Thermosetting maleimide resin composition, and sheet-like or film-like composition, adhesive composition, primer composition, substrate composition, coating material composition, and semiconductor device using same

Abstract

The purpose of the present invention is to provide a thermosetting maleimide resin composition which has a cured product that has a high glass transition temperature (Tg), excellent dielectric properties, excellent adhesion to a metal foil, and good intermiscibility, and which is uniformly hardened without causing uneven hardening during hardening. A thermosetting maleimide resin composition containing (I) a bismaleimide compound and (II) a reaction accelerator, wherein the bismaleimide compound (I) is obtained by reacting an aromatic diamine (A) represented by formula (1), a tetrabasic acid dianhydride (C), and maleic anhydride, and has a cyclic imide bond. In formula (1), R1 each independently represents a hydrogen atom, 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. And l each independently represents an integer of 1 to 4.

Description

Technical Field

[0001] The present invention relates to thermosetting maleimide resin compositions and sheet or film compositions, adhesive compositions, primer compositions, substrate compositions, coating material compositions and semiconductor devices using the same. Background Technology

[0002] In recent years, the miniaturization and high performance of electronic devices have progressed rapidly. This has led to demands for finer and higher-density wiring in the surface protective films or interlayer insulating films of semiconductor components, as well as in the insulating films of rewiring layers. In addition, the use of high-frequency band materials in next-generation communication technologies necessitates the reduction of transmission loss as a noise countermeasure, thus requiring the development of insulating materials with excellent dielectric properties.

[0003] As an insulating material for multilayer printed circuit boards, epoxy resin compositions containing epoxy resin, specific phenolic curing agents, phenoxy resins, rubber particles, and polyvinyl acetal resins, as disclosed in Patent Documents 1 or 2, are known. However, it is understood that these materials cannot meet the requirements for high-frequency band applications, such as those represented by 5G. In contrast, Patent Document 3 proposes an epoxy resin composition containing epoxy resin, an active ester compound, and a cresol-phenolic resin containing triazine, which is effective in achieving low dielectric tangent. However, for high-frequency band applications, this material requires further low dielectric tangent reduction.

[0004] On the other hand, Patent Document 4 proposes a resin film composed of a resin composition containing a bismaleimide resin with long-chain alkyl groups as a non-epoxy material and a curing agent, which has excellent low dielectric properties. However, it is essentially a combination of a bismaleimide resin with long-chain alkyl groups and a hard, low-molecular-weight aromatic maleimide. It has poor compatibility and is prone to producing uneven properties or curing. Furthermore, it is extremely difficult to achieve the high glass transition temperature (Tg) of 100°C or higher required for substrate applications.

[0005] Furthermore, recent studies have revealed that the design of bismaleimide resins with long-chain alkyl groups presents a trade-off: achieving high Tg results in deteriorated dielectric properties, while improving dielectric properties leads to low Tg. Moreover, when aiming for high Tg, even bismaleimide resins with the same long-chain alkyl groups exhibit resin aggregation or separation, and their compatibility deteriorates.

[0006] Furthermore, Patent Documents 5 and 6 disclose resin compositions containing polyimide, which is derived from aromatic tetracarboxylic anhydride and dimer diamines or alicyclic diamines derived from dimers of unsaturated fatty acids such as oleic acid. However, the polyimide described in either document is difficult to use under single curing conditions and has poor compatibility with other resins. In addition, the polyimide undergoes ring-closure dehydration during curing, so when the resin composition containing this polyimide is laminated onto a metal foil, for example, expansion is easily caused due to the different conditions, which is not preferable.

[0007] Against this backdrop, as disclosed in Patent Documents 7 and 8, polyphenylene ether resins (PPEs) that can be thermosetting by modifying the functional groups at the ends of the molecular chains have become the main resins used in 5G substrates in recent years. The cured modified PPE has a high Tg of over 200°C and excellent reliability.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent document 1: Japanese Patent Application Publication No. 2007-254709.

[0011] Patent Document 2: Japanese Patent Application Publication No. 2007-254710.

[0012] Patent document 3: Japanese Patent Application Publication No. 2011-132507.

[0013] Patent document 4: International Publication No. 2016 / 114287.

[0014] Patent document 5: Japanese Patent Application Publication No. 2017-119361.

[0015] Patent document 6: Japanese Patent Application Publication No. 2019-104843.

[0016] Patent document 7: Japanese Patent Application Publication No. 2017-128718.

[0017] Patent document 8: Japanese Patent Application Publication No. 2018-95815. Summary of the Invention

[0018] [The problem that the invention aims to solve]

[0019] In 5G applications, from the perspective of surface effects, transmission loss is high when using metal foils with rough surfaces, so it is preferable to use metal foils with low surface roughness. However, anchoring effect cannot be obtained when using metal foils with low surface roughness, so a resin with higher adhesion to metal foil is desired. The modified PPE described in Patent Documents 7 and 8 presents a challenge in terms of adhesion to metal foil.

[0020] Therefore, the object of the present invention is to provide a thermosetting maleimide resin composition with a high glass transition temperature (Tg) of the cured material, excellent dielectric properties, excellent adhesion to metal foil, good compatibility with other resins, and uniform curing without uneven curing during curing. Furthermore, this object is to provide an adhesive, substrate material, primer, coating material, and semiconductor device using this thermosetting maleimide resin composition.

[0021] Therefore, the object of the present invention is to provide a thermosetting maleimide resin composition that has good compatibility with other resins and can achieve high Tg.

[0022] [Technical means used to solve the problem]

[0023] The inventors conducted careful research to solve the above-mentioned problems and found that the following thermosetting maleimide resin composition can achieve the above-mentioned objectives, thus completing the present invention.

[0024] That is, the present invention relates to the following <1> to <18>.

[0025] <1>

[0026] A thermosetting maleimide resin composition is a thermosetting maleimide resin composition containing (I) a bismaleimide compound and (II) a reaction accelerator.

[0027] The aforementioned (I) bismaleimide compound is a bismaleimide compound with cyclic imide bonds obtained by reacting an aromatic diamine (A) represented by the following formula (1) with a tetrabasic acid dianhydride (C) and maleic anhydride.

[0028]

[0029] In formula (1), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4.

[0030] <2>

[0031] The thermosetting maleimide resin composition as described in <1> further comprises: (III) a thermosetting resin having at least one group selected from epoxy, maleimide, hydroxyl, acid anhydride, alkenyl, (meth)acrylic acid, thiol, cyano, phenolic, oxetane, benzoxazine, and carbodiimide as a reactive group capable of reacting with the maleimide group.

[0032] <3>

[0033] The thermosetting maleimide resin composition as described in <1> or <2>, wherein the aforementioned (I) bismaleimide compound is obtained by reacting a divalent organic diamine (B) with 6 to 200 carbon atoms other than the aforementioned aromatic diamine (A), the aforementioned tetrabasic acid dianhydride (C), and the aforementioned maleic anhydride.

[0034] <4>

[0035] The thermosetting maleimide resin composition as described in any one of <1> to <3>, wherein the aforementioned (I) bismaleimide compound is represented by the following general formula (2).

[0036]

[0037] In equation (2), m is 1 to 100, and n is 0 to 100. Furthermore, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block, or random. C independently represents a tetravalent organogroup containing a cyclic structure; W is A or B. B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms. A independently represents a divalent organogroup represented by the following equation (3).

[0038]

[0039] In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4. * indicates a bonding portion with other parts.

[0040] <5>

[0041] The thermosetting maleimide resin composition as described in any one of <1> to <4>, wherein the aforementioned tetrabasic dianhydride (C) is selected from the group consisting of compounds represented by the following formulas (4) to (12).

[0042]

[0043] In equation (7), Y represents C(CF3)2, SO2, CO, oxygen atom, direct bond, or divalent bond group as represented by equation (13) below.

[0044]

[0045] In equation (13), * represents the bonding part with other parts.

[0046] <6>

[0047] The thermosetting maleimide resin composition as described in any one of <1> to <5>, wherein the aforementioned (I) bismaleimide compound is a maleimide derivative of an amine compound represented by the following formula (14).

[0048]

[0049] In equation (14), m is 1 to 100, and n is 0 to 100. Furthermore, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block, or random. C independently represents a tetravalent organogroup containing a cyclic structure. W is A or B. B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms. A independently represents a divalent organogroup represented by the following equation (3).

[0050]

[0051] In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4. * indicates a bonding portion with other parts.

[0052] <7>

[0053] The thermosetting maleimide resin composition as described in any one of <1> to <6> contains: the aforementioned bismaleimide compound (I) in which the aforementioned tetrabasic dianhydride (C) is a compound of the following formula (15).

[0054]

[0055] <8>

[0056] The thermosetting maleimide resin composition as described in any one of <1> to <6> contains: (I) a bismaleimide compound in which the aforementioned tetrabasic dianhydride (C) is a compound of the following formula (8).

[0057]

[0058] <9>

[0059] The thermosetting maleimide resin composition as described in any one of <1> to <6> contains: (I) a bismaleimide compound in which the aforementioned tetrabasic dianhydride (C) is a compound of the following formula (5).

[0060]

[0061] <10>

[0062] The thermosetting maleimide resin composition as described in any one of <1> to <6> contains: (I) a bismaleimide compound in which the aforementioned tetrabasic dianhydride (C) is a compound of the following formula (9).

[0063]

[0064] <11>

[0065] The thermosetting maleimide resin composition as described in any one of <1> to <6> contains: (I) a bismaleimide compound in which the aforementioned tetrabasic dianhydride (C) is a compound of the following formula (10).

[0066]

[0067] <12>

[0068] The thermosetting maleimide resin composition as described in any one of <2> to <11>, wherein the aforementioned (III) is a thermosetting resin having at least one group selected from epoxy, maleimide, hydroxyl, acid anhydride, alkenyl, (meth)acrylic acid and thiol, cyano, phenolic, oxo, benzoxazine, carbodiimide as a reactive group capable of reacting with the maleimide group, and is one or more of the group consisting of maleimide compounds other than the aforementioned bismaleimide compound (I), cyanate ester compounds, phenolic resins, epoxy resins, oxo resins, benzoxazine compounds, carbodiimide compounds and compounds having vinyl unsaturated groups.

[0069] <13> A sheet or film composition comprising a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0070] <14>

[0071] An adhesive composition comprising a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0072] <15>

[0073] A primer composition comprising a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0074] <16>

[0075] A substrate composition comprising a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0076] <17>

[0077] A coating composition comprising a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0078] <18>

[0079] A semiconductor device is a cured product having a thermosetting maleimide resin composition as described in any one of <1> to <12>.

[0080] [The effects of the invention]

[0081] The thermosetting maleimide resin composition of the present invention exhibits a high glass transition temperature, excellent dielectric properties, and excellent adhesion to metal foils. Furthermore, the maleimide compounds contained in the thermosetting maleimide resin composition of the present invention demonstrate excellent compatibility. In particular, it exhibits excellent compatibility with other resins with dissimilar structures, making it easy to blend with other resins and readily complement each other's properties to achieve better performance. Additionally, the thermosetting maleimide resin composition of the present invention exhibits uniform curing without uneven curing, especially when molded into sheets, films, or substrates, with minimal changes in curability or physical properties.

[0082] Therefore, the thermosetting maleimide resin composition of the present invention is suitable for use in adhesives, substrate materials, primers, coatings and semiconductor devices. Detailed Implementation

[0083] The present invention is a thermosetting maleimide resin composition containing (I) a bismaleimide compound and (II) a reaction promoter.

[0084] The following is a detailed description of the present invention.

[0085] <(I) Bismaleimide compounds>

[0086] (I) The bismaleimide compound (hereinafter also referred to as component (I)) is a compound having two maleimide groups, and the anhydride is an aromatic diamine that forms a cyclic imide bond. This (I) bismaleimide compound can be obtained by reacting an aromatic diamine (A) represented by the following formula (1) with a tetrabasic acid dianhydride (C) and a maleic anhydride.

[0087]

[0088] In formula (1), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4.

[0089] In addition to the aforementioned diamine (A), the aforementioned tetracarboxylic acid dianhydride (C), and the aforementioned maleic anhydride, an imide bond can be formed by reacting a divalent organic diamine (B) with 6 to 200 carbon atoms other than the aforementioned aromatic diamine (A), thereby introducing a divalent hydrocarbon group with 6 to 200 carbon atoms into the bismaleimide compound.

[0090] The aforementioned (I) bismaleimide compound is represented by the following general formula (2).

[0091]

[0092] In equation (2), m is 1 to 100, and n is 0 to 100. Furthermore, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block, or random. C independently represents a tetravalent organogroup containing a cyclic structure. W is A or B. B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms. A independently represents a divalent organogroup represented by the following equation (3).

[0093]

[0094] In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4. * indicates a bonding portion with other parts.

[0095] In the aforementioned formula (1), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms.

[0096] The alkyl group having 1 to 6 carbon atoms, whether linear or branched, is not particularly limited, but examples include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, especially methyl, ethyl, n-propyl, and isopropyl, due to their excellent adhesion to chips and substrates, as well as their relatively good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins.

[0097] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0098] The linear or branched alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, and tert-butoxy. Among these, alkoxy groups having 1 to 4 carbon atoms are preferred, especially methoxy, ethoxy, n-propoxy, and isopropoxy, due to their excellent adhesion to chips and substrates, as well as their relatively good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins.

[0099] In addition to its excellent adhesion to chips and substrates, R1 also exhibits good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins. Therefore, R1 is preferably composed of hydrogen atoms, methyl, ethyl, hydroxyl, methoxy, and ethoxy, especially hydrogen atoms, methyl, and hydroxyl, and more preferably hydrogen atoms.

[0100] In the aforementioned formula (1), l independently represents an integer from 1 to 4. In addition to excellent adhesion to chips and substrates, it exhibits good solubility in solvents, low melting point, low water absorption and good compatibility with other resins. Since R1 is preferably composed entirely of hydrogen atoms, l is preferably 4.

[0101] Specific examples of the aromatic diamine (A) represented by formula (1) include m-xylene diamine (formula (17) below), p-xylene diamine (formula (18) below), and o-xylene diamine (formula (19) below). M-xylene diamine (MXDA: manufactured by Mitsubishi Gas Chemical Co., Ltd.) is readily available commercially. The aromatic diamine (A) represented by formula (1) above is preferably m-xylene diamine (formula (17) below).

[0102]

[0103] (I) The bismaleimide compound is not particularly limited as long as it achieves the effects of the present invention. From the perspective of good solubility in solvents, low melting point, low water absorption, and good compatibility with other resins, the weight-average molecular weight is preferably 100 to 100,000, and more preferably 500 to 30,000. In this embodiment, "weight-average molecular weight" refers to the weight-average molecular weight converted from polystyrene standard by gel permeation chromatography (GPC).

[0104] Typically, due to the poor light transmittance of maleimide compounds, when a resin composition contains maleimide compounds other than (I) bismaleimide compounds, light does not sufficiently reach the photocuring initiator dispersed in the resin composition, making it difficult for the photocuring initiator to generate free radicals. Therefore, the photoradical reaction of maleimide compounds is generally difficult to carry out, and even if the free radical polymerization or dimerization reaction of maleimide monomers occurs, the reactivity of the photoradical reaction of maleimide compounds is extremely low. However, in the maleimide compound of this embodiment, the maleimide group is bonded to the aromatic ring through a methylene group, resulting in a shorter conjugation length, and for this reason, the light transmittance becomes extremely excellent. Therefore, light sufficiently reaches the photocuring initiator, efficiently inducing the photoradical reaction of maleimide. When a maleimide compound is prepared as a chloroform solution containing 1% by mass, and the light transmittance of this chloroform solution is measured using light with a wavelength of 405 nm (h-rays), the transmittance exhibits extremely excellent light transmittance of 3% or more. Therefore, for example, when using the direct-draw exposure method to manufacture printed wiring boards with high-density and high-fineness wiring formation (patterns), even when using active energy lines containing wavelengths of 405 nm (h-rays), photoradical reactions of maleimide are efficiently induced.

[0105] When using an active energy line containing a wavelength of 405 nm (h-rays), polymerization cannot proceed if the photocuring initiator does not absorb light at the wavelength of 405 nm (h-rays) and generate free radicals. Therefore, in this case, the photocuring initiator described below is preferably a photocuring initiator with an absorbance of 0.1 or higher at the wavelength of 405 nm (h-rays) and exhibits extremely excellent absorption at this wavelength.

[0106] As mentioned above, due to the excellent light transmittance of the maleimide compound in this embodiment, even when using light with a wavelength of, for example, 405 nm, the light sufficiently reaches the photocuring initiator, and the free radical reaction of the free radicals generated by the photocuring initiator is carried out. Photocuring can also be performed in a resin composition in which a large amount of maleimide compound is incorporated.

[0107] Furthermore, the cured product obtained from the resin composition of this embodiment has excellent light curing properties, heat resistance and thermal stability, and is therefore suitable for forming protective films and insulating layers.

[0108] Furthermore, in the aforementioned formula (2), B is independently a divalent hydrocarbon group with 6 to 200 carbon atoms, more preferably 8 to 100, and even more preferably 10 to 50. Among these, one or more hydrogen atoms in the aforementioned divalent hydrocarbon group are preferably branched divalent hydrocarbon groups substituted with alkyl or alkenyl groups with 6 to 200 carbon atoms, more preferably 8 to 100, and even more preferably 10 to 50 carbon atoms. The branched divalent hydrocarbon group can be any of a saturated aliphatic hydrocarbon group or an unsaturated hydrocarbon group, and may also have an alicyclic structure or an aromatic ring structure in the middle of the molecular chain. Specifically, the aforementioned branched divalent hydrocarbon group can be exemplified by hydrocarbon groups from two-terminal diamines called dimer diamines. The so-called dimer diamine, as shown in the following formulas (20) to (25), is a dimer acid having two carboxyl groups replaced with primary amino groups in a dimer of an unsaturated fatty acid such as oleic acid (see Japanese Patent Application Publication No. 9-12712, etc.). Examples of commercially available dimerized diamines include: PRIAMINE (registered trademark) 1074 and PRIAMINE (registered trademark) 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These can be used individually or in mixtures of two or more. The following are non-limiting general formulas representing dimerized diamines. In these formulas, m+n = 6 to 17, and p+q = 8 to 19, where the dashed lines indicate carbon-carbon single or double bonds.

[0109]

[0110] Furthermore, the tetracarboxylic dianhydride (C) used in the synthesis of the aforementioned (I) bismaleimide compounds is not particularly limited as long as it has two anhydride groups in one molecule. Specific examples of components (C) include: pyromellitic dianhydride, ethylene glycol-bis(anhydrotrimellitate), glycerol-bis(anhydrotrimellitate) monoacetate, 1,2,3,4'-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylketonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 5-(2,5-di-side-oxytetrahydro-3-furanyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-epoxyphenyl))bis(oxy))bis(isobenzofuran-1,3-dione), 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-bisphenol A dianhydride, etc. From the perspectives of solvent solubility and adhesion to the substrate, 4,4'-oxyphthalic anhydride, 4,4'-(hexafluoroisopropylidene)phthalic anhydride, and 4,4'-bisphenol A dianhydride are preferred. One or a mixture of two or more of these can be used.

[0111] From the viewpoint of the solvent solubility of the final obtained bismaleimide resin, the tetrabasic dianhydride (C) used in the synthesis of the aforementioned (I) bismaleimide compound is preferably selected from the group consisting of compounds represented by the following formulas (4) to (12).

[0112]

[0113] In equation (7), Y represents C(CF3)2, SO2, CO, oxygen atom, direct bond, or divalent bond group as represented by equation (13) below.

[0114]

[0115] In equation (13), * represents the bonding part with other parts.

[0116] In the aforementioned (I) bismaleimide compounds, tetrabasic dianhydride (C) is more preferably represented by the following general formula (15).

[0117]

[0118] In the aforementioned (I) bismaleimide compounds, tetrabasic dianhydride (C) is more preferably represented by the following general formula (8).

[0119]

[0120] In the aforementioned (I) bismaleimide compounds, tetrabasic dianhydride (C) is more preferably represented by the following general formula (5).

[0121]

[0122] In the aforementioned (I) bismaleimide compounds, tetrabasic dianhydride (C) is more preferably represented by the following general formula (9).

[0123]

[0124] In the aforementioned (I) bismaleimide compounds, tetrabasic dianhydride (C) is more preferably represented by the following general formula (10).

[0125]

[0126] Alternatively, the aforementioned (I) bismaleimide compound can also be a bismaleimide compound obtained by reacting the aforementioned aromatic diamine (A) with an organic diamine (B) other than the aforementioned aromatic diamine (A) with the aforementioned tetracarboxylic acid dianhydride (C) and the aforementioned maleic anhydride. By copolymerizing the aforementioned organic diamine (B) other than the aforementioned aromatic diamine (A), optional desired properties, such as further improving the heat resistance of the obtained cured material, can be controlled.

[0127] The term "organic diamine (B) other than the aforementioned aromatic diamine (A)" (hereinafter also referred to as "organic diamine (B)" as appropriate) in this invention refers to a diamine other than the diamine contained in the aforementioned aromatic diamine (A). This organic diamine (B) is not particularly limited, and examples include: aliphatic diamines such as 1,6-hexanediamine; alicyclic diamines such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine, and norcamphene diamine; and 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(aminomethyl)benzene, and 1,3-bis(4-aminophenyl)benzene. Aromatic diamines such as (-oxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, and 4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenyl sulfone; 3,3'-diaminodiphenyl sulfone; 4,4-diaminodiphenyl ketone; 4,4-diaminodiphenyl sulfide; and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Among these, from the viewpoint of obtaining a cured product with high heat resistance, aliphatic diamines with 6 to 12 carbon atoms, such as 1,6-hexamethylenediamine, and diaminocyclohexanes such as 1,3-bis(aminomethyl)cyclohexane, isophorone diamine, and norcamphene diamine are particularly preferred. Furthermore, when using these organic diamines (B) to obtain the aforementioned (I) bismaleimide compounds, one or more of these organic diamines (B) may be used alone or in combination.

[0128] The aforementioned (I) bismaleimide compounds, especially (I) bismaleimide compounds having an aromatic ring skeleton, exhibit excellent compatibility with other resins with different structures. Therefore, they are easily blended with other resins, readily complementing each other's properties to achieve better performance. Furthermore, the bismaleimide compounds of the present invention, especially bismaleimide compounds having an aromatic ring skeleton, can provide a bismaleimide resin composition that exhibits minimal variation in curability or physical properties when molded into a film or substrate form, and imparts a high glass transition point (Tg) to the cured product.

[0129] (I) Method for manufacturing bismaleimide compounds

[0130] There are no particular limitations on the method of manufacturing the aforementioned (I) bismaleimide compound, which can be efficiently manufactured by, for example, the methods shown below.

[0131] The basic process involves synthesizing amic acid from tetracarboxylic acid dianhydride and diamine, followed by a ring-closure dehydration step A, then reacting maleic anhydride to synthesize maleamic acid, and finally performing a ring-closure dehydration step B to seal the molecular chain end with maleimide groups to obtain (I) bismaleimide compound.

[0132] In the above manufacturing method, each step can be roughly divided into two reactions: the synthesis reaction of amyl acid or maleamyl acid and the ring-closure dehydration reaction. The following is a detailed description.

[0133] In step A, a specific tetracarboxylic acid dianhydride is first reacted with a specific diamine to synthesize an amide acid. This reaction is generally carried out 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.

[0134] Next, the ring-closure dehydration reaction of the amic acid is carried out at 90 to 120°C while removing the water byproduct generated by the condensation reaction from the system. To promote the ring-closure dehydration reaction, organic solvents (such as nonpolar solvents, high-boiling-point aprotic polar solvents, etc.) or acid catalysts may be added.

[0135] Organic solvents include: toluene, xylene, anisole, biphenyl, naphthalene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc. These can be used individually or in combination of two or more. Additionally, acid catalysts include: sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. These can be used individually or in combination of two or more.

[0136] The preferred molar ratio of diamine to tetracarboxylic acid dianhydride is diamine / tetracarboxylic acid dianhydride = 2.5 to 1.02 / 1.0, and more preferably diamine / tetracarboxylic acid dianhydride = 2.0 to 1.15 / 1.0. By adjusting the ratio, copolymers with amine groups at both ends can be synthesized.

[0137] Copolymers having amine groups at both ends can use amine compounds represented by the following formula (14).

[0138]

[0139] In equation (14), m is 1 to 100, and n is 0 to 100. Furthermore, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block, or random. C independently represents a tetravalent organogroup containing a cyclic structure. W is A or B. B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms. A independently represents a divalent organogroup represented by the following equation (3).

[0140]

[0141] In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. l independently represents an integer from 1 to 4. * indicates a bonding portion with other parts.

[0142] That is, the aforementioned (I) bismaleimide compound is more preferably a maleimide derivative of the amine compound represented by formula (14).

[0143] In step B, the copolymer with amino groups at both ends obtained in step A is reacted with maleic anhydride at room temperature (25°C) to 100°C to synthesize maleamic acid. Finally, at 95°C to 120°C, ring-closure dehydration is performed while removing water generated in the system as a byproduct, thereby sealing the molecular chain ends with maleimide groups to obtain the target bismaleimide compound. When the aforementioned chain-sealing reaction with maleimide groups at the molecular chain ends is carried out below 120°C, side reactions or polymers are less likely to form, which is therefore preferred.

[0144] If this manufacturing method is used, the resulting bismaleimide compound has a block copolymer structure, which can uniformly improve the compatibility of the synthesized resin with other resins.

[0145] The purification method for the compounds of the present invention can be a commonly used method, such as re-precipitation.

[0146] In the resin solids of the present invention, (I) the bismaleimide compound component is preferably 1 to 99% by mass, and more preferably 5 to 95% by mass.

[0147] (II) Reaction Accelerators

[0148] The reaction promoter (also referred to as component (II) below) is added to promote the cross-linking reaction of the maleimide compound (I) or the reaction of the maleimide group in component (I) with the reactive group in component (III) that can react with the maleimide group.

[0149] (II) There are no particular restrictions on the components as long as they can promote cross-linking reactions. Examples include: imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organophosphorus compounds, organophosphonium salts, and other ionic catalysts; as well as organic peroxides such as diallyl peroxide, dialkyl peroxide, carbonate peroxide, and hydrogen peroxide; and free radical polymerization initiators such as azoisobutyronitrile. Examples of imidazoles include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole. Examples of amines include triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, tri(dimethylaminomethyl)phenol, and benzyldimethylamine. Examples of phosphines include triphenylphosphine, tributylphosphine, and trioctylphosphine. Among these, when reacting with component (I) alone, or when the reactive group in component (III) is a carbon-carbon double bond such as a maleimide group, alkenyl group, or (meth)acrylic acid group, an organic peroxide or free radical polymerization initiator is preferred. When the reactive group in component (III) is an epoxy group, hydroxyl group, or an anhydride group, a basic compound such as an imidazole or tertiary amine is preferred.

[0150] (II) The reaction accelerator is preferably formulated in the range of 0.05 to 10 parts by weight, particularly 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of thermosetting resin components such as (I) or (III). Outside of this range, there is concern that the curing of the maleimide resin composition may become very slow or rapid during molding, and therefore this is not preferred. Furthermore, there is concern that the heat resistance and moisture resistance of the resulting cured product may become uneven.

[0151] (III) A thermosetting resin having reactive groups that can react with maleimide groups (also referred to below as component (III)).

[0152] In the aforementioned thermosetting maleimide resin composition, a thermosetting resin having a reactive group that can react with maleimide groups may be added as component (III).

[0153] Examples of reactive groups that can react with maleimide groups include: epoxy groups, maleimide groups, hydroxyl groups, acid anhydride groups, allyl or vinyl-like alkenyl groups, (meth)acrylate groups, thiol groups, cyano groups, phenolic groups, oxo groups, benzoxazine groups, carbodiimides, etc. However, in thermosetting resins having maleimide groups as reactive groups, maleimide compounds corresponding to component (I) are excluded from component (III). From the viewpoint of reactivity, the reactive groups of thermosetting resins as component (III) are preferably selected from epoxy groups, maleimide groups, hydroxyl groups, acid anhydride groups, and alkenyl groups. Furthermore, from the viewpoint of dielectric properties, alkenyl groups or (meth)acrylate groups are particularly preferred.

[0154] (III) The average molecular weight of the thermosetting resin of the component is preferably from 350 to 6,000, and more preferably from 1,000 to 5,000.

[0155] (III) Components may be used alone or in combination with two or more. (III) Components are preferably blended at 5 to 90% by mass relative to 100% by mass of the resin component, and more preferably at 15 to 85% by mass.

[0156] The composition containing the above-mentioned (I) bismaleimide compound is preferably a thermosetting resin having a reactive group that can react with the maleimide group.

[0157] Thermosetting resins having reactive groups that can react with maleimide groups may contain one or more of the following: maleimide compounds selected from (I) bismaleimide compounds (hereinafter also referred to as "other maleimide compounds"), cyanate ester compounds, phenolic resins, epoxy resins, oxy-resins, benzoxazine compounds, carbodiimide compounds, and compounds having vinyl unsaturated groups. The following describes the components of thermosetting resins having reactive groups that can react with maleimide groups.

[0158] ((I) Maleimide compounds other than bismaleimide compounds)

[0159] Other maleimide compounds are not particularly limited as long as they are compounds other than the maleimide compound (I) of this embodiment and have one or more maleimide groups in their molecules. Specific examples include: N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinephenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimide hexanoic acid, 4-maleimide butyric acid, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl- 4-Maleimide phenyl)methane, phenylmethane maleimide, o-phenyl bismaleimide, m-phenyl bismaleimide, p-phenyl bismaleimide, o-phenylene biscitraconimide, m-phenyl biscitraconimide, p-phenyl biscitraconimide, 2,2-bis(4-(4-maleimide phenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenyl bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 1, 5-Dimaleimide-2-methylpentane, 1,6-Dimaleimide hexane, 1,6-Dimaleimide-(2,2,4-trimethyl)hexane, 1,8-Dimaleimide-3,6-dioxooctane, 1,11-Dimaleimide-3,6,9-trioxadecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4-diphenylmethane bisciconimide, 2,2-bis[ [4-(4-citrconium imide phenoxy)phenyl]propane, bis(3,5-dimethyl-4-citrconium imide phenyl)methane, bis(3-ethyl-5-methyl-4-citrconium imide phenyl)methane, bis(3,5-diethyl-4-citrconium imide phenyl)methane, polyphenylmethane maleimide, polyphenylmethane maleimide, and other maleimide compounds represented by formula (6), maleimide compounds represented by formula (7), fluorescent yellow-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. These maleimide compounds may be used alone or appropriately mixed in combination of two or more.

[0160] Other maleimide compounds represented by formula (26) are also available in commercially available products, such as BMI-2300 (trade name) manufactured by Yamato Chemical Industries, Ltd. Other maleimide compounds represented by formula (27) are also available in commercially available products, such as MIR-3000 (trade name) manufactured by Nippon Chemical Industries, Ltd. Other maleimide compounds represented by formula (28) are also available in commercially available products, such as MIR-5000 (trade name) manufactured by Nippon Chemical Industries, Ltd.

[0161]

[0162] In the composition of this embodiment, the total content of other maleimide compounds is not particularly limited, but it is more preferably 0.01 to 50 parts by weight of resin solids per 100 parts by weight in the composition of this embodiment.

[0163] (Cyanate ester compounds)

[0164] Cyanate ester compounds are cyanate ester compounds obtained by reacting phenolic resins with cyanide halides. Specific examples include: benzene dicyanate, benzene tricyanate, naphthalene dicyanate, biphenyl dicyanate, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfone, bis(4-cyanophenyl) sulfide, phenol-phenolic cyanate esters, and cyanate groups converted from phenol-dicyclopentadiene cocondensates, but are not limited to these.

[0165] Furthermore, the cyanate compound for which the synthesis method is disclosed in Japanese Patent Application Publication No. 2005-264154 is particularly preferred as a cyanate compound due to its excellent low hygroscopicity, flame retardancy, and dielectric properties.

[0166] The cyanate compound may optionally contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octanoate, tin octanoate, lead acetoacetate, and dibutyltin maleate to optionally trimerize the cyanate group to form a symmetrical triazine ring. The catalyst is typically used in amounts of 0.0001 to 0.10 parts by weight relative to 100 parts by weight of the total composition, and more preferably 0.00015 to 0.0015 parts by weight.

[0167] In the composition of this embodiment, the total content of cyanate ester compounds is not particularly limited, but it is more preferably 0.01 to 50 parts by weight of resin solids per 100 parts by weight in the composition of this embodiment.

[0168] (Phenolic resin)

[0169] Phenolic resins that have two or more hydroxyl groups in one molecule can be used, as long as they are generally known. Examples include: bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol-phenolic resin, bisphenol A phenolic resin, glycidyl ester type phenolic resin, aralkyl phenolic resin, biphenyl aralkyl phenolic resin, cresol-phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol-phenolic resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, resin containing polymerizable unsaturated hydrocarbon groups, and hydroxyl-containing polysiloxane resins, etc., but there are no particular limitations. These phenolic resins can be used alone or in appropriate mixtures of two or more.

[0170] In the composition of this embodiment, the total content of phenolic resin is not particularly limited, but the resin solids in the composition of this embodiment are preferably 0.01 to 50 parts by weight per 100 parts by weight.

[0171] There are no particular limitations on the epoxy resin used; any commonly known type can be used. Examples include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A phenolic epoxy resin, biphenyl type epoxy resin, phenol-phenolic epoxy resin, cresol-phenolic epoxy resin, xylene-phenolic epoxy resin, polyfunctional phenolic epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified phenolic epoxy resin, naphthalene ether type epoxy resin, phenolic alkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, triglycidyl isocyanate, and glycidyl ester type epoxy resin. Epoxy resins, alicyclic epoxy resins, dicyclopentadiene phenolic epoxy resins, biphenyl phenolic epoxy resins, phenolic alkylphenolic epoxy resins, naphthol alkylphenolic epoxy resins, arylalkylphenolic epoxy resins, naphthol alkylalkyl epoxy resins, dicyclopentadiene epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidylamine, compounds obtained by epoxidizing double bonds of butadiene, compounds obtained by reacting hydroxyl-containing polysiloxane resins with epichlorohydrin, and their halides. These epoxy resins can be used alone or in appropriate mixtures of two or more.

[0172] In the composition of this embodiment, the total content of epoxy resin is not particularly limited, but it is more preferably 0.01 to 50 parts by weight of resin solids per 100 parts by weight in the composition of this embodiment.

[0173] (Oxygen and resin)

[0174] Oxygen resins that are generally known can be used. Examples include: alkyl oxygens such as 2-methyl oxygen, 2,2-dimethyl oxygen, 3-methyl oxygen, and 3,3-dimethyl oxygen; 3-methyl-3-methoxymethyl oxygen, 3,3-di(trifluoromethyl)perfluoro oxygen, 2-chloromethyl oxygen, 3,3-bis(chloromethyl) oxygen, biphenyl-type oxygen, OXT-101 (manufactured by Dong-A Synthetic Co., Ltd., trade name), and OXT-121 (manufactured by Dong-A Synthetic Co., Ltd., trade name), etc., but there are no particular limitations. These oxygen resins can be used alone or in appropriate mixtures of two or more.

[0175] In the composition of this embodiment, the total content of oxygen and resin is not particularly limited, but the resin solids in the composition of this embodiment are preferably 0.01 to 40 parts by weight per 100 parts by weight.

[0176] (Benzoxazine compounds)

[0177] Benzooxazine compounds can be used as long as they have two or more dihydrobenzooxazine rings in one molecule. Examples include: bisphenol A type benzooxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol F type benzooxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), bisphenol S type benzooxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd., trade name), phenolphthalein type benzooxazine, etc., but there are no particular limitations. These benzooxazine compounds can be used alone or in appropriate mixtures of two or more.

[0178] In the composition of this embodiment, the total content of benzoxazine compounds is not particularly limited, but the resin solids in the composition of this embodiment are preferably 0.01 to 40 parts by weight per 100 parts by weight.

[0179] (Carbodiimide compound)

[0180] Carbodiimide compounds are not particularly limited as long as they have at least one carbodiimide group in the molecule, and generally known ones can be used. Examples include: dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, diphenylcarbodiimide, di(tert-butyl)carbodiimide, di(β-naphthyl)carbodiimide, N,N'-di(2,6-diisopropyl)phenylcarbodiimide, 2,6,2',6'-tetraisopropyldiphenylcarbodiimide, cyclic carbodiimides, Carbodilite (registered trademark: Nisshinbo Chemical Co., Ltd.), and polycarbodiimides such as Stabaxol (registered trademark: LANXESS Deutschland GmbH). These carbodiimide compounds can be used alone or in appropriate mixtures of two or more.

[0181] In the composition of this embodiment, the total content of carbodiimide compounds is not particularly limited, but it is more preferably 0.01 to 40 parts by weight of resin solids per 100 parts by weight in the composition of this embodiment.

[0182] (Compounds containing vinyl unsaturated groups)

[0183] There are no particular limitations on whether a compound has an ethylene unsaturated group in one molecule.

[0184] Specific examples of compounds containing vinyl unsaturated groups include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenyl ethyl methacrylate, isoborneol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetrahydrofuran methyl methacrylate, dibutyl methacrylate, hexanediol methacrylate, neopentyl methacrylate, nonanediol methacrylate, dimethyl methacrylate, diethyl methacrylate, polyethylene glycol dimethacrylate, trimethacryloyl ethyl isocyanate, polypropylene... Diol di(meth)acrylate, di(meth)acrylate adipate epoxy ester, di(meth)acrylate bisphenol ethylene oxide ester, (meth)acrylate hydrogenated bisphenol ethylene oxide ester, di(meth)acrylate bisphenol ester, di(meth)acrylate ε-caprolactone modified hydroxytrimethylacetic acid neopentyl glycol ester, hexa(meth)acrylate ε-caprolactone modified dipentaerythritol ester, poly(meth)acrylate ε-caprolactone modified dipentaerythritol ester, poly(meth)acrylate dipentaerythritol ester, tri(meth)acrylate trimethylolpropane ester, tri(meth)acrylate triethylolpropane ester and their ethylene oxide adducts; tri(meth)acrylate pentaerythritol ester and its ethylene oxide adducts; tetra(meth)acrylate pentaerythritol ester, hexa(meth)acrylate dipentaerythritol ester and its ethylene oxide adducts, etc.

[0185] In addition, specific examples of compounds having ethylene unsaturated groups include: ethyl methacrylates containing both (meth)acrylyl and ethyl methacrylate bonds within the same molecule; polyester (meth)acrylates containing both (meth)acrylyl and ester bonds within the same molecule; epoxy methacrylates derived from epoxy resins and containing (meth)acrylyl groups; and reactive oligomers that use these bonds in combination.

[0186] The term "(meth)acrylate aminocarboxylate" can be exemplified by: hydroxyl-containing (meth)acrylates and polyisocyanates, as well as other alcohols used optionally. Examples include: hydroxyalkyl methacrylates such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate; glyceryl monomethacrylate, glyceryl dimethacrylate, and glyceryl dimethacrylate; glycosyl dimethacrylates such as pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol pentamethacrylate, and pentaerythritol hexamethacrylate; and polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norcamphene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and isocyanates of these, and biuret reactants, etc.

[0187] Examples of so-called polyester (meth)acrylates include: monofunctional (poly)acrylate (meth)acrylate (poly ...

[0188] In addition, examples include: mono-, di-, tri-, or tetra(meth)acrylates of triols obtained by adding 1 mole or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerol to 1 mole of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane; mono(meth)acrylates or poly(meth)acrylates of triols, tetraols, pentaols, or hexaols obtained by adding 1 mole or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerol to 1 mole of dipentaerythritol.

[0189] Additionally, examples include: (meth)acrylates of polyester polyols containing diols such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butanediol, 3-methyl-1,5-pentanediol, and hexanediol, and reacting with polyprotic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimeric acid, sebacic acid, azelaic acid, 5-sodium sulfonate isophthalic acid, and their anhydrides; and (meth)acrylates of polyester diols modified with cyclic lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone, etc., which are polyfunctional (poly)acrylates (meth)acrylates.

[0190] So-called (meth)acrylate epoxy esters are compounds containing epoxy groups and carboxylic acid esters of (meth)acrylate. Examples include: phenol-phenolic epoxy esters of (meth)acrylate, cresol-phenolic epoxy esters of (meth)acrylate, trihydroxyphenylmethane epoxy esters of (meth)acrylate, dicyclopentadienol epoxy esters of (meth)acrylate, bisphenol A epoxy esters of (meth)acrylate, bisphenol F epoxy esters of (meth)acrylate, biphenol epoxy esters of (meth)acrylate, bisphenol A phenolic epoxy esters of (meth)acrylate, naphthalene-containing epoxy esters, glyoxal epoxy esters of (meth)acrylate, heterocyclic epoxy esters of (meth)acrylate, and acrylic anhydride-modified epoxy esters of these.

[0191] For example, ethylene ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrene such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; or compounds containing vinyl groups such as triallyl isocyanate, trimethylallyl isocyanate, and bisallylnadimide can also be listed as specific examples of compounds containing vinyl unsaturated groups.

[0192] Compounds containing vinyl unsaturated groups are commercially available, such as: KAYARAD (registered trademark) ZXR-801H (trade name, manufactured by Nippon Kayaku Co., Ltd.), propylene glycol monomethyl ether acetate (a dicyclopentadiene acrylate epoxy ester compound manufactured by Nippon Kayaku Co., Ltd.), KAYARAD (registered trademark) ZXR-1806H (trade name), KAYARAD (registered trademark) ZXR-1810H (trade name), and KAYARAD (registered trademark) ZXR-1889H (trade name). These compounds containing vinyl unsaturated groups can be used alone or in appropriate mixtures of two or more.

[0193] In the composition of this embodiment, the total content of compounds having vinyl unsaturated groups is not particularly limited, but it is more preferably 0.01 to 60 parts by weight of resin solids per 100 parts by weight in the composition of this embodiment.

[0194] The aforementioned composition contains components other than those represented by the aforementioned compound of general formula (2). Other components contained in the aforementioned resin composition may include, for example, organic solvents, photopolymerization initiators, curing agents and curing catalysts having reactive groups that can react with maleimide groups, adhesion enhancers such as coupling agents, fillers, etc. Various components other than those mentioned above may be used without particular limitation depending on the intended use or application of the resin composition. Since it is easy to process, a resin composition containing an organic solvent is preferred.

[0195] Furthermore, the aforementioned (I) bismaleimide compound can undergo self-polymerization, and therefore can be used without the use of photopolymerization initiators, hardeners, and hardening catalysts.

[0196] (Photopolymerization initiator)

[0197] The aforementioned bismaleimide compound represented by general formula (2) can undergo self-polymerization alone, but it can also undergo self-polymerization in combination with a photopolymerization initiator or a hardening catalyst in the aforementioned compound represented by general formula (2) after forming a composition. By using a photopolymerization initiator, self-polymerization can be carried out by light irradiation. In addition, by using a hardening catalyst, the heating temperature during self-polymerization can be lowered compared to when no hardening catalyst is used.

[0198] There are no particular restrictions on the photopolymerization initiators that can be used in self-polymerization; those previously used can be appropriately employed. Specific examples of photopolymerization initiators include: acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, and Michler's ketone. Ketone), benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, [2-Methyl-propanoyl]-benzyl]phenyl}-2-methyl-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione = 2-(O-benzyl oxime), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]acetone 1-(O-acetyl oxime), 2,4-dimethylthioxanone, etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0199] Among these, from the viewpoint that fine patterning can be achieved using a reduction projection exposure machine (stepper; light source wavelength: 365nm, 436nm) that is standardly used in manufacturing processes such as protective films for semiconductors, it is more preferable to use one that can efficiently generate free radicals at an exposure wavelength of 310 to 436nm (especially 365nm). Preferred photopolymerization initiators include, for example: 1-[4-(phenylthio)phenyl]-1,2-octanedione = 2-(O-benzyl oxime) (manufactured by BASF JAPAN, "IRGACURE OXE-01"), 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl] ethyl ketone 1-(O-acetyl oxime) (manufactured by BASF JAPAN, "IRGACURE OXE-02"), 2,4-dimethylthioxanone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one (manufactured by IGM Resins BV, "Omirad 907").

[0200] The amount of photopolymerization initiator relative to 100 parts by mass of the compound represented by formula (1) is preferably 0.1 to 20 parts by mass, and more preferably 1 to 5 parts by mass.

[0201] Sensitizers can also be used in conjunction with photopolymerization initiators. There are no particular limitations on the sensitizers that can be used, as long as they are generally known in the past; examples include 4,4'-bis(diethylamino)diphenyl ketone, etc.

[0202] The amount of sensitizer used is preferably 2 parts by mass or less, and more preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the compound represented by formula (2). By using the sensitizer in combination, the sensitivity to light during self-polymerization can be improved.

[0203] (Cure catalyst)

[0204] The hardening catalyst that can be used in conjunction with the self-polymerization process is not particularly limited as long as it can promote the self-polymerization of the maleimide groups at both ends of the compound represented by formula (1) by heating, and conventionally used catalysts may be appropriately used. Specific examples of hardening catalysts include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol and benzyldimethylamine; and triphenylphosphine, tri... Phosphine derivatives such as butylphosphine and trioctylphosphine; organometallic salts such as tin octoate, zinc octoate, dibutyltin maleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; organic peroxides such as bis(tert-butyl) peroxide and dicumyl peroxide; azo compounds such as azobisisobutyronitrile and azobis(dimethylvaleronitrile); 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.

[0205] The amount of hardening catalyst used is more preferably 10 parts by mass or less, and more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the compound represented by formula (1).

[0206] There are no particular limitations on the aforementioned curing agent, and conventionally used ones may be appropriately used. The curing agent is not particularly limited as long as it is a compound having functional groups (or structures) such as amine, cyanate, phenolic hydroxyl, or alcoholic hydroxyl that can undergo cross-linking reactions with maleimide compounds. Furthermore, maleimide compounds other than (I) bismaleimide compounds may also be used in combination.

[0207] (Organic solvents)

[0208] The organic solvent is not particularly limited, but examples include: γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxy propionate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethyl sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methylpentanone, etc. These organic solvents can be used alone or in combination of two or more. Using organic solvents in combination is a preferred approach in terms of improving the processing properties of the composition.

[0209] There is no particular limitation on the content of organic solvent in the composition of the present invention. Generally, the content of solvent in the composition is 95% by mass or less, and more preferably 20% to 90% by mass.

[0210] (Coupled agent)

[0211] There are no particular limitations on silane coupling agents, but examples include: 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, 3-methpropenoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-ureapropyltriethoxysilane, etc. These can be used alone or in combination of two or more.

[0212] Since the silane coupling agent is not reactive with the compounds of the present invention (compounds, self-polymerizing compounds, benzoxazole), it may remain as a residual component after curing, in addition to the component that acts at the substrate interface. Therefore, there are concerns that using the adhesion enhancer in large quantities may lead to adverse effects such as reduced physical properties. Depending on the type of substrate, it is more appropriate to use it within a range that will not cause adverse effects, considering that it is effective even in small amounts. This usage rate relative to the composition is generally 15% by mass or less, preferably more than 0% by mass and less than 5% by mass, and the upper limit of the usage rate may vary depending on the type of substrate.

[0213] (Thermoplastic resin)

[0214] Examples of thermoplastic resins include polyethersulfone, polystyrene, and polycarbonate. Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium dioxide, carbon black, and naphthalene black. Examples of tackifiers include organic bentonite, bentonite, and montmorillonite. Examples of heat-inhibiting agents include hydroquinone and 2,6-bis(tert-butyl)-p-cresol. Examples of defoamers include polysiloxane-based, fluorinated, and polymeric defoamers.

[0215] The amount of these additives in the compositions of the present invention, preferably less than 30% by mass, is only a general standard and can be appropriately increased or decreased depending on the purpose of use.

[0216] (filler material)

[0217] In the resin composition of this embodiment, a filler may also be included to improve various properties such as coating properties or heat resistance. The filler is preferably insulating and does not impede the penetration of light at a wavelength of 405 nm (h-rays). There are no particular limitations on the filler materials, but examples include: silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, aluminum oxide, 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, micro-powdered glass (e.g., E glass, T glass, D glass, etc.)), polysiloxane powder, fluoropolymer fillers, urethane resin fillers, (meth)acrylic resin fillers, polyethylene fillers, styrene-butadiene rubber, and polysiloxane rubber, etc. These fillers can be used alone or in appropriate mixtures of two or more.

[0218] Among these, one or more are selected from the group consisting of silica, boehmite, barium sulfate, polysiloxane powder, fluoropolymer filler, ethyl carbamate resin filler, (meth)acrylic acid resin filler, polyethylene filler, styrene-butadiene rubber, and polysiloxane rubber.

[0219] These fillers can also be surface-treated using silane coupling agents, etc., as described later.

[0220] From the viewpoint of improving the heat resistance of the cured product obtained by curing the resin composition of this embodiment and obtaining good coating properties, silica is preferred, and fused silica is even more preferred. Specific examples of silica include: SFP-130MC manufactured by Denka Co., Ltd., SC2050-MB, SC1050-MLE, YA010C-MFN and YA050C-MJA manufactured by Admatechs Co., Ltd.

[0221] The particle size of the filler is not particularly limited, but is usually 0.005 to 100 μm, and more preferably 0.01 to 50 μm.

[0222] In the resin composition of this embodiment, the content of filler is not particularly limited. From the viewpoint of improving the heat resistance of the cured product, it is more preferably set to 1000 parts by weight or less of the resin solids in the resin composition relative to 100 parts by weight, more preferably 500 parts by weight or less, and most preferably 300 parts by weight or less. Furthermore, when filler is included, the lower limit is not particularly limited. From the viewpoint of improving various properties such as coating properties or heat resistance, it is generally 1 part by weight relative to 100 parts by weight of the resin solids in the resin composition.

[0223] <Other Additives>

[0224] In the thermosetting maleimide resin composition of the present invention, various additives may be optionally formulated without impairing the effects of the present invention. Examples of such additives include: organopolysiloxanes having reactive functional groups, non-functional polysiloxane oils, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, photosensitizers, light stabilizers, polymerization inhibitors, flame retardants, pigments, dyes, adhesives, etc. Furthermore, ion traps and other additives may be formulated to improve the electrical properties of the cured thermosetting maleimide resin composition.

[0225] The thermosetting maleimide resin composition of the present invention can also be dissolved in organic solvents to form a varnish. The thermosetting maleimide resin composition, by forming a varnish, is easily formed into sheets or films, and is also easily coated or impregnated onto glass cloth made of E-glass, low-dielectric glass, quartz glass, etc. There are no particular limitations on the use of any organic solvent that can dissolve the thermosetting resin component (I) or (III). Suitable organic solvents include, for example, toluene, xylene, methoxybenzene, cyclohexanone, cyclopentanone, etc. The above-mentioned organic solvents can be used alone or in mixtures of two or more. The concentration of the thermosetting maleimide resin composition of the present invention in the varnish is preferably 5 to 80% by mass, and more preferably 10 to 75% by mass.

[0226] This thermosetting maleimide resin composition can be used as an adhesive, primer, coating material primarily for semiconductor devices, and as a substrate material. There are no particular limitations on its application methods or forms. The following are illustrative examples, but are not intended to limit its use.

[0227] For example, after applying a thermosetting maleimide resin composition (varnish) dissolved in an organic solvent to a substrate, it is typically heated at a temperature of 80°C or higher, preferably 100°C or higher, for 0.5 to 5 hours to remove the organic solvent, and then heated at a temperature of 150°C or higher, preferably 175°C or higher, for 0.5 to 10 hours. This forms a smooth and robust maleimide resin cured film. The drying process for removing the organic solvent and the subsequent heating and curing process can be at constant temperatures, but it is preferable to gradually increase the temperature. This allows for efficient removal of the organic solvent from the composition and efficient resin curing.

[0228] The cured coating obtained by curing the thermosetting maleimide resin composition of the present invention exhibits excellent heat resistance, mechanical properties, electrical properties, adhesion to substrates, and solvent resistance, and also possesses a low dielectric constant. Therefore, it can be applied in applications such as semiconductor devices, specifically as passivation or protective films on the surface of semiconductor elements, bonding protective films at the junctions of diodes, transistors, etc., alpha-ray shielding films for VLSI, interlayer insulating films, ion implantation masks, etc. Furthermore, it can be applied as conformal coatings for printed circuit boards, alignment films for liquid crystal surface elements, protective films for glass fibers, and surface protective films for solar cells. Additionally, when an inorganic filler is incorporated into the thermosetting maleimide resin composition of the present invention, it can be applied to printing paste compositions; when a conductive filler is incorporated, it can be applied to conductive paste compositions and other widely used applications.

[0229] Methods for coating a thermosetting maleimide resin composition dissolved in an organic solvent onto a substrate include rotary coaters, slot coaters, spray coaters, dip coaters, and bar coaters, but there are no particular limitations.

[0230] Furthermore, after forming the aforementioned hardened coating, molding the epoxy resin molding material for semiconductor sealing improves the adhesion between the epoxy resin molding material and the substrate. In the resulting semiconductor device, no cracking or peeling of the epoxy resin molding material from the substrate was observed during solder reflow after moisture absorption, demonstrating high reliability.

[0231] In this case, the epoxy resin molding material for semiconductor sealing can be a commonly known epoxy resin composition for semiconductor sealing, which contains: epoxy resin having two or more epoxy groups in one molecule, phenolic resin, acid anhydride or other epoxy resin curing agent, and inorganic filler, etc., and commercially available products can also be used.

[0232] In this case, when the substrate is made of an easily oxidizable metal such as copper, a nitrogen environment is preferably used for the primary curing of the thermosetting maleimide resin composition or the epoxy resin molding material for semiconductor sealing of the present invention in order to resist oxidation.

[0233] In addition, the resin composition of the present invention can also be coated onto a support sheet to form a film for use. The support sheet can be any commonly used material, such as: polyethylene (PE) resin, polypropylene (PP) resin, polystyrene (PS) resin, and other polyolefin resins; polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, and other polyester resins. The surface of these support sheets can also be demolded. Furthermore, the coating method is not particularly limited, and examples include gap coating machines, curtain coating machines, roller coating machines, and laminating machines. Furthermore, the thickness of the coating layer is not particularly limited; the thickness after solvent distillation is between 1 and 100 μm, preferably between 3 and 80 μm. Additionally, a coating film can be used on top of the coating layer.

[0234] Alternatively, copper foil can be attached to the coating layer and configured as resin-coated copper foil for use as a substrate material.

[0235] In addition, the resin composition after clearing can be impregnated in glass cloth made of E glass, low dielectric glass, quartz glass, etc., and the organic solvent can be removed to convert it into B-stage, which can then be used as a prepreg.

[0236] Example

[0237] The present invention will be described in more detail below with reference to embodiments and comparative examples, but the present invention is not limited to the following embodiments. In the embodiments, "parts" and "%" refer to mass.

[0238] The conditions for determining molecular weight are as follows.

[0239] Model: GPC TOSOH HLC-8220GPC

[0240] Column: Super HZM-N

[0241] Dissolution solution: THF (tetrahydrofuran); 0.35 ml / min, 40℃

[0242] Detector: RI (Differential Refractometer)

[0243] Molecular weight standard: Polystyrene

[0244] Synthesis Example 1 (I-1)

[0245] 162 g of toluene and 162 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, 32.4 g (0.24 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, followed by the slow addition of 22.9 g (0.24 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing. Then, 52.8 g (0.12 mol) of 4,4'-(hexafluoroisopropylidene) phthalic anhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. The theoretical amount of water obtained from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 28.0 g (0.29 mol) of maleic anhydride was added to a flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted starting materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol for a reprecipitation process to remove the solvent and dry, yielding 78 g (78% yield, Mw = 3,600) of the target light brown solid bismaleimide compound (I-1).

