Compound having cross-linked structure between aromatic rings, composition containing the compound, polybenzoxazole, and semiconductor device

Abstract

To provide a novel compound having a cross-linked structure between aromatic rings.SOLUTION: A compound comprises a structural unit represented by formula (1), wherein X denotes a direct bond or a bivalent linking group; Z denotes a monovalent substituent bonded to a ring; Y denotes a direct bond or a bivalent linking group bonded to an aromatic ring; R1 denotes a monovalent substituent or a linking group having two or more valences; and R2 denotes a monovalent substituent or a linking group having two or more valences including a nitrogen atom directly bonded to an aromatic ring.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound having a crosslinked structure between aromatic rings, a composition using the same, polybenzoxazole, and a semiconductor device. The compound having a crosslinked structure between aromatic rings of the present invention can be applied to a protective film for a semiconductor device, an interlayer insulating film, an insulating film for a rewiring layer, and the like. [Background technology]

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

[0003] Thin films of polyimide resins and polybenzoxazole resins, which have excellent heat resistance and mechanical properties, are generally obtained by thermally dehydrating and cyclizing coatings of their precursors, which usually require baking at a high temperature of around 350°C. However, next-generation memories such as MRAM (Magnetoresistive Random Access Memory) and resins used to seal these memories are weak at high temperatures. For this reason, polyimide resins and polybenzoxazole resins used in the surface protection film of such elements and the interlayer insulating film of fan-out wafer-level packages that form a rewiring structure on the sealing resin are required to be cured by baking at a low temperature of about 225°C or less and to have properties comparable to those of conventional materials baked at a high temperature of around 350°C.

[0004] In addition, conventionally used polyimide resins require the use of a large amount of organic solvents such as N-methyl-2-pyrrolidone in the development process, which makes the cost expensive. Therefore, not only the need for cost reduction but also the increasing safety and environmental concerns in recent years have led to the demand for organic solvent-free processes. In response to this, 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, such as a method of mixing polyamic acid with a compound having an amino group, an amide group, a urethane group, or the like, and heating after exposure in the presence of a photoinitiator (Patent Document 3), a method of mixing quinone diazide with a salt of polyamic acid and an amine compound having a phenolic hydroxyl group (Patent Document 4), and a method of mixing polyamic acid with a base generator such as nifedipine (Patent Document 5). All of these methods use positive-type photosensitive compositions based on polyamic acid. Although such photosensitive compositions show 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. Moreover, these compositions have the disadvantage that a large amount of free carboxylic acid is present in the polymer main chain, and the main chain is hydrolyzed over time due to the acidity of the polymer itself, resulting in extremely low storage stability.

[0005] Patent Document 6 proposes a negative photosensitive material in which the hydroxyl group derived from the epoxy ring generated when introducing a photosensitive group via an ester bond by reacting glycidyl methacrylate with the carboxyl group of a polyamic acid is blocked with an intramolecular cyclic acid anhydride. However, the photosensitive material of the same document also has a large amount of free carboxylic acid in the polymer, so there is a concern that the storage stability is low due to the influence of hydrolysis over time of the main chain and the photosensitive side chain. In addition, in such a photosensitive material, there are various problems such as the imidization reaction progressing due to heating during the introduction of the photosensitive group, making it impossible to obtain the desired polymer.

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

[0007] In addition, the shape of interlayer insulating films is becoming finer, making the resolution of photosensitive materials important. High resolution enables the miniaturization and high functionality of electronic components. [Prior art documents] [Patent documents]

[0008] [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]

[0009] An object of the present invention is to provide a novel compound having a crosslinked structure between aromatic rings. It is a further object of the present invention 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, when used with a dilute alkaline aqueous solution, provides a cured film which is excellent in developability and preferably has excellent electrical properties. [Means for solving the problem]

[0010] As a result of extensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a polymer having a crosslinked structure between specific aromatic rings.

[0011] That is, aspects of the present invention and some preferred embodiments are as follows. [1] A compound having a structural unit represented by the following general formula (1): [ka]

[0012] In formula (1), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (1), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to the aromatic ring, and when a plurality of Y's are present in the compound, the plurality of Y's may be the same or different. R1 represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R1 are present, the plurality of R1 may be the same or different. R2 represents a monovalent substituent or a divalent or higher linking group containing a nitrogen atom directly bonded to an aromatic ring, and when there are multiple R2, the multiple R2 may be the same or different from each other. [2] The compound according to [1], wherein at least one of R2 contains an amide bond. [3] The compound according to [1] or [2], wherein at least one of R1 is a hydrogen atom. [4] The compound according to any one of [1] to [3], wherein at least one of Y's is a divalent linking group represented by the following formula (2):

[0013] [ka]

[0014] [5] The compound according to any one of [1] to [4], wherein X is a divalent linking group represented by (a) to (f).

