of 25°C and 20% humidity for one day, and then the relative permittivity (Dk) and dielectric loss tangent (Df) at 10 GHz were measured using a cavity resonator dielectric constant measuring device. The measuring instrument used was an AET vector network analyzer ADMSO10c1, and the cavity resonator used was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Applied Development Co., Ltd. The results are shown in Tables 1 and 2.

[0296]

[0297] *1: Evaluation of cured film formation, evaluation, and photopatternability was not possible due to low compatibility with the solvent. *2: Evaluation was not possible because the photocurability was low and it was impossible to form a cured film.

[0298] As is clear from the results shown in Tables 1 and 2, the photosensitive resin composition of the present invention was shown to produce excellent cured products with good compatibility, photocurability, developability, and crack resistance, as well as low dielectric properties, a high glass transition temperature of 200°C or higher, and high thermal decomposition resistance of 380°C or higher.

[0299] (Examples 12-22 and Comparative Examples 5-8) <Preparation of thermosetting resin compositions, resin films and copper foil laminates> Thermosetting resin compositions for Examples 12-22 and Comparative Examples 5-8 were prepared by blending components (A) to (B) and (D) in the amounts (parts by mass) shown in Tables 3 and 4, and 103 parts by mass of cyclopentanone as the organic solvent (H). Using an applicator, the thermosetting resin composition was applied onto 12 μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (product name), manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) on a hot plate heated to 60°C, and a heat treatment was performed in an oven at 120°C for 30 minutes to produce a resin film in the B stage with a thickness of 100 μm. Subsequently, a 12 μm ultra-low roughness electrolytic copper foil (CF-T4X-SV (product name), manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) was further laminated onto the obtained B-stage resin film using a laminator, and the film was heated at 220°C for 2 hours to complete the heat curing process, thereby producing a copper foil laminate.

[0300] <Characteristic Evaluation> The following characteristics were measured for the prepared thermosetting resin composition, the resin film in the B-stage state, and the copper foil laminate. The results are shown in Tables 3 and 4.

[0301] [Compatibility] Visual compatibility refers to the state of the thermosetting resin composition after mixing components (A) to (B), (D), and (H) and stirring, as observed visually. Good compatibility means that there are no precipitates, etc., and it is possible to apply the mixture to a substrate, etc. Poor compatibility means that there are precipitates, etc., and it is difficult to apply the mixture to a substrate, etc. (Evaluation criteria) ○: No precipitates ×: Precipitates present

[0302] [Dielectric Properties (abbreviated as Dk, Df in the table)] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, a cured resin film was obtained. The cured resin film was cut to prepare 80 × 3 mm test pieces. The obtained test pieces were left in an environment of 25°C and 20% humidity for one day, and then the relative permittivity and dielectric loss tangent at 10 GHz were measured using a cavity resonator dielectric constant measuring device. The measuring instrument used was an AET vector type network analyzer ADMSO10c1, and the cavity resonator used was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Applied Development Co., Ltd. The results are shown in Table 3.

[0303] [Glass Transition Temperature Evaluation (Abbreviation in Table: Tg)] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, a cured resin film was obtained. The dynamic viscoelasticity of this resin film was measured using a dynamic viscoelasticity analyzer (DMA) (RSA-G2, T.A. Instruments, Inc.) (frequency 1 Hz, tensile mode, heating rate 5°C / min), and the glass transition temperature was determined by the maximum value of the loss tangent (tanδ). Furthermore, the tanδ peak waveform was examined from the viewpoint of compatibility, and the number of peaks was counted. The results are shown in Tables 3 and 4.

[0304] [Thermal Decomposition Resistance (abbreviated as Td5 in the table)] The copper foil on both sides of the copper foil laminate was removed by etching, and after drying at 130°C for 30 minutes, the cured resin film was cut into 4 mm squares, and 1.0 to 5.0 mg was weighed into a measuring pan. The temperature at which a 5% weight loss occurred was measured by thermogravimetric analysis (TGA) under conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. The measuring device used was TGA / DSC1 (manufactured by METTLER TOLEDO).

[0305] [Insulation Reliability Evaluation (abbreviated as HAST in the table)] A thermosetting resin composition was applied to an Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd.: base imide thickness 25 μm, Cu thickness 18 μm) with a comb-shaped pattern of L / S = 100 μm / 100 μm formed by screen printing to a thickness of 25 μm, and the coating film was dried in a hot air dryer at 120°C for 60 minutes. Next, Aflex (Grade: 25N NT) (manufactured by AGC Inc.) was placed over the resin surface and heated at 220°C for 2 hours to obtain a test substrate for HAST evaluation. The electrode portions of the obtained substrate were wired together by soldering, and the substrate was placed in an environment of 130°C and 85% RH, and a voltage of 100 V was applied. The resistance values ​​after 200 hours are shown in Tables 3 and 4.

[0306] [Copper Adhesion Evaluation (Abbreviation in Table: Adhesion)] A thermosetting resin composition was applied to a copper-clad laminate (ELC-4762 (product name), manufactured by Sumitomo Bakelite) to a thickness of 25 μm by screen printing, and the coating was dried in a hot air dryer at 120°C for 60 minutes. Next, Aflex (Grade: 25N NT) (manufactured by AGC Inc.) was placed over the resin surface and heated at 220°C for 2 hours to obtain a cured product on the copper-clad laminate. The degree of peeling of the cured film was evaluated using a grid peel test (JIS K 5400-8.5). (Evaluation Criteria) ○: 100 squares remaining △: 50 to 99 squares remaining ×: 0 to 49 squares remaining

[0307]

[0308] *3: The creation and evaluation of the cured film cannot be performed due to its low compatibility with the solvent.

[0309] As is clear from the results shown in Tables 3 and 4, the photosensitive resin composition of the present invention was shown to produce a cured product with good compatibility, low dielectric properties, a high glass transition temperature of 200°C or higher, high thermal decomposition resistance of 380°C or higher, and excellent adhesion to the substrate.

[0310] (Examples 23-30 and Comparative Examples 9-12) The photosensitive resin compositions of Examples 23-30 and Comparative Examples 9-12 were prepared by blending components (A), (C), (E), and (G) in the amounts (parts by mass) shown in Tables 5 and 6, and 103 parts by mass of cyclopentanone as the organic solvent (H).

[0311] <Characteristic Evaluation> The following characteristics were measured for the prepared photosensitive resin composition and cured film. The results are shown in Tables 1 and 2.

[0312] [Photo-patterning evaluation (in table: patternability)] The photosensitive resin compositions obtained in Examples 23-30 and Comparative Examples 9-12 were spin-coated onto silicon substrates and heated at 100°C for 2 minutes to form coatings with a thickness of 10-15 μm. Then, reduction projection exposure was performed using a USHIO "500W Multi-Light" ultra-high pressure mercury lamp with the h-line (405 nm) through a via pattern mask. The exposure dose was 2000 mJ / cm². ２The results were as follows: After exposure, the samples were heated at 150°C for 15 minutes and developed using propylene glycol monomethyl ether glycol. Photopatternability was determined by observing the via patterns after development under a microscope and checking whether resin residue remained in vias with a diameter of 100 μm. (Photopatternability determination criteria) ○: No residue ×: Residue present The results of the photopatternability are shown in Tables 1 and 2.

[0313] [Glass Transition Temperature Evaluation (Tg in the table)] The photosensitive resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. This film-like photosensitive resin composition was exposed to an active energy ray including a wavelength of 405 nm (h-ray) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at an exposure dose of 3000 mJ / cm². ２ The copper foil was removed by etching after exposure, and then heated at 250°C for 60 minutes under a nitrogen atmosphere to cure it, thereby obtaining a cured film. The dynamic viscoelasticity of the cured bismaleimide prepared as described above was measured using a dynamic viscoelasticity analyzer (DMA) (RSA-G2, T.A. Instruments, Inc.) (frequency 1 Hz, tensile mode, heating rate 5°C / min), and the glass transition temperature was determined by the maximum value of the loss tangent (tanδ). Furthermore, the tanδ peak waveform was examined from the viewpoint of compatibility, and the number of peaks was counted. The results are shown in Tables 1 and 2.

[0314] [Dielectric Properties (Table: Dk, Df)] First, the photosensitive resin compositions obtained in each example and comparative example were applied to 18 μm thick rolled copper foil (BHY-82F-HA-V2 (product name), manufactured by JX Metals Corporation) using an applicator, and then dried at 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film thickness of the dried film-like photosensitive resin composition was 20 μm. This film-like photosensitive resin composition was exposed to an active energy ray including a wavelength of 405 nm (h-ray) using a light source (USHIO Corporation's ultra-high pressure mercury lamp 500W Multi-Light (product name)) at an exposure dose of 3000 mJ / cm². ２ The resin film was exposed to light, then heated at 250°C for 60 minutes under a nitrogen atmosphere to cure it, and finally the copper foil was removed by etching to obtain a cured film. The cured resin film was cut to prepare 80 x 3 mm test pieces. The obtained test pieces were left for one day in an environment of 25°C and 20% humidity, and then the relative permittivity and dielectric loss tangent at 10 GHz were measured using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.). The measuring instrument used was an AET vector network analyzer ADMSO10c1, and the cavity resonator used was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Applied Development Co., Ltd. The results are shown in Tables 1 and 2.

[0315] [Insulation Reliability Evaluation (abbreviated as HAST in the table)] A photosensitive resin composition was applied to an Espanex M series (manufactured by Nippon Steel Chemical Co., Ltd.: base imide thickness 25 μm, Cu thickness 18 μm) with a comb-shaped pattern of L / S = 100 μm / 100 μm formed by screen printing to a thickness of 25 μm, and the coating film was dried in a hot air dryer at 120°C for 60 minutes. Next, Aflex (Grade: 25N NT) (manufactured by AGC Inc.) was placed over the resin surface and heated at 250°C for 1 hour to obtain a test substrate for HAST evaluation. The electrode portions of the obtained substrate were wired together by soldering, placed in an environment of 130°C and 85% RH, and the resistance values ​​after 200 hours under a voltage of 100 V are shown in Tables 1 and 2.

[0316] [Copper Adhesion Evaluation (Abbreviation in the table: Adhesion)] The photosensitive resin composition was applied to a copper-clad laminate (ELC-4762 (trade name), manufactured by Sumitomo Bakelite) to a thickness of 25 μm by the screen printing method, and the coating film was dried in a hot air dryer at 120 °C for 60 minutes. Next, an aflex (Grade: 25N NT) (manufactured by AGC Inc.) was placed on the resin surface and heated at 250 °C for 1 hour to obtain a cured product on the copper-clad laminate. The peeling condition of the film after curing was evaluated by the cross-cut peeling test (JIS K 5400-8.5). (Evaluation Criteria) ○: The number of remaining squares is 100. △: The number of remaining squares is 50-99. ×: The number of remaining squares is 0-49.

[0317]

[0318]

[0319] As is clear from the results shown in Tables 5 and 6, it was shown that by using the resin composition of the present invention, an excellent cured product having patterning properties, a high glass transition temperature, low dielectric properties, good insulation reliability, and excellent adhesion can be obtained.

Claims

1. A resin composition comprising a bismaleimide compound (A) containing a structural unit represented by the following (1) and at least one maleimide compound (B) selected from the group consisting of compounds represented by the following formulas (2) to (8). A in the general formula (1) １ represents a tetravalent organic group containing a cyclic structure. B １ is a divalent hydrocarbon group having no cyclic structure and having 13 to 200 carbon atoms. When there are a plurality of structural units of the general formula (1) in the bismaleimide compound, the plurality of A １ are each independent and may be the same or different, and the plurality of B １ are also each independent and may be the same or different. In formula (2), R １ , R ２ , and R ３ each independently represent a hydrogen atom, a hydroxy group, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. n represents an integer of 1 to 10. In formula (3), R ４ each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 to 10. In formula (4), R ５ , R ６ , and R ７ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent. In formula (5), R ８ each independently represents a hydrogen atom, a methyl group, or an ethyl group, and R ９ each independently represents a hydrogen atom or a methyl group. In formula (6), R １０ each independently represents a hydrogen atom, a methyl group, or an ethyl group. In formula (7), R １１ each independently represents a hydrogen atom or a methyl group. n represents an integer of 1 to 10. In formula (8), the plurality of R １２ each independently represent an alkyl group having 1 to 5 carbon atoms. m represents an integer of 0 to 3. n is the number of repetitions, and its average value n ａｖｅ is 1 < n ａｖｅ < 5 2. A resin composition comprising a bismaleimide compound (A) containing the structural unit represented by (1) below, and at least one polymer (E) containing the structural unit represented by formula (12) and / or (13) below. A in general formula (1) １ This represents a tetravalent organic group containing a cyclic structure. B １ A is a divalent hydrocarbon group having 13 to 200 carbon atoms and not having a cyclic structure. When multiple constituent units of general formula (1) are present in a bismaleimide compound, multiple A １ Each of them is independent, and they may be the same or different, and there may be multiple B １ Each of them is independent and can be the same or different. In formula (12), A ２ This indicates a tetravalent organic group, B ２ R indicates a divalent organic group. １３ and R １４ Each of these independently represents a hydrogen atom or a monovalent organic group. There may be multiple structural units represented by formula (12), and A in multiple structural units ２ , B ３、 R １３ and R １４ These may be the same or different. １３ and R １４ The combination of each element is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. In formula (13), A ２ is a tetravalent organic group, B ２ represents a divalent organic group. Furthermore, it may have multiple structural units represented by formula (13), and A in multiple structural units ２ and B ２ These may be the same or different.

3. The resin composition according to claim 1 or 2, wherein the bismaleimide compound (A) further comprises a constituent unit represented by the following formula (9), and has a dielectric loss tangent of 0.010 or less and a weight-average molecular weight of 1,000 to 75,000 when cured. A in equation (9) ３ This independently represents a tetravalent organic group containing a cyclic structure. B ３ It has a cyclic structure and represents hydrocarbon groups other than the divalent hydrocarbon group derived from the dimer acid. When multiple constituent units of general formula (9) are present in a bismaleimide compound, multiple A ３ Each of them is independent, and they may be the same or different, and there may be multiple B ３ Each of these units is independent and may be identical or different. Furthermore, the order of each repeating unit is not restricted, and the combination can be alternating, block-based, or random.

4. A in the general formula (1) １ Or A in the general formula (9) above ３ The resin composition according to claim 3, wherein the organic group constituting the is selected from the group consisting of the following structural formulas. In the above structural formula, the bond marked with * is the A １ Or A ３ This shows the locations where the organic group and imide group that make up the compound are bonded.

5. In the above general formula (1), B １ The hydrocarbon group constituting is an alkylene group or alkenylene group having 14 to 30 carbon atoms, and is either linear or has a branched chain of one or more C1 to C4 alkyl groups and / or alkenyl groups, and in the general formula (9) B ３ The resin composition according to claim 3 or 4, comprising a bismaleimide compound (A) in which the hydrocarbon group constituting the is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure.

6. In the general formula (1) above, B １ The hydrocarbon group constituting the hydrocarbon group is a hydrocarbon group having 2n carbon atoms (where n is an integer between 6 and 14) of alkylene or alkenylene groups in the main chain portion, and is a hydrocarbon group having a branched chain composed of an ethyl group or a methyl group, in the general formula (9) above, B ３ The resin composition according to claim 3 or 4, comprising a bismaleimide compound (A) in which the hydrocarbon group constituting the is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure.

7. In the above general formula (1), B １ The hydrocarbon group constituting is a hydrocarbon group obtained by removing the amine group from 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, or 8,13-dimethyloctadecanediamine-8,12-ene, and in the general formula (9) above, B ３ The resin composition according to claim 3 or 4, comprising a bismaleimide compound (A) in which the hydrocarbon group constituting the is a divalent hydrocarbon group having an aromatic ring structure or an aliphatic ring structure.

8. The above B ３ The resin composition according to claim 3 or 4, wherein the hydrocarbon group constituting the is a hydrocarbon group having an aromatic ring structure represented by the following formula (10), or a hydrocarbon group having an aliphatic ring structure selected from the group represented by the following formula (11). R １５ Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. l represents an integer from 0 to 4. Bonds marked with an asterisk (*) in the structural formula represent bonding. R １６ Each of these independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. p represents an integer from 0 to 10, p' represents an integer from 0 to 14, and p'' represents an integer from 0 to 7. Bonds marked with an asterisk (*) in the structural formula represent bonding.

9. The resin composition according to any one of claims 1 to 8, further comprising a photopolymerization initiator (C).

10. The resin composition according to any one of claims 1 to 8, further comprising a thermosetting initiator.

11. The resin composition according to any one of claims 1 to 8, further comprising a curing accelerator (D).

12. The resin composition according to claim 11, wherein the curing accelerator (D) comprises at least one selected from a thermal radical polymerization initiator and an imidazole compound.

13. The resin composition according to any one of claims 1 to 12, further comprising a crosslinking agent (G).

14. A cured product comprising the resin composition according to any one of claims 1 to 13.

15. A semiconductor element comprising a surface protective film, an interlayer insulating film, or an insulating film of a redistribution layer containing the resin composition according to any one of claims 1 to 14.

16. A dry film resist comprising a resin composition according to any one of claims 1 to 13, and a substrate sandwiching the resin composition.

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