[0246] Synthesis Example 2 (I-2)

[0247] 165 g of toluene and 165 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, 26.6 g (0.20 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 11.7 g (0.02 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) were added, followed by the slow addition of 20.9 g (0.22 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to combine, and then 48.2 g (0.11 mol) of 4,4'-(hexafluoroisopropylidene)phthalic anhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. Up to this point, the theoretical amount of water produced from the condensation was obtained. The reaction mixture was cooled to below room temperature, and 25.5 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water produced. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted starting materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol to carry out a reprecipitation process, remove the solvent, and dry to obtain 72 g (72% yield, Mw = 4,000) of the target light brown solid bismaleimide compound (I-2).

[0248] Synthesis Example 3 (I-3)

[0249] 165 g of toluene and 165 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, 29.7 g (0.22 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, followed by the slow addition of 21.0 g (0.22 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to mix, and then 56.8 g (0.11 mol) of 4,4'-bisphenol A dianhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours under reflux to form an amine-terminated diimide. The theoretical amount of water produced from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 25.7 g (0.26 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted raw materials, yielding a varnish of the bismaleimide compound. The varnish was then dropped into 1,000 g of methanol to carry out a reprecipitation process, remove the solvent, and dry to obtain 78 g of the target light brown solid of the bismaleimide compound (yield 80%, Mw = 4,500) (I-3).

[0250] Synthesis Example 4 (I-4)

[0251] 150 g of toluene and 150 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, 43.9 g (0.32 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, followed by the slow addition of 31.0 g (0.32 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing. Then, 36.1 g (0.16 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours under reflux to form an amine-terminated diimide. The theoretical amount of water produced from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 37.9 g (0.38 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of generated water. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted raw materials, yielding a varnish of the bismaleimide compound. The varnish was then dropped into 1,000 g of methanol to carry out a reprecipitation process, remove the solvent, and dry to obtain 78 g of the target white solid bismaleimide compound (yield 78%, Mw = 3,000) (I-4).

[0252] Synthesis Example 5 (I-5)

[0253] 150 g of toluene and 150 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, 41.2 g (0.30 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, followed by the slow addition of 29.1 g (0.30 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing. Then, 40.0 g (0.15 mol) of 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. The theoretical amount of water obtained from this condensation is shown at this point. The reaction mixture was cooled to below room temperature, and 35.6 g (0.36 mol) of maleic anhydride was added to a flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted starting materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol to carry out a reprecipitation process, remove the solvent, and dry to give 75 g (75% yield, Mw = 3,500) of the target white solid bismaleimide compound (I-5).

[0254] Synthetic Example 6 (I-6)

[0255] 154 g of toluene and 154 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, 39.1 g (0.28 mol) of m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added, followed by the slow addition of 27.6 g (0.28 mol) of methanesulfonic acid to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing. Then, 43.1 g (0.14 mol) of 4-(2,5-dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride was slowly added to the stirred mixture. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. The theoretical amount of water obtained from this condensation is shown at this point. The reaction mixture was cooled to below room temperature, and 33.8 g (0.34 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, the organic layer was washed with water (100 ml × 5 times) to remove salts or unreacted starting materials, yielding a varnish of the bismaleimide compound. The varnish was then added dropwise to 1,000 g of methanol to carry out a reprecipitation process, remove the solvent, and dry to give 75 g (75% yield, Mw = 3,200) of the target white solid bismaleimide compound (I-6).

[0256] Comparative Synthesis Example 1 (BMI-1)

[0257] 110 g of toluene and 36 g of N-methylpyrrolidone were added to a 500 ml round-bottom flask equipped with a fluoropolymer-coated stir bar. Next, 90.9 g (0.17 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) was added, followed by the slow addition of 16.4 g (0.17 mol) of methanesulfonic anhydride to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing, and then 18.6 g (0.08 mol) of pyrocalcite dianhydride was slowly added to the stirred mixture. A Dean-Stark trap with a condenser was installed in the flask. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. The theoretical amount of water produced from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 20.0 g (0.20 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, 200 ml of toluene was added to the flask. The diluted organic layer was then washed with water (100 ml × 3 times) to remove salts or unreacted starting materials. The solvent was then removed under vacuum to give 102 g of a brown, waxy bismaleimide compound (yield 85%, Mw = 3,800).

[0258] The bismaleimide compound of Comparative Synthesis Example 1 is readily available from DESIGNER MOLECURES Inc., “BMI-3000”.

[0259]

[0260] Comparative Synthesis Example 2 (BMI-2)

[0261] 110 g of toluene and 36 g of N-methylpyrrolidone were added to a 500 ml round-bottom flask equipped with a fluoropolymer-coated stir bar. Next, 85.3 g (0.16 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) was added, followed by the slow addition of 15.4 g (0.16 mol) of methanesulfonic anhydride to form a salt. The mixture was stirred for approximately 10 minutes to allow mixing, and then 24.8 g (0.08 mol) of 4,4'-oxyphthalic dianhydride was slowly added to the stirred mixture. A Dean-Stark trap and condenser were installed in the flask. The mixture was heated for 6 hours and refluxed to form an amine-terminated diimide. The theoretical amount of water produced from this condensation was obtained up to this point. The reaction mixture was cooled to below room temperature, and 18.8 g (0.19 mol) of maleic anhydride was added to the flask. The mixture was further refluxed for 8 hours to obtain the desired amount of water. After cooling to room temperature, 200 ml of toluene was added to the flask. The diluted organic layer was then washed with water (100 ml × 3 times) to remove salts or unreacted starting materials. The solvent was then removed under vacuum to give 106 g of a brown, waxy bismaleimide compound (yield 88%, Mw = 3,700).

[0262] The bismaleimide compound of Comparative Synthesis Example 2 is readily available from DESIGNER MOLECURES Inc., “BMI-1500”.

[0263]

[0264] Comparative Synthesis Example 3 (BMI-3)

[0265] The bismaleimide compound (BMI-3) was synthesized using the method described in Example 1 of Japanese Patent Application Publication No. 2021-123672 and by known methods.

[0266] 37.25 g (0.219 mol) of isophorone diamine, 76.94 g (0.35 mol) of pyrocalcite dianhydride, and 350 g of toluene were added to a 2 L four-necked glass flask equipped with a stirrer, a Dean-Stark apparatus, a cooling condenser, and a thermometer. The mixture was stirred at 80 °C for 3 hours to synthesize ammonium acid. Then, under these conditions, the temperature was raised to 110 °C, and the mixture was stirred for 4 hours while distilling off the byproduct water to synthesize a block copolymer.

[0267] Next, 116.88 g (0.219 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.) was added to a flask containing a block copolymer solution cooled to room temperature, and stirred at 80°C for 3 hours to synthesize amyl acid. Then, under these conditions, the temperature was raised to 110°C, and the mixture was stirred for 4 hours while distilling off the byproduct water to synthesize the diterminated diamine.

[0268] After cooling the flask containing the obtained diamine solution to room temperature, 18.88 g (0.193 mol) of maleic anhydride was added, and the mixture was heated again and stirred at 80 °C for 3 hours to synthesize amyl acid. Then, under this condition, the temperature was raised to 110 °C, and the mixture was stirred for 15 hours while distilling off the byproduct water. The mixture was then washed five times with 300 g of water to obtain a varnish of the bismaleimide compound. The varnish was then added dropwise to 3,000 g of isopropanol (IPA) for a reprecipitation process to remove the solvent and dry, yielding the desired dark brown solid (yield 85%, Mw = 8,000).

[0269]

[0270] The following are the materials used in this embodiment.

[0271] [(I) Ingredients; Bismaleimide compound]

[0272] I: Bismaleimide compounds represented by synthetic examples (I-1) to (I-6) and bismaleimide compounds (BMI-1) to (BMI-3) represented by comparative synthetic examples 1 to 3.

[0273] [(II) Components; Reaction Accelerator]

[0274] (II-1) Dicumyl peroxide (Percumyl D, manufactured by Nippon Oil Company Limited)

[0275] (II-2) Imidazole is a hardening accelerator (2E4MZ, manufactured by Shikoku Chemical Co., Ltd.)

[0276] [(III) Components; Thermosetting resin]

[0277] (III-1): Aromatic maleimide resin represented by the following formula (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.)

[0278]

[0279] (III-2): Aromatic maleimide resin represented by the following formula (MIR-5000, manufactured by Nippon Kayaku Co., Ltd.)

[0280]

[0281] (III-3) Solid bisphenol A type epoxy resin (jER-1001, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 475)

[0282] (III-4) The terminal styrene-modified polyphenylene ether resin (OPE-2St-1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., quantity average molecular weight 1,200) is represented by the following formula.

[0283]

[0284] In the formula, x' ranges from 0 to 20, y' ranges from 0 to 20, and x' and y' will not both be 0 at the same time.

[0285] (Examples 1 to 10 and Comparative Examples 1 to 3)

[0286] The components were dissolved or dispersed in methoxybenzene according to the mixing amounts (parts by mass) shown in Tables 1 to 3, and the amount of non-volatile components was adjusted to 50% by mass to obtain a varnish (varnish 1) of the resin composition. The varnish 1 of the aforementioned resin composition was coated onto a 38 μm thick PET film using a roller coater and dried at 80°C for 15 minutes to obtain an uncured resin film with a thickness of 50 μm. In the evaluation tests described below, the uncured resin film was used after the PET film was peeled off from the uncured resin film produced on the PET film.

[0287] Evaluation of thermosetting resin compositions

[0288] The thermosetting resin compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated as shown below. The results are summarized and presented in Tables 1 to 3.

[0289] <Transparency of varnish>

[0290] The methoxybenzene solution was prepared using the proportions shown in Tables 1 to 3 to form a varnish (varnish 1) with a non-volatile content of 50% by mass. The transparency of the prepared varnish 1 was evaluated under the following two conditions, with ○ indicating that both conditions were met and × indicating otherwise.

[0291] No dissolved residue or turbidity was observed visually.

[0292] • When varnish 1 is placed in a quartz unit and the transmittance of orthorectified light with a path length of 1 mm and a wavelength of 740 nm is measured using a U-4100 spectrophotometer (manufactured by Hitachi High-Tech Science Co., Ltd.), the transmittance of orthorectified light is greater than 50%.

[0293] <Appearance of hardened material>

[0294] Using a vacuum molding machine, the aforementioned uncured resin film was cured at 250°C for 2 hours to harden it, and the appearance of the resulting cured resin film was visually confirmed. A film with no uneven curing and a uniform overall color was designated as ○, while a film with uneven curing or separation, resulting in localized color differences, was designated as ×.

[0295] <Dielectric properties (relative permittivity Dk, dielectric tangent Df)>

[0296] The uncured resin film was cured at 250°C for 2 hours using a vacuum molding machine to obtain a cured resin film. The resin film was then cut into pieces 60 mm long, 2 mm wide, and 0.3 mm thick and used as test pieces. The dielectric properties (relative permittivity Dk, dielectric tangent Df) were then measured using the cavity resonance perturbation method. The measuring instrument was an ADMSO10c1 vector network analyzer manufactured by AET Corporation, and the cavity resonator was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd. The conditions were set to a frequency of 10 GHz and a measurement temperature of 25°C.

[0297] <Glass Transfer Temperature>

[0298] Using a vacuum molding machine, the aforementioned uncured resin film was cured at 250°C for 2 hours to obtain a cured resin film.

[0299] The dynamic viscoelasticity of the bismaleimide curing material prepared in the above manner was measured using a dynamic viscoelasticity measuring device (DMA) (TA Instruments RSA-G2) (frequency 1 Hz, pull mode, heating rate 3 °C / min), and the glass transition temperature was obtained from the maximum value of the loss tangent (tanδ).

[0300] Copper foil adhesion

[0301] First, at 80°C, the aforementioned uncured resin film is laminated onto an E-glass plate measuring 80mm in length, 25mm in width, and 1mm in thickness. Next, a 12μm thick ultra-low roughness electrolytic copper foil (CF-T4X-SV (trade name), manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) is placed on the surface of the glass plate where the uncured resin film is laminated. Vacuum molding is then performed for 120 minutes at a pressure of 1MPa and a temperature of 250°C to obtain a copper-clad laminate bonded to the glass plate with a cured resin film in between. The glass plate is then fixed, and the copper foil is continuously peeled off in 50mm increments at a speed of 50mm per minute using the method described in JIS C6481:1996. The minimum load during this process is defined as the tensile strength, and the adhesion force between the copper foil and the resin is defined as the tensile strength.

[0302] [Table 1]

[0303]

[0304] [Table 2]

[0305]

[0306] [Table 3]

[0307]

[0308] In the thermosetting resin compositions of Examples 1 to 9, which combined the bismaleimide compounds of Synthetic Examples 1 to 6 with the thermosetting resin, no dissolution residue or turbidity was observed in the varnish, and the resulting cured resin film exhibited a uniform overall color. On the other hand, in the thermosetting resin compositions of Comparative Examples 1 to 3, which combined the bismaleimide compounds of Comparative Examples 1 to 3 with the thermosetting resin, dissolution residue or turbidity occurred in the varnish, and uneven curing or separation occurred in the resulting cured resin film. Therefore, it can be confirmed that the thermosetting resin compositions of the present invention have good compatibility with the thermosetting resin.

[0309] From the results shown in Tables 1 to 3, it can be seen that the thermosetting resin composition of the present invention has a high glass transition temperature, excellent dielectric properties, excellent adhesion to metal foil, good compatibility with other resins, and uniform curing without uneven curing. Therefore, it can be confirmed that the composition of the present invention is suitable for use in adhesives, substrate materials, primers, coatings, and semiconductor devices.

[0310] This application claims priority based on Japanese Patent Application No. 2023-046184, filed on March 23, 2023.

Claims

1. A thermosetting maleimide resin composition comprising (I) a bismaleimide compound and (II) a reaction accelerator, The aforementioned (I) bismaleimide compound is a bismaleimide compound with cyclic imide bonds obtained by reacting an aromatic diamine (A) represented by the following formula (1) with a tetrabasic acid dianhydride (C) and maleic anhydride. In formula (1), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms; l independently represents an integer from 1 to 4.

2. The thermosetting maleimide resin composition according to claim 1, further comprising: (III) a thermosetting resin having at least one group selected from epoxy, maleimide, hydroxyl, acid anhydride, alkenyl, (meth)acrylic acid, thiol, cyano, phenolic, oxetane, benzoxazine, and carbodiimide as a reactive group capable of reacting with the maleimide group.

3. The thermosetting maleimide resin composition according to claim 1 or 2, wherein the aforementioned (I) bismaleimide compound is a bismaleimide compound obtained by reacting a divalent organic diamine (B) with 6 to 200 carbon atoms other than the aforementioned aromatic diamine (A), the aforementioned tetrabasic acid dianhydride (C), and the aforementioned maleic anhydride.

4. The thermosetting maleimide resin composition according to claim 3, wherein the aforementioned (I) bismaleimide compound is represented by the following general formula (2), In equation (2), m is 1 to 100 and n is 0 to 100; furthermore, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block or random; C independently represents a tetravalent organic group containing a cyclic structure; W is A or B; B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms; A independently represents a divalent organic group represented by the following equation (3); In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms; l independently represents an integer from 1 to 4; and * represents a bonded part with other parts.

5. The thermosetting maleimide resin composition according to claim 1 or 2, wherein the aforementioned tetrabasic dianhydride (C) is selected from the group consisting of compounds represented by the following formulas (4) to (12). In equation (7), Y represents C(CF3)2, SO2, CO, oxygen atom, direct bond, or divalent bond group represented by equation (13) below; In equation (13), * represents the bonding part with other parts.

6. The thermosetting maleimide resin composition according to claim 1 or 2, wherein the aforementioned (I) bismaleimide compound is a maleimide derivative of an amine compound represented by the following formula (14), In formula (14), m is 1 to 100 and n is 0 to 100; in addition, the order of the repeating units enclosed in m and n is not limited, and the bonding pattern can be alternating, block or random; C independently represents a tetravalent organic group containing a cyclic structure; W is A or B; B independently represents a divalent hydrocarbon group with 6 to 200 carbon atoms; A independently represents a divalent organic group represented by the following formula (3); In formula (3), R1 independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms; l independently represents an integer from 1 to 4; and * represents a bonded part with other parts.

7. The thermosetting maleimide resin composition according to claim 1 or 2, wherein it is a (I) bismaleimide compound containing: the aforementioned tetrabasic dianhydride (C) being a compound of the following formula (15), 8. The thermosetting maleimide resin composition according to claim 1 or 2, wherein it is a (I) bismaleimide compound containing: the aforementioned tetrabasic dianhydride (C) being a compound of formula (8) below, 9. The thermosetting maleimide resin composition according to claim 1 or 2, wherein it is a (I) bismaleimide compound containing: the aforementioned tetrabasic dianhydride (C) being a compound of formula (5) below, 10. The thermosetting maleimide resin composition according to claim 1 or 2, wherein it is a (I) bismaleimide compound containing: the aforementioned tetrabasic dianhydride (C) being a compound of formula (9) below, 11. The thermosetting maleimide resin composition according to claim 1 or 2, wherein it is a (I) bismaleimide compound containing: the aforementioned tetrabasic dianhydride (C) being a compound of formula (10) below, 12. The thermosetting maleimide resin composition according to claim 2, wherein the aforementioned (III) is a thermosetting resin having at least one group selected from epoxy, maleimide, hydroxyl, acid anhydride, alkenyl, (meth)acrylic acid, thiol, cyano, phenolic, oxo, benzoxazine, and carbodiimide as a reactive group capable of reacting with the maleimide group, and is one or more of the group consisting of maleimide compounds other than the aforementioned bismaleimide compound (I), cyanate ester compounds, phenolic resins, epoxy resins, oxo resins, benzoxazine compounds, carbodiimide compounds, and compounds having vinyl unsaturated groups.

13. A sheet or film composition comprising a thermosetting maleimide resin composition according to any one of claims 1 to 12.

14. An adhesive composition comprising a thermosetting maleimide resin composition according to any one of claims 1 to 12.

15. A primer composition comprising a thermosetting maleimide resin composition according to any one of claims 1 to 12.

16. A substrate composition comprising a thermosetting maleimide resin composition according to any one of claims 1 to 12.

17. A coating composition comprising a thermosetting maleimide resin composition according to any one of claims 1 to 12.

18. A semiconductor device is a cured form of a thermosetting maleimide resin composition according to any one of claims 1 to 12.

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