[0015] [ka]

[0016] [6] The compound according to [5], wherein X is a divalent linking group represented by (c). [7] A compound having a structural unit represented by the following formula (3), in which at least one of R2' is (g) or (h).

[0017] [ka]

[0018] In formula (3), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (3), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to the aromatic ring, and when a plurality of Y's are present in the compound, the plurality of Y's may be the same or different. R1 represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R1 are present, the plurality of R1 may be the same or different. R2' represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R2's are present, the plurality of R2's may be the same or different. [8] A compound having a structural unit represented by formula (4), wherein at least one of R2' is (g) or (h).

[0019] [ka]

[0020] (In formula (4), Z represents a monovalent substituent bonded to the ring, and when a plurality of Z's are present in formula (4), the plurality of Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when a plurality of L's are present in the compound, the plurality of L's may be the same as or different from each other, and when a plurality of M's are present in the compound, the plurality of M's may be the same as or different from each other.) R2' represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R2's are present, the plurality of R2's may be the same or different. [9] A composition comprising the compound according to any one of [1] to [8] above and a photopolymerization initiator or a curing catalyst.

[12] A composition comprising the compound according to any one of [1] to [8] above and a compound capable of reacting with the compound according to any one of [1] to [8] above.

[13] A polybenzoxazol, which is an intramolecular dehydration ring-closure product obtained by heating the compound according to any one of [1] to [8] above.

[14] A dry film resist obtained by sandwiching a composition containing the compound according to any one of

[11] to [8] above between substrates.

[15] A dry film resist obtained by sandwiching a composition containing the compound according to

[13] above between substrates.

[16] A compound having a structural unit represented by the following general formula (5):

[0021] [ka] In formula (5), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (5), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to the aromatic ring, and when a plurality of Y's are present in the compound, the plurality of Y's may be the same or different. R1 represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R1 are present, the plurality of R1 may be the same or different.

[17] A mixture obtained by reacting a diaminodiphenol compound with an aldehyde or a crosslinking agent other than an aldehyde.

[18] A mixture obtained by reacting a diaminodiphenol compound with an aldehyde or a crosslinking agent other than an aldehyde, and then reacting the resulting mixture with a carboxylic acid and / or a carboxylic acid chloride. Effect of the Invention

[0022] The compound of the present invention can be developed with an alkaline aqueous solution, and a cured film containing polybenzoxazole can be obtained by using a polymer formed from the compound. In addition, the cured film according to the preferred embodiment of the present invention has excellent electrical properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. The compound of the present invention having a bridged structure between aromatic rings (hereinafter, also simply referred to as "the compound of the present invention") is a compound having a repeating unit represented by the following formula (1).

[0024] [ka]

[0025] In formula (1), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. The divalent linking group represented by X in formula (1) is not particularly limited as long as it is a divalent linking group of a known diamine compound in which two 2-aminophenol compounds, which may have a substituent, are bonded via a divalent linking group. As an example of the divalent linking group in the diamine compound, for example, the divalent linking group of 3,3'-diamino-4,4'-dihydroxydiphenyl ether is an oxygen atom, and the divalent linking group of 3,3'-diamino-4,4'-dihydroxydiphenyl methane is a methylene group. As the divalent linking group represented by X in formula (1), from the viewpoint of the solubility of the finally obtained polybenzoxazole and the film properties of the cured product of the composition containing the polybenzoxazole, a divalent linking group represented by any one of the following formulas (a) to (f) is preferred. Another preferred example of the divalent linking group represented by X is -O-Ph-O-. A divalent linking group represented by the following formula (c) is more preferred.

[0026] [ka]

[0027] X in formula (1) is preferably a direct bond or a divalent linking group containing at least one selected from the group consisting of a carbon atom, a fluorine atom, a sulfur atom, and an oxygen atom, more preferably a direct bond or a divalent linking group represented by any one of the above formulas (a) to (f), and even more preferably a direct bond or a divalent linking group represented by the above formula (c).

[0028] In formula (1), Z represents a monovalent substituent bonded to a ring, and when a plurality of Z's are present in formula (1), the plurality of Z's may be the same or different. The monovalent substituent represented by Z in formula (1) 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 a plurality of Zs are present, each Z may be the same or different. Specific examples of the halogen atom which is a preferred embodiment of Z in the formula (1) include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, with a fluorine atom being 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 which is a preferred embodiment of Z in formula (1) include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a cyclohexane group, an alkenyl group having 1 to 6 carbon atoms such as propene, and an alkynyl group having 1 to 6 carbon atoms such as propyne, etc. A methyl group is preferred. The aromatic group, which is a preferred embodiment of Z in formula (1), is a residue obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound. The aromatic compound is not limited to any of aromatic hydrocarbon compounds, aromatic heterocyclic compounds, and heterocyclic condensed aromatic compounds, so long as it has aromaticity. Specific examples of the aromatic group which is a preferred embodiment of Z in the formula (1) include a phenyl group and a naphthyl group, etc. 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-propoxycarbonyl group, a benzyloxycarbonyl group, and a phenoxycarbonyl group. 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 -CONH2, -CONH(CH3), and -CONH(i-C3H7); and arylamide groups such as benzamide, naphthamide, pt-butylbenzamide, o-chlorobenzamide, and -CON(Ph)2. A benzamide group is preferred. In this specification, Ph represents a phenyl group. Z in formula (1) is preferably an aliphatic group because the polymer easily undergoes intramolecular dehydration ring closure at low temperatures.

[0029] In formula (1), L and M are the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3. When a compound has a plurality of L's, the plurality of L's may be the same as or different from one another, and when a compound has a plurality of M's, the plurality of M's may be the same as or different from one another. In formula (1), L and M are preferably each independently an integer of 0 or 1.

[0030] In formula (1), Y represents a direct bond or a divalent linking group bonded to an aromatic ring, and when a plurality of Y's are present in a compound, the plurality of Y's may be the same or different. The divalent linking group represented by Y in formula (1) is not particularly limited and may be a direct bond, but is preferably an alkylene group having 1 to 11 carbon atoms, or a divalent aromatic group obtained by removing two hydrogen atoms from the aromatic ring of a hydrocarbon compound, and a divalent group containing an alkylene group having 1 to 11 carbon atoms. The alkylene group is not limited to a linear one, and may be a branched or cyclic alkylene group. The divalent aromatic group obtained by removing two hydrogen atoms from the aromatic ring of a hydrocarbon compound and the divalent group containing an alkylene group having 1 to 11 carbon atoms may be a divalent linking group in which one alkylene group is bonded to one aromatic group, a divalent linking group in which one alkylene group is bonded to multiple aromatic groups, a divalent linking group in which two alkylene groups are bonded to one aromatic group, or a divalent linking group in which multiple alkylene groups are bonded to multiple aromatic groups, so long as the total number of carbon atoms in the main chain of the alkylene group portion is 11 or less. As the divalent linking group represented by Y in formula (1), a divalent linking group represented by the following formula (2) is more preferable from the viewpoints of the solubility of the finally obtained polybenzoxazole and the film properties of a cured film containing the polybenzoxazole.

[0031] [ka]

[0032] In formula (1), R1 represents a monovalent substituent or a divalent or higher linking group, and when a plurality of R1 are present, the plurality of R1 may be the same or different. The monovalent substituent represented by R1 in formula (1) is not particularly limited, but is preferably a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an acetyl group, a glycidyl group, a (meth)acrylic group, a carboxy group, an ester group, an amide group, a trifluoromethyl group, an imide group, or a urea group. When a plurality of R1 are present, each R1 may be the same or different from each other. Specific examples of the halogen atom which is a preferred embodiment of R1 in the formula (1) include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom. The aliphatic group, which is a preferred embodiment of R1 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 which is a preferred embodiment of R1 in formula (1) include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a cyclohexane group, an alkenyl group having 1 to 6 carbon atoms such as propene, and an alkynyl group having 1 to 6 carbon atoms such as propyne. The aromatic group, which is a preferred embodiment of R1 in formula (1), is a residue obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound. The aromatic compound is not limited to any of aromatic hydrocarbon compounds, aromatic heterocyclic compounds, and heterocyclic condensed aromatic compounds, so long as it has aromaticity. Specific examples of the ester group, which is a preferred embodiment of R1 in formula (1), include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, a benzyloxycarbonyl group, and a phenoxycarbonyl group. Specific examples of the amide group, which is a preferred embodiment of R1 in formula (1), include alkylamide groups such as -CONH2, -CONH(CH3), and -CONH(i-C3H7); and arylamide groups such as benzamide, naphthamide, pt-butylbenzamide, o-chlorobenzamide, and -CON(Ph)2. A benzamide group is preferred. In this specification, Ph represents a phenyl group. R1 in formula (1) may be a monovalent substituent obtained by removing a hydroxyl group from a carboxylic acid, or a monovalent substituent obtained by removing a chlorine atom from a carboxylic acid chloride. Examples of carboxylic acids and carboxylic acid chlorides that can be monovalent substituents include (meth)acrylic acid, propiolic acid, maleimidocarboxylic acid, lauric acid, diphenylcarbamoyl chloride, 2,2-dimethylbutyryl chloride, pentafluorobenzoyl chloride, 3,5,5-trimethylhexanoyl chloride, 1-adamantanecarbonyl chloride, 3,4,5-trimethoxybenzoyl chloride, heptafluorobutyryl chloride, and 3,5-bis(trifluoromethyl)benzoyl chloride, but are not limited thereto. Examples of maleimidocarboxylic acids include the following compounds No. 1 to 4.

[0033] [ka]

[0034] R1 in formula (1) being monovalent means that there is no bond with * in formula (1), that is, it is a structural unit represented by the following formula (1'): R2, L, M, X, Y, and Z in formula (1') are the same as those in formula (1) above.

[0035] [ka]

[0036] R1 in formula (1) is divalent when * in formula (1) is a structural unit represented by formula (1). The divalent or higher substituent represented by R1 in formula (1) represents a divalent linking group obtained by removing two hydroxyl groups from a saturated aliphatic dicarboxylic acid compound, a divalent linking group obtained by removing two hydroxyl groups from an aromatic dicarboxylic acid compound, or a divalent linking group other than a divalent linking group obtained by removing two hydroxyl groups from a saturated aliphatic dicarboxylic acid compound and a divalent linking group obtained by removing two hydroxyl groups from an aromatic dicarboxylic acid compound (hereinafter simply referred to as "other divalent linking group"). Examples of saturated aliphatic dicarboxylic acid compounds that can serve as a divalent linking group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, and pimellate. Examples of the fatty acid include, but are not limited to, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, pentacosane diacid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid. The fatty acid chain may partially contain heteroatoms such as oxygen atoms and sulfur atoms. R1 in formula (1) is preferably monovalent or divalent. R1 in formula (1) is more preferably monovalent. From the viewpoint of alkali solubility, R1 in formula (1) is most preferably a hydrogen atom.

[0037] In formula (1), R2 represents a monovalent substituent or a divalent or higher linking group containing a nitrogen atom directly bonded to an aromatic ring, and when there are multiple R2's, the multiple R2's may be the same or different. Examples of the monovalent substituent containing a nitrogen atom directly bonded to the aromatic ring represented by R2 in formula (1) include an amino group, an amide group, an imide group, and a maleimide group. Alternatively, examples of the monovalent substituent include a portion obtained by removing a carboxyl group from a carboxylic acid and a portion obtained by removing a carbonyl group and a chlorine atom from a carboxylic acid chloride are monovalent substituents bonded via an amide bond. Examples of the carboxylic acid and carboxylic acid chloride that can be the monovalent substituent include, but are not limited to, (meth)acrylic acid, propiolic acid, maleimidocarboxylic acid, lauric acid, diphenylcarbamoyl chloride, 2,2-dimethylbutyryl chloride, pentafluorobenzoyl chloride, 3,5,5-trimethylhexanoyl chloride, 1-adamantanecarbonyl chloride, 3,4,5-trimethoxybenzoyl chloride, heptafluorobutyryl chloride, and 3,5-bis(trifluoromethyl)benzoyl chloride. Examples of the maleimidocarboxylic acid include compounds No. 1 to 4 listed above.

[0038] R2 in formula (1) being monovalent means that there is no bond to * in formula (1), that is, it is a structural unit represented by the following formula (1''). In formula (1''), R1, L, M, X, Y, and Z are the same as those in formula (1) above.

[0039] [ka]

[0040] R2 in formula (1) is divalent when * in formula (1) is a structural unit represented by formula (1). The divalent or higher substituent represented by R2 in formula (1) represents a divalent linking group obtained by removing two carboxy groups from a saturated aliphatic dicarboxylic acid compound, a divalent linking group obtained by removing two carboxy groups from an aromatic dicarboxylic acid compound, or a divalent linking group other than a divalent linking group obtained by removing two carboxy groups from a saturated aliphatic dicarboxylic acid compound and a divalent linking group obtained by removing two carboxy groups from an aromatic dicarboxylic acid compound (hereinafter simply referred to as "other divalent linking group"). Examples of saturated aliphatic dicarboxylic acid compounds that can serve as a divalent linking group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, and pimellate. Examples of the fatty acid include, but are not limited to, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, pentacosane diacid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid. The fatty acid chain may partially contain heteroatoms such as oxygen atoms and sulfur atoms. R2 in formula (1) is preferably monovalent or divalent, and more preferably monovalent because it provides superior adhesion. When R2 in formula (1) is monovalent, it is preferred that at least one of R2 is a monovalent linking group to which a moiety obtained by removing a carboxyl group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond. It is more preferred that 20% or more of R2 are monovalent linking groups to which a moiety obtained by removing a carboxyl group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond. It is even more preferred that 30% or more of R2 (corresponding to formula (3) above) are monovalent linking groups to which a moiety obtained by removing a carboxyl group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond. It is most preferred that 50% or more of R2 are monovalent linking groups to which a moiety obtained by removing a carboxyl group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond. When R2 in formula (1) is divalent, at least one of R2 is preferably a divalent linking group obtained by removing two carboxy groups from sebacic acid.

[0041] It is more preferable to combine the above-mentioned preferred forms. That is, in the above formula (1), it is more preferable that X is a divalent linking group represented by the above formula (c), Y is a divalent linking group represented by the above formula (2), R1 is a hydrogen atom, and at least one of R2 is a monovalent linking group to which a moiety obtained by removing a carboxy group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond, more preferably 20% or more of R2 are monovalent linking groups to which a moiety obtained by removing a carboxy group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond, more preferably 30% or more of R2 are monovalent linking groups to which a moiety obtained by removing a carboxy group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond, and most preferably 50% or more of R2 are monovalent linking groups to which a moiety obtained by removing a carboxy group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond.

[0042] The weight-average molecular weight of the compound represented by formula (1) is preferably 700 to 200,000, more preferably 700 to 100,000. By having a weight-average molecular weight of 700 or more, the strength and film properties of the cured film containing polybenzoxazole obtained from the polymer of the compound of the present invention can be improved, and further, when the composition containing the compound of the present invention is formed into a film by spin coating, it becomes easy to obtain a desired film thickness. In addition, by having a weight-average molecular weight of 200,000 or less, the solubility of the composition in an alkaline developer and the resolution of the composition when irradiated with light can be highly maintained. Here, the weight-average molecular weight is a value obtained by measuring by gel permeation chromatography and converting from a standard polystyrene calibration curve.

[0043] The precursor of the compound of the present invention can be synthesized by reacting a diaminodiphenol compound or a compound having a phenolic hydroxyl group with an aldehyde or other crosslinking agent. The precursor can be a compound of formula (1) in which R2 is an amino group (corresponding to formula (5) above). Thereafter, the amino group and the phenolic hydroxyl group of the precursor of the compound of the present invention obtained above can be reacted with a halide derivative of a carboxylic acid compound to obtain the compound of the present invention. Examples of the diaminodiphenol compound used in producing the precursor of the compound of the present invention include the following compounds No. 5 to No. 12. These diaminodiphenol compounds can be used alone or in combination of two or more. The diaminodiphenol compound used in producing the precursor of the compound of the present invention is preferably the following compound No. 5. When the compound of the present invention is synthesized using the following compound No. 5, it is preferable that in the above formula (1), X is a divalent linking group represented by the above formula (c), Y is a divalent linking group represented by the above formula (2), R1 is a hydrogen atom, and at least one of R2 is a monovalent linking group to which a portion obtained by removing a carboxyl group from maleimide carboxylic acid or (meth)acrylic acid is bonded via an amide bond (corresponding to the above formula (4)).

[0044] [ka]

[0045] Examples of compounds having a phenolic hydroxyl group include phenol, cresol, ethylphenol, n-propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, dipropylphenol, dibutylphenol, guaiacol, guetol, trimethylphenol, naphthol, methylnaphthol, bisphