Bismaleimide compound, composition containing said compound, polybenzoxazole and semiconductor element

Abstract

To provide: a novel photosensitive resin precursor that can undergo alkali development, can undergo ring closure even at a low temperature, and preferably has excellent heat characteristics and electrical characteristics after curing; and use thereof.SOLUTION: Disclosed are: a bismaleimide compound having two partial structures in a molecule, in which partial structure a carbon atom having a substituent represented by the following formula (A) (in the formula, Y represents a direct bond or a divalent linking group) and a carbon atom having a hydroxyl group are directly bonded; a polymer which is a self-polymerized polymer of the bismaleimide compound; and benzoxazole which is an intramolecular dehydration cyclization product of the polymer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Patent Application No. 2021-042386, filed with the Japan Patent Office on March 16, 2021, the entire contents of which are incorporated herein by reference. The present invention relates to a bismaleimide compound, a composition using the same, a polybenzoxazole, and a semiconductor device. The bismaleimide compound of the present invention can be used in protective films, interlayer insulating films, insulating films for rewiring layers, and the like for semiconductor devices. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance and mechanical properties, have been widely used for surface protection films, interlayer insulating films, and the like of semiconductor elements (Patent Document 1). When using polyimide resins or polybenzoxazole resins as surface protection films or interlayer insulating films, a known method is to form through-holes and the like by etching using a positive photoresist containing these resins. However, this method has the problem of requiring complicated processes such as applying and peeling off the photoresist. Therefore, heat-resistant materials that have been given photosensitivity have been investigated with the aim of streamlining the work process (Patent Document 2).

[0003] Thin films of polyimide and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, are generally obtained by thermally dehydrating and cyclizing coatings of their precursors, which typically require baking at high temperatures of around 350°C. However, next-generation memories, such as magnetoresistive random access memory (MRAM), and the resins used to encapsulate these memories are susceptible to high temperatures. Therefore, polyimide and polybenzoxazole resins used as surface protection films for such devices and as interlayer insulating films in fan-out wafer-level packages (WLPs) that form rewiring structures on the encapsulating resin are required to be cured at low temperatures of around 300°C or below, while still exhibiting properties comparable to those of conventional materials sintered at high temperatures of around 350°C.

[0004] Furthermore, conventionally used polyimide resins require the use of large amounts of organic solvents such as N-methyl-2-pyrrolidone in the development process, resulting in relatively high costs. Therefore, not only is there a need for cost reduction, but safety and recent growing environmental concerns have led to a demand for the elimination of organic solvents. In response to this demand, methods have been proposed that use various heat-resistant resin materials that can be developed (patterned) with a dilute alkaline aqueous solution, similar to photoresists. For example, methods have been proposed in which a polyamic acid is mixed with a compound having an amino group, an amide group, a urethane group, or the like, and then exposed to light in the presence of a photoinitiator and then heated (Patent Document 3), a salt of a polyamic acid and an amine compound having a phenolic hydroxyl group is mixed with quinone diazide (Patent Document 4), and a base generator such as nifedipine is mixed with a polyamic acid (Patent Document 5). All of these methods use positive-tone photosensitive compositions based on polyamic acid. While such photosensitive compositions exhibit relatively good developability, the difference in solubility between exposed and unexposed areas is small, resulting in significant film loss in the pattern and insufficient photosensitivity. Furthermore, these compositions have the drawback of having very low storage stability due to the large amount of free carboxylic acid present in the polymer main chain, which hydrolyzes the main chain over time due to the acidity of the polymer itself.

[0005] Patent Document 6 proposes a negative-type photosensitive material in which the hydroxyl groups derived from the epoxy rings generated when photosensitive groups are introduced via ester bonds by reacting glycidyl methacrylate with the carboxyl groups of polyamic acid are blocked with intramolecular cyclic acid anhydrides. However, the photosensitive material in this document also contains a large amount of free carboxylic acid in the polymer, raising concerns about poor storage stability due to the effects of hydrolysis over time of the main chain and photosensitive side chains. In addition, such photosensitive materials have various problems, such as the imidization reaction occurring when heated during the introduction of photosensitive groups, making it impossible to obtain the desired polymer.

[0006] Furthermore, the amount of data traffic from communication devices, such as smartphones, is steadily increasing, and communication frequencies are becoming higher in order to transmit data in a short time. To increase communication frequencies, it is necessary to suppress transmission loss, and materials with low dielectric constants and low dielectric loss tangents are needed. However, it has been difficult to achieve both the above-mentioned properties and dielectric properties at the same time. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 11-199557 [Patent Document 2] Japanese Patent Application Publication No. 11-24271 [Patent Document 3] Japanese Patent Application Publication No. 6-289626 [Patent Document 4] Japanese Patent Application Publication No. 6-161102 [Patent Document 5] Japanese Patent Application Publication No. 5-5995 [Patent Document 6] Special Publication No. 2-37934 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a novel bismaleimide compound. A further object of the present invention is to provide a composition, a polybenzoxazole and a semiconductor device containing the novel compound. It is still another object of the present invention to provide a compound which has excellent developability and can give a cured film (preferably a cured film having excellent thermal properties and electrical properties) even when subjected to heat treatment at a low temperature of 300°C or less (or light irradiation and heat treatment at 300°C or less). [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that by using polybenzoxazole, which is a dehydrated ring-closed product of a polymer of a bismaleimide compound (heat-resistant resin) having a specific structure, a cured film can be obtained even by heat treatment at a low temperature of 300°C or less (or by light irradiation and heat treatment at 300°C or less).

[0010] That is, the various aspects of the present invention are as follows. [1]. The following formula (A) [ka] (In the formula, Y represents a direct bond or a divalent linking group.) a carbon atom having a substituent represented by A bismaleimide compound that has two partial structures in one molecule in which a carbon atom having a hydroxyl group is directly bonded. [2]. The following formula (1) [ka] (In the formula, ring a represents a benzene ring or a cyclohexane ring. X and Y each independently represent a direct bond or a divalent linking group, and multiple Ys may be the same or different. Z represents a monovalent substituent bonded to ring a, and when multiple Zs are present, each Z may be the same or different. L and M represent the number of substituents Z, and each independently represent an integer of 0 to 3.) The bismaleimide compound according to the above item [1], represented by the formula: [3]. The bismaleimide compound according to item [2] above, wherein X is a direct bond or a divalent linking group containing at least one atom selected from the group consisting of a carbon atom, a fluorine atom, a sulfur atom, and an oxygen atom. [4]. X is a direct bond or a compound represented by the following formula (a) to (f): [ka] The bismaleimide compound according to item [3], wherein the divalent linking group is represented by any one of the following: [5]. [4] The bismaleimide compound according to any one of [1] to [4] above, wherein Y is an alkylene group having 1 to 11 carbon atoms or an alkylene group having 1 to 11 carbon atoms and containing a divalent aromatic group. [6]. A composition comprising the bismaleimide compound according to any one of items [1] to [5] above and a compound capable of reacting with a maleimide group. [7]. A composition comprising the bismaleimide compound according to any one of items [1] to [5] above, and a photopolymerization initiator or a curing catalyst. [8]. The following formula (2) [ka] (In the formula, X, Y, Z, L, M, and ring a have the same meanings as X, Y, Z, L, M, and ring a in formula (1) described in the preceding paragraph [1].) A polymer having 2 to 150 structural units represented by the following formula: [9]. The following formula (3) [ka] (In the formula, X, Y, Z, L, M, and ring a have the same meanings as X, Y, Z, L, M, and ring a in formula (1) described in the preceding paragraph [1].) A polybenzoxazole having 2 to 150 structural units represented by the following formula:

[10] . A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film for a rewiring layer, which contains the polybenzoxazole according to the above item [9].

[11] . A dry film resist obtained by sandwiching a composition containing the bismaleimide compound according to any one of items [1] to [5] above and a photopolymerization initiator between substrates. [Effects of the Invention]

[0011] The composition containing the compound of the present invention can be developed with an alkaline aqueous solution, and by using the composition, a cured film can be obtained even by heat treatment at a low temperature of 300° C. or less (or by light irradiation and heat treatment at 300° C. or less). Furthermore, the cured film according to a preferred embodiment of the present invention has excellent thermal and electrical properties. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. The bismaleimide compound of the present invention (hereinafter also simply referred to as "the compound of the present invention") is characterized in that it has, in one molecule, two partial structures in which a carbon atom having a substituent represented by the following formula (A) is directly bonded to a carbon atom having a hydroxyl group:

[0013] [ka]

[0014] In formula (A), Y represents a direct bond or a divalent linking group. The divalent linking group represented by Y in formula (A) is not particularly limited, but is preferably an alkylene group having 1 to 11 carbon atoms or an alkylene group containing a divalent aromatic group having 1 to 11 carbon atoms. The divalent alkylene group referred to here is not limited to a linear one, and may be a branched or cyclic divalent alkylene group.

[0015] From the viewpoints of film properties and solubility, the divalent linking group represented by Y in formula (A) is more preferably an alkylene group having 1 to 11 carbon atoms, even more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 5 carbon atoms or an alkylene group represented by the following formula (g), and most preferably an alkylene group represented by the following formula (g): The direct bond represented by Y in formula (A) is a structure in which the nitrogen atom in the maleimide ring and the carbon atom in the carbonyl group shown in formula (A) are directly bonded by a single bond without any intervening atoms.

[0016] [ka]

[0017] The direct bond between the carbon atom having a substituent represented by formula (A) and the carbon atom having a hydroxyl group may be any of a single bond, a double bond, or a carbon-carbon bond accompanied by resonance in an aromatic compound or the like. The partial structure represented by formula (A) in which a carbon atom having a substituent and a carbon atom having a hydroxyl group are directly bonded by a single bond is a tetravalent linking group represented by formula (B) below, and the partial structure represented by formula (A) in which a carbon atom having a substituent and a carbon atom having a hydroxyl group are directly bonded by a double bond is a divalent linking group represented by formula (C) below. Furthermore, an example of a partial structure represented by formula (A) in which a carbon atom having a substituent and a carbon atom having a hydroxyl group are directly bonded by a carbon-carbon bond involving resonance is shown in formula (D) below. In formula (D), Ar is an aromatic ring.

[0018] [ka]

[0019] The direct bond between the carbon atom having a substituent represented by formula (A) and the carbon atom having a hydroxyl group is preferably a single bond or a carbon-carbon bond accompanied by resonance in aromatic compounds, etc. It is more preferred that two adjacent carbon atoms on a cycloring each have a substituent represented by formula (A) and a hydroxyl group, or that two adjacent carbon atoms on an aromatic ring each have a substituent represented by formula (A) and a hydroxyl group. It is even more preferred that two adjacent carbon atoms on a cyclohexane ring each have a substituent represented by formula (A) and a hydroxyl group, or that two adjacent carbon atoms on a benzene ring each have a substituent represented by formula (A) and a hydroxyl group. That is, an example of a preferred compound of the present invention is a compound represented by formula (1) below.

[0020] [ka]

[0021] In formula (1), ring a represents a benzene ring or a cyclohexane ring. That is, the bismaleimide compound represented by formula (1) is a compound having a skeleton in which two benzene rings are bonded together via a direct bond or a divalent linking group, or two cyclohexane rings are bonded together via a direct bond or a divalent linking group. In formula (1), X and Y each independently represent a direct bond or a divalent linking group, and multiple Ys may be the same or different. The divalent linking group represented by X in formula (1) is not particularly limited, and examples thereof include a Group 16 element such as an oxygen atom, a methylene group (methanediyl group), an ethane-1,2-diyl group, an ethane-2,2-diyl group, a propane-2,2-diyl group (isopropylidene group), a propane-1,3-diyl group, a propane-2,3-diyl group, a trifluoromethylmethanediyl group, a di(trifluoromethyl)methanediyl group (hexafluoroisopropylidene group), a sulfonyl group, and a fluorenyl group. From the viewpoint of film properties and solubility, the divalent linking group represented by X in formula (1) is preferably an oxygen atom, a methylene group (methanediyl group), an ethane-1,2-diyl group, an ethane-2,2-diyl group, a propane-2,2-diyl group, a propane-1,3-diyl group, a propane-2,3-diyl group, a trifluoromethylmethanediyl group, a di(trifluoromethyl)methanediyl group, a sulfonyl group, or a fluorenyl group. An oxygen atom, a propane-2,2-diyl group, a di(trifluoromethyl)methanediyl group, or a sulfonyl group is more preferred, and a di(trifluoromethyl)methanediyl group or a sulfonyl group is even more preferred. X in formula (1) is preferably a direct bond or a divalent linking group containing one or more atoms selected from the group consisting of carbon atoms, fluorine atoms, sulfur atoms, and oxygen atoms. The "divalent linking group containing one or more atoms selected from the group consisting of carbon atoms, fluorine atoms, sulfur atoms, and oxygen atoms" referred to here is not particularly limited as long as it is a divalent linking group containing one or more of these atoms, but is more preferably a divalent linking group represented by any of the following formulas (a) to (f): That is, X in formula (1) is more preferably a direct bond or a divalent linking group represented by any one of the following formulae (a) to (f). The direct bond represented by X in formula (1) is a structure in which the two rings a specified in formula (1) are directly bonded by a single bond without any atoms or the like intervening therebetween.

[0022] [ka]

[0023] Examples of the divalent linking group represented by Y in formula (1) include the divalent linking group represented by Y in formula (A). In addition, preferred examples of the divalent linking group represented by Y in formula (1) are the same as the divalent linking group represented by Y in formula (A).

[0024] In formula (1), Z represents a monovalent substituent possessed by the benzene ring or cyclohexane ring, which is ring a. That is, of the six carbon atoms on the benzene ring or cyclohexane ring, which is ring a, three carbon atoms not substituted with the substituent represented by formula (A), a hydroxyl group, or X have the substituent Z or are bonded to a hydrogen atom. The monovalent substituent represented by Z is not particularly limited, but is preferably a halogen atom, a hydroxyl group, a nitro group, a cyano group, an aliphatic group, an aromatic group, an acetyl group, a carboxyl group, an ester group, an amide group, a trifluoromethyl group, an imide group, or a urea group. When multiple Zs are present, each Z may be the same or different. L and M represent the number of substituents Z, and each independently represent an integer of 0 to 3, preferably an integer of 0 or 1. Specific examples of the halogen atom, which is a preferred embodiment of Z in formula (1), include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, of which a fluorine atom is preferred. The aliphatic group, which is a preferred embodiment of Z in formula (1), is a residue obtained by removing one hydrogen atom from a non-aromatic hydrocarbon compound. The hydrocarbon compound is not limited to being linear, branched, or cyclic, and may be a compound having a plurality of these shapes. Specific examples of the aliphatic group that is a preferred embodiment of Z in formula (1) include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and cyclohexane, alkenyl groups having 1 to 6 carbon atoms such as propene, and alkynyl groups having 1 to 6 carbon atoms such as propyne, etc. Of these, a methyl group is preferred.

[0025] The aromatic group, which is a preferred embodiment of Z in formula (1), is a residue obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound. The aromatic compound is not limited to any of aromatic hydrocarbon compounds, heterocyclic compounds, and heterocyclic fused aromatic compounds, as long as it has aromaticity. Specific examples of the aromatic group that is a preferred embodiment of Z in formula (1) include a phenyl group and a naphthyl group, among which a phenyl group is preferred. Specific examples of the ester group, which is a preferred embodiment of Z in formula (1), include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propylcarbonyl group, a benzyloxycarbonyl group, and a phenoxycarbonyl group, of which the phenoxycarbonyl group is preferred. Specific examples of the amide group, which is a preferred embodiment of Z in formula (1), include alkylamide groups such as -CONH, -CONH(CH), and -CONH(i-C3H), and arylamide groups such as benzamide, naphthamide, pt-butylbenzamide, o-chlorobenzamide, and -CON(Ph). Of these, benzamide is preferred. In this specification, Ph represents a phenyl group. As Z in formula (1), an aliphatic group is more preferred because it readily undergoes dehydration and ring closure at low temperatures.

[0026] Although there are no particular limitations on the method for producing the compound of the present invention, a common method involves converting maleimide carboxylic acid into a halide derivative using a halogenating agent, and then reacting the halide derivative with a diaminodiphenol compound or a cyclohexane ring compound obtained by hydrogenating the benzene ring of a diaminodiphenol compound (hereinafter referred to as a diaminodiphenol compound or a hydrogenated product thereof). In the reaction between the halide derivative and the diaminodiphenol compound or a hydrogenated product thereof, it is preferable to use a halide derivative in a molar amount of 2 to slightly more than 2 times the molar amount of the diaminodiphenol compound or a hydrogenated product thereof. The halide derivative is preferably a chloride derivative. Examples of halogenating agents used in converting maleimidocarboxylic acid to a chloride derivative include thionyl chloride, oxalyl chloride, phosphoryl chloride, and phosphorus chloride, which are used in ordinary acid chlorination reactions. The maleimide carboxylic acid may be synthesized from the amino acid by a known method, or a commercially available product may be used.

[0027] Examples of maleimide carboxylic acids used in producing the compound of the present invention include, but are not limited to, the following compounds Nos. 1 to 4. These maleimide carboxylic acids can be used alone or in combination of two or more.

[0028] [ka]

[0029] Examples of diaminodiphenol compounds or hydrogenated products thereof used in producing the compound of the present invention include, but are not limited to, the following compounds Nos. 5 to 12 and cyclohexane ring compounds obtained by hydrogenating the benzene ring in compounds Nos. 5 to 12. These diaminodiphenol compounds or hydrogenated products thereof can be used alone or in combination of two or more.

[0030] [ka]

[0031] The reaction of a halide derivative with a diaminodiphenol compound or its hydrogenated product is preferably carried out in an organic solvent in the presence of a dehalogenating agent. Examples of suitable dehalogenating agents include organic bases such as pyridine, picoline, and triethylamine. Examples of suitable organic solvents include sulfolane, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N,N-dimethylformamide. The concentration of these reaction components relative to the total reaction system, including the solvent, is not particularly limited, but is preferably 20 to 80% by mass, more preferably 40 to 60% by mass. In a specific synthesis procedure, maleimidocarboxylic acid is first dissolved in an organic solvent, and a halide derivative is synthesized using a halogenating agent. Subsequently, a diaminodiphenol compound or its hydrogenated product is added in the presence of a dehalogenating agent. The temperature at which the diaminodiphenol compound or its hydrogenated product is added is preferably −20 to 25°C, more preferably 0 to 20°C. The reaction temperature for the reaction between the halide derivative and the diaminodiphenol compound or its hydrogenated product is preferably 0 to 80°C, more preferably 50 to 70°C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 8 hours. After the reaction is complete, the target compound can be obtained by adding water to the resulting reaction solution. The compound obtained by the above procedure can be treated with an acidic aqueous solution, an alkaline aqueous solution, a neutral aqueous solution, and further with an organic solvent or the like to remove impurities.

[0032] Next, the polymer of the present invention will be described. The compound represented by formula (1) of the present invention can be a polymer (self-polymer) formed by self-polymerization of the compound represented by formula (1) via maleimide groups at both ends, or a polymer (copolymer) formed by copolymerization of the compound represented by formula (1) with a compound capable of reacting with maleimide groups, and can be the polymer of the present invention having a structural unit represented by formula (2) below. That is, the self-polymer has a structure in which unit structures represented by formula (2) below are directly bonded. Furthermore, the copolymer has a structure in which unit structures represented by formula (2) below are bonded via a linking group other than formula (2). The number of unit structures represented by formula (2) in the polymer of the present invention is not particularly limited, but is preferably 2 to 150. In addition, X, Y, Z, L, M and ring a in the unit structure represented by formula (2) have the same meanings as X, Y, Z, L, M and ring a in formula (1), and preferred ones are also the same as preferred ones in formula (1).

[0033] [ka]

[0034] The compound represented by formula (1) can typically be self-polymerized simply by heating at 40 to 150°C for about 30 to 300 minutes. The conditions for self-polymerization are not particularly limited, as long as they are the conditions typically used for reacting maleimide groups together. Under relatively mild heating conditions, for example, at 50 to 70°C for about 60 to 180 minutes, a mixture of the compound represented by formula (1) as the main component and the self-polymerized product is obtained. Under relatively severe heating conditions, for example, at 80 to 120°C for 30 to 120 minutes, a mixture of the compound represented by formula (1) as the main component and the self-polymerized product is obtained. The ratio of the compound represented by formula (1) to the self-polymerized product in the mixture affects handling and other aspects when the mixture is subjected to subsequent steps, so the ratio (reaction conditions) of the two can be selected taking handling and other factors into consideration. Even in a mixture containing the compound represented by formula (1) as the main component, self-polymerization occurs due to heating during the ring-closure reaction for benzimidazolization. Therefore, the component composition of the mixture is unlikely to have an undesirable effect on the physical properties of the final polybenzimidazole.

[0035] The compound represented by formula (1) can self-polymerize by itself, but it can also be self-polymerized by combining the compound represented by formula (1) with a photopolymerization initiator or a curing catalyst to form a composition. The use of a photopolymerization initiator makes it possible to self-polymerize by irradiation with light. Furthermore, the use of a curing catalyst can reduce the heating temperature during self-polymerization compared to when no curing catalyst is used.

[0036] The photopolymerization initiator that can be used in combination with the self-polymerization is not particularly limited, and conventionally used ones can be appropriately adopted. Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxyacetophenone, p-dimethylaminoacetophenone, Michler's ketone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzil dimethyl ketal, thioxathon, 2-chlorothioxathon, 2-methylthioxathon, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 2,4-diethylthioxanthone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

[0037] Among these, it is preferable to use a compound that efficiently generates radicals at an exposure wavelength of 310 to 436 nm (more preferably 365 nm) from the viewpoint that fine patterns can be formed using a stepper (light source wavelength: 365 nm, 436 nm) that is standardly used in the manufacturing process of semiconductor protective films, etc. Preferred examples of the photopolymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (manufactured by BASF Japan, "IRGACURE OXE-01"), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (manufactured by BASF Japan, "IRGACURE OXE-02"), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S"), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins BV, "Omirad 907"). The amount of the photopolymerization initiator used (when used) is preferably 0.1 to 20 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the compound represented by formula (1).

[0038] The photopolymerization initiator may be used in combination with a sensitizer. The sensitizer that can be used in combination is not particularly limited as long as it is a conventionally known sensitizer, and examples thereof include 4,4'-bis(diethylamino)benzophenone. The amount of the sensitizer used (if used) is preferably 2 parts by mass or less, more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the compound represented by formula (1). By using a sensitizer in combination, the sensitivity to light during self-polymerization can be increased.

[0039] The curing catalyst that can be used in combination during self-polymerization is not particularly limited as long as it can promote the self-polymerization of the maleimide groups at both ends of the compound represented by formula (1) of the present invention by heating, and conventionally used catalysts can be appropriately adopted. Specific examples of the curing catalyst include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine; triphenylphosphine; tributylphosphine; organic metal salts such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Lewis acids such as boron trifluoride; and salts such as sodium carbonate and lithium chloride. The amount of the curing catalyst used (if used) is preferably 10 parts by weight or less, more preferably 1 to 5 parts by weight, per 100 parts by weight of the compound represented by formula (1).

[0040] Compounds that can react with a maleimide group and are used for copolymerization with the compound represented by formula (1) include compounds having multiple unsaturated double bonds, such as acrylic groups, methacrylic groups, allyl groups, and styryl groups. Copolymerization using these compounds in combination with light irradiation is a preferred embodiment because it can increase sensitivity to light, and polyfunctional acrylates are more preferred because they facilitate crosslinking reactions by photopolymerization.

[0041] Specific examples of compounds having multiple acrylic groups include hydrogenated dicyclopentadienyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, and diethylene glycol diacrylate. Examples of the hydroxypivalic acid ester include bis(acryloxyethoxy)bisphenol A, bis(acryloxyethoxy)tetrabromobisphenol A, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol monohydroxypentaacrylate.

[0042] Specific examples of compounds having a plurality of methacrylic groups include compounds in which the acrylic groups in the above-mentioned compounds having a plurality of acrylic groups are replaced with methacrylic groups. Specific examples of compounds having a plurality of allyl groups include diallyl adipate, diallyl fumarate, diallyl hexahydrophthalate, pentaerythritol tetraallyl ether, glycerol diallyl ether, and triallyl citrate. Specific examples of compounds having multiple styryl groups include bis(vinylphenyl)methane, bis(vinylphenyl)ethane, and bis(vinylphenyl)hexane.

[0043] The ratio of the compound represented by formula (1) to the compound capable of reacting with a maleimide group used in copolymerization is not particularly limited, but can be appropriately adjusted depending on the molecular weight of the compound capable of reacting with a maleimide group, the number of polymerizable functional groups, etc. For example, the amount of the compound capable of reacting with a maleimide group per mole of the compound represented by formula (1) is preferably 0.01 to 10 moles, more preferably 0.1 to 1 mole. Copolymerization may be carried out under the same conditions as those for self-polymerization, and may also be carried out using a photopolymerization initiator, a sensitizer, or a curing catalyst in combination. The methods for using these are the same as those described in the section on self-polymerization.

[0044] The polybenzoxazole of the present invention is an intramolecular dehydration ring-closure product of the above-mentioned polymer (self-polymer and copolymer) of the present invention, and has a unit structure represented by the following formula (3). In addition, X, Y, Z, L, M and ring a in the unit structure represented by formula (3) have the same meanings as X, Y, Z, L, M and ring a in formula (1), and preferred ones are also the same as preferred ones in formula (1). Throughout this specification and the appended claims, for convenience, the intramolecular dehydration ring-closure products of polymers having a unit structure represented by formula (3) will be collectively referred to as "polybenzoxazole", including not only the case where ring a is a benzene ring but also the case where the benzene ring is hydrogenated to form a cyclohexane ring.

[0045] [ka]

[0046] The conditions for dehydrating and cyclizing the polymer of the present invention are not particularly limited, as long as they are conditions typically used for converting a benzoxazole precursor into benzoxazole by dehydration and cyclization. The dehydration and cyclization can be carried out using, for example, a hot plate, an oven, or a temperature-programmable heating oven. The atmospheric gas used for the thermal conversion may be air, or an inert gas such as nitrogen or argon. The dehydration ring-closure reaction of the polymer of the present invention can be advantageously carried out at a low temperature of not more than 300° C. The temperature of the dehydration ring-closure reaction may be preferably less than 300° C., more preferably not more than 290° C.

[0047] The composition of the present invention may contain a bismaleimide compound having two partial structures in one molecule, each of which has a carbon atom having a substituent and a carbon atom having a hydroxyl group directly bonded, as represented by formula (A), or a component other than the bismaleimide compound represented by formula (1). Examples of other components that may be contained in the composition of the present invention include organic solvents, photopolymerization initiators, thermoplastic resins, colorants, thickeners, thermal polymerization inhibitors, antifoaming agents, leveling agents, curing agents or curing catalysts having a reactive group capable of reacting with a maleimide group, and adhesion enhancers such as coupling agents. Various other components may also be used without particular limitation depending on the intended use and method of use of the composition. Compositions containing organic solvents are preferred because of their ease of handling. Furthermore, the compound of the present invention can undergo a self-polymerization reaction and therefore can be used without using a photopolymerization initiator, a curing agent, a curing catalyst, or the like.

[0048] The curing agent is not particularly limited, and conventionally used compounds can be appropriately used. The curing agent is not particularly limited as long as it is a compound having a functional group (or structure) capable of crosslinking with a maleimide group, such as an amino group, a cyanate group, a phenolic hydroxyl group, or an alcoholic hydroxyl group. In addition, a bismaleimide compound other than the bismaleimide compound of the present invention may be used in combination.

[0049] The organic solvent is not particularly limited, but examples thereof include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methyl amyl ketone. These organic solvents can be used alone or in combination of two or more. The use of organic solvents in combination is a preferred embodiment in that it improves the handleability of the composition. The content of the organic solvent in the composition of the present invention is not particularly limited, but is usually 95% by mass or less, preferably 20 to 90% by mass, based on the total weight of the composition.

[0050] The coupling agent is not particularly limited, but may typically be a silane coupling agent. Examples of silane coupling agents include, but are not limited to, 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. These may be used alone or in combination of two or more. Because silane coupling agents are unreactive with the compounds of the present invention (compounds, self-polymerized products, polybenzoxazole), components other than those acting at the substrate interface may remain as residual components after curing. Therefore, using large amounts of adhesion enhancers may have undesirable effects, such as reduced physical properties. Depending on the type of substrate, even small amounts can be effective, so it is appropriate to use them within a range that does not cause undesirable effects. The proportion of the silane coupling agent used is usually 15% by mass or less, preferably greater than 0% by mass and less than 5% by mass, based on the total weight of the composition; however, the upper limit of the proportion may vary depending on the type of substrate.

[0051] Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of thickeners include Orben, Bentone, and montmorillonite. Examples of the thermal polymerization inhibitor include hydroquinone and 2,6-di-tert-butyl-p-methylphenol. Examples of the antifoaming agent include silicone-based, fluorine-based and polymer-based antifoaming agents. The amount of these additives used (when used) in the composition of the present invention is preferably 30% by mass or less, for example, as a rough guide, but this amount can be increased or decreased as appropriate depending on the purpose of use.

[0052] The composition of the present invention may contain inorganic fillers such as barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc. The blending ratio of the inorganic filler (if used) in the composition of the present invention is preferably 60 mass % or less.

[0053] A cured film of a heat-resistant resin formed from the polybenzoxazole of the present invention can be used in electronic components such as semiconductor devices and multilayer wiring boards, and organic EL display devices. Specifically, this cured film is suitable for applications such as a passivation film for semiconductors, a surface protection film for semiconductor elements, an interlayer insulating film, an interlayer insulating film for multilayer wiring for high-density packaging, an insulating film for redistribution layers, an interlayer insulating film for electronic components such as inductors and SAW filters, and an insulating film or planar layer for organic electroluminescent devices, but is not limited thereto and can have a variety of structures.

[0054] The compound and composition of the present invention can also be used in the form of a dry film resist. Specifically, the compound and composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, or the like, followed by drying in a drying oven set at 45 to 140°C to remove a predetermined amount of solvent, and optionally by laminating a cover film or the like to produce a dry film resist. In this case, the thickness of the resist on the base film is adjusted to 2 to 200 μm. Examples of the base film and cover film include films made of polyester, polypropylene, polyethylene, TAC, polyimide, and the like. These films may be treated with a silicone-based release treatment agent or a non-silicone-based release treatment agent, if necessary. Supplying the composition as a dry film resist eliminates the steps of coating and drying on a substrate, making it easier to use the composition of the present invention. [Example]

[0055] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" are by mass.

[0056] Example 1 <Synthesis of compound represented by general formula (1) (compound A-1)> A 500 ml round-bottom flask equipped with a Teflon®-coated stir bar was charged with 6.76 parts (0.040 mol) of 3-maleimidopropionic acid (compound No. 1 above) and 20 parts of DMF. After cooling the mixture on ice, 10.15 parts (0.080 mol) of oxalyl chloride was slowly added and the mixture was stirred at room temperature for 2 hours. Next, a solution of 7.33 parts (0.020 mol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) (compound No. 5 above) in 10 parts of DMF was added and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, 300 parts of water was added and the precipitated solid was collected by filtration. The solid obtained above was dissolved in 30 parts of cyclopentanone, and then washed with 10 parts of dilute hydrochloric acid and then with 10 parts of water to remove unreacted raw materials. The organic layer was concentrated under vacuum to obtain 5.3 parts of a compound A-1 solution (solid content 40%) (yield 16%).

[0057] [ka]

[0058] Example 2 <Synthesis of compound represented by general formula (1) (compound A-2)> A 500 ml round-bottom flask equipped with a Teflon®-coated stir bar was charged with 8.44 parts (0.040 mol) of 6-maleimidohexanoic acid (compound No. 2 above) and 20 parts of DMF. After ice-cooling the mixture, 10.15 parts (0.080 mol) of oxalyl chloride was slowly added and the mixture was stirred at room temperature for 2 hours. Next, a solution of 7.33 parts (0.020 mol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) (compound No. 5 above) in 10 parts of DMF was added and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, 300 parts of water was added and the precipitated solid was collected by filtration. The solid obtained above and 100 parts of methanol were placed in a flask and stirred and washed at 40°C. Cyclopentanone was then added and the mixture was concentrated under vacuum to obtain 22.5 parts of Compound A-2 solution (solids content 68%) (yield 47%).

[0059] [ka]

[0060] Example 3 <Synthesis of compound represented by general formula (1) (compound A-3)> A 500 ml round-bottom flask equipped with a Teflon®-coated stir bar was charged with 9.50 parts (0.040 mol) of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid (compound No. 4 above) and 20 parts of DMF. After ice-cooling the mixture, 10.15 parts (0.080 mol) of oxalyl chloride was slowly added and the mixture was stirred at room temperature for 2 hours. Next, a solution of 7.33 parts (0.020 mol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) (compound No. 5 above) in 10 parts of DMF was added and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, 300 parts of water was added and the precipitated solid was collected by filtration. The solid obtained above was dissolved in 180 parts of cyclopentanone, and then washed three times with 60 parts of dilute hydrochloric acid and once with 60 parts of sodium bicarbonate water to remove unreacted raw materials. The organic layer was then concentrated under vacuum to obtain 31 parts of a compound A-3 solution (solid content 40%) (yield 77%).

[0061] [ka]

[0062] Example 4 <Synthesis of compound represented by general formula (1) (compound A-4)> A 500 ml round-bottom flask equipped with a Teflon®-coated stir bar was charged with 8.44 parts (0.040 mol) of 6-maleimidohexanoic acid (compound No. 2 above) and 20 parts of DMF. After ice-cooling the mixture, 10.15 parts (0.080 mol) of oxalyl chloride was slowly added and stirred at room temperature for 2 hours. Next, a solution of 4.33 parts (0.020 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl (compound No. 6 above) in 10 parts of DMF was added and stirred at 60°C for 3 hours. After cooling to room temperature, 300 parts of water was added and the precipitated solid was collected by filtration. The resulting solid and 100 parts of methanol were placed in a flask and stirred and washed at 40°C. The unreacted raw materials were removed and the solid was collected by filtration, yielding 9.6 parts of compound A-4 (80% yield).

[0063] [ka]

[0064] Example 5 <Synthesis of compound represented by general formula (1) (compound A-5)> A 500 ml round-bottom flask equipped with a Teflon®-coated stir bar was charged with 9.49 parts (0.040 mol) of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid (compound No. 4 above) and 20 parts of DMF. After ice-cooling the mixture, 10.15 parts (0.080 mol) of oxalyl chloride was slowly added and the mixture was stirred at room temperature for 2 hours. Next, a solution of 4.33 parts (0.020 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl (compound No. 6 above) in 10 parts of DMF was added and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, 300 parts of water was added and the precipitated solid was collected by filtration. The resulting solid and 100 parts of methanol were added to a flask and stirred at 40°C. The solid was then collected by filtration to remove unreacted raw materials, yielding 4.0 parts of compound A-5 (30% yield).

[0065] [ka]

[0066] Example 6 <Synthesis of compound represented by general formula (1) (compound A-6)> A 500 mL round-bottom flask equipped with a Teflon-coated stir bar was charged with 19.3905 g (0.0918 mol) of 6-maleimidohexanoic acid (compound No. 2 above) and 44.6085 g of NMP. After cooling the mixture on ice, 12.5655 g (0.1056 mol) of thionyl chloride was slowly added and stirred at 5°C or below for 30 minutes. A solution of 7.9046 g (0.0306 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (compound No. 7 above), 0.019 g of BHT, 10.4572 g of NMP, and 7.1202 g of picoline was then added and stirred for 50 minutes. After 50 minutes, the entire solution was slowly added dropwise to 1000 g of water to obtain the desired solid. The solid was then dissolved in 80 g of acetone, and the entire solution was slowly added dropwise to 1000 g of water to reprecipitate. The solid was dried under vacuum and stored in a can, and the amount of the obtained solid (compound A-6) was 16.77 g, and the yield was 85%.

[0067] [ka]

[0068] Example 7 <Synthesis of compound represented by general formula (1) (compound A-7)> A 500 mL round-bottom flask equipped with a Teflon-coated stir bar was charged with 18.9922 g (0.0800 mol) of 4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid (compound No. 4 above) and 83.72 g of NMP. After cooling the mixture on ice, 20.40 g (0.1600 mol) of thionyl chloride was slowly added and stirred at 5°C or below for 30 minutes. A solution of 12.2114 g (0.040 mol) of bis(3-amino-4-hydroxyphenyl)sulfone (compound No. 8 above), 0.019 g of BHT, 12.9168 g of NMP, and 10.13 g of picoline was then added and stirred for 50 minutes. After 50 minutes, the entire solution was slowly added dropwise to 1000 g of water to obtain the desired solid. The solid was then dissolved in 80 g of acetone, and the entire solution was slowly added dropwise to 1000 g of water to reprecipitate. The solid was dried under vacuum and stored in a can, and the amount of the obtained solid (compound A-7) was 15.00 g, and the yield was 52%.

[0069] [ka]

[0070] Example 8 <Synthesis of compound represented by general formula (1) (compound A-8)> A 500 mL round-bottom flask equipped with a Teflon-coated stir bar was charged with 19.3905 g (0.0918 mol) of 6-maleimidohexanoic acid (compound No. 2 above) and 44.6085 g of NMP. After cooling the mixture on ice, 12.5655 g (0.1056 mol) of thionyl chloride was slowly added and stirred at 5°C or below for 30 minutes. A solution of 8.5776 g (0.0306 mol) of bis(3-amino-4-hydroxyphenyl)sulfone (compound No. 8 above), 0.019 g of BHT, 10.4572 g of NMP, and 7.1202 g of picoline was then added and stirred for 50 minutes. After 50 minutes, the entire solution was slowly added dropwise to 1000 g of water to obtain the desired solid. The solid was then dissolved in 80 g of acetone, and the entire solution was slowly added dropwise to 1000 g of water to reprecipitate. The solid was dried under vacuum and stored in a can, and the amount of the obtained solid (compound A-8) was 20.40 g, and the yield was 76%.

[0071] [ka]

[0072] Example 9 (Evaluation of the intramolecular (dehydration) ring closure temperature of the compound of the present invention) The intramolecular (dehydration) ring-closure temperatures of the compounds (A-1) to (A-8) obtained in Examples 1 to 8 were measured in nitrogen at a heating rate of 10°C / min using a differential scanning thermogravimeter (TG / DTA6200 manufactured by Seiko Instruments Inc.) The intramolecular (dehydration) ring-closure temperatures of the compounds (A-1) to (A-8) were all less than 300°C.

[0073] Examples 10 to 17 (Preparation of Compositions of the Present Invention) The components were blended in the amounts shown in Table 1 to prepare compositions of the present invention.

[0074] Comparative Example 1 (Preparation of the composition of Comparative Example 1) A comparative composition was prepared by blending the components in the amounts shown in Table 1. The bismaleimide compound C-1 was synthesized by a known method using the technique described in patent document US Pat. No. 5,973,166A.

[0075] [ka]

[0076] The components used in the compositions of Examples 10 to 17 and Comparative Example 1 shown in Table 1 are as follows. A-1 to A-8: Bismaleimide compounds A-1 to A-8 obtained in Examples 1 to 8 C-1: Bismaleimide compound C-1 Photopolymerization initiator 2-1: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (BASF Japan, "IRGACURE OXE-02") Photopolymerization initiator 2-2: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., "DETX-S")

[0077] (Preparation of Polymer Films and Polybenzoxazole Films of the Present Invention and Comparative Cured Films) The compositions obtained in each of Examples 10 to 17 were applied to copper foil having a thickness of 18 μm using an applicator, and then dried at 100° C. for 120 minutes to form a composition layer having a thickness of 20 μm on the copper foil. The composition layer on the copper foil thus obtained was exposed to light at a wavelength of 365 nm using a conveyor UV irradiation device CS30L-1-1 manufactured by GS Yuasa Corporation at an exposure dose of 1000 mJ / cm. 2 The film was then heated at 150°C for 60 minutes to obtain a film of the cured polymer of the present invention on the copper foil. This polymer film was then heated at 300°C for 60 minutes to cause a ring-closing reaction, thereby obtaining a polybenzoxazole film of the present invention on the copper foil. The copper foil was then removed by etching to obtain a polybenzoxazole film of the present invention separated from the copper foil. Furthermore, using the composition obtained in Comparative Example 1, a comparative cured film was obtained which was separated from the copper foil in the same manner as above.

[0078] (Dielectric properties of polybenzoxazole film and comparative cured film: Evaluation of dielectric constant Dk and dielectric loss tangent Df) Each polybenzoxazole film obtained above was cut into a length of 60 mm and a width of 3 mm, and multiple pieces were stacked to prepare polybenzoxazole film test pieces with thicknesses of 50 to 300 μm. The resulting polybenzoxazole film test pieces were dried for 12 hours in a desiccator filled with silica gel, and the dielectric properties, namely, the permittivity Dk and the dielectric loss tangent Df, were measured by the cavity resonator perturbation method using an AET vector network analyzer ADMSO10c1 and a Kanto Electronics Application Development Co., Ltd. CP531 (10 GHz band resonator) cavity resonator. The measurement conditions were a frequency of 10 GHz and a temperature of 25°C. The dielectric properties of a comparative cured film were also measured in the same manner. The results are shown in Table 1.

[0079] (Evaluation of 5% weight loss temperature of polybenzoxazole film and comparative cured film) The weight loss temperature of each of the polybenzoxazole films prepared according to the above "Preparation of Polybenzoxazole Films of the Present Invention" was measured using a differential scanning thermogravimeter (TG / DTA6200, manufactured by Seiko Instruments Inc.) in nitrogen at a temperature increase rate of 10°C / min to determine the 5% weight loss temperature. Similarly, the 5% weight loss temperature of a comparative cured film was also measured. The results are shown in Table 1.

[0080] (Evaluation of the glass transition temperature (Tg) of polybenzoxazole films and comparative cured films) The dynamic viscoelasticity of each of the polybenzoxazole films prepared according to the above "Preparation of Polybenzoxazole Films of the Present Invention" was measured using a dynamic viscoelasticity analyzer (DMA) (RSA-G2, manufactured by TA Instruments) (frequency 1 Hz, tensile mode, heating rate 3°C / min), and the glass transition temperature was determined from the maximum value of the loss tangent (tanδ). The glass transition temperature of a comparative cured film was also measured in the same manner. The results are shown in Table 1.

[0081] (Evaluation of Alkali Solubility of Composition) The compositions obtained in Examples 10 to 17 and Comparative Example 1 were each applied to a silicon substrate using a spin coater and then dried at 95°C for 15 minutes to form a 10 μm-thick composition layer on the silicon substrate. The resulting composition layer on the silicon substrate was immersed in 100 g of a 2.38% aqueous solution of tetramethylammonium hydroxide (Tokuso SD-1, manufactured by Tokuyama Corp.) for 5 minutes to confirm solubility. Solubility was evaluated using a three-level scale: good (◯), fair (△), and poor (×).

[0082] [Table 1]

[0083] The polymer of the present invention having a structural unit represented by formula (2) is a photosensitive polybenzoxazole precursor capable of forming a negative pattern, and an alkaline aqueous solution can be used for pattern formation. This allows for the complete elimination of industrial waste organic solvents, which have been generated in large quantities until now. Furthermore, the final polybenzoxazole film has excellent heat resistance and electrical properties, making it suitable for use in commonly used semiconductor surface protection films, interlayer insulating films, and insulating films for rewiring layers. The present invention relates to the resin skeleton itself used in the photosensitive resin composition and a method for producing the same. These are based on completely novel inventions, and it is easy to understand that they are unique and extremely excellent inventions. In view of the above detailed description of the invention, other modifications and variations will become apparent to those skilled in the art, and it is evident, however, that such other modifications and variations can be made without departing from the spirit and scope of the invention.

Claims

1. The following formula (A) 【Chemical 1】 (In the formula, Y represents an alkylene group having 1 to 11 carbon atoms or an alkylene group having 1 to 11 carbon atoms and containing a divalent aromatic group.) a carbon atom having a substituent represented by A bismaleimide compound having two partial structures in one molecule in which a carbon atom having a hydroxyl group is directly bonded, and represented by the following formula (1): 【Chemistry 2】 (In the formula, ring a represents a benzene ring or a cyclohexane ring. X represents a direct bond or a divalent linking group. A plurality of Ys represent alkylene groups having 1 to 11 carbon atoms or alkylene groups having 1 to 11 carbon atoms containing a divalent aromatic group, and may be the same as or different from each other. Z represents a monovalent substituent bonded to ring a, and when a plurality of Zs are present, each Z may be the same as or different from each other. L and M represent the number of substituents Z, and each independently represents an integer of 0 to 3.)

2. 2. The bismaleimide compound according to claim 1, wherein X is a direct bond or a divalent linking group containing at least one atom selected from the group consisting of a carbon atom, a fluorine atom, a sulfur atom, and an oxygen atom.

3. X is a direct bond or a group represented by the following formulas (a) to (f): 【Chemistry 3】 The bismaleimide compound according to claim 1 or 2, wherein the divalent linking group is represented by any one of the following:

4. The bismaleimide compound according to claim 1, wherein Y is an alkylene group having 1 to 11 carbon atoms.

5. A composition comprising the bismaleimide compound according to claim 1 and a photopolymerization initiator or a curing catalyst.

6. The following formula (2) 【Chemistry 4】 (In the formula, X, Y, Z, L, M and ring a have the same meanings as X, Y, Z, L, M and ring a in formula (1) described in claim 1.) 5. A polymer having 2 to 150 structural units represented by the following formula: wherein the polymer is a self-polymerization product of the bismaleimide compound according to claim 1 .

7. The following formula (3) 【Chemistry 5】 (In the formula, X, Y, Z, L, M and ring a have the same meanings as X, Y, Z, L, M and ring a in formula (1) described in claim 1.) 7. A polybenzoxazole having 2 to 150 structural units represented by the following formula: wherein the polybenzoxazole is an intramolecular dehydration ring-closure product of the polymer according to claim 6.

8. A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film of a rewiring layer, which contains the polybenzoxazole according to claim 7.

9. A dry film resist obtained by sandwiching a composition containing the bismaleimide compound according to claim 1 and a photopolymerization initiator between substrates.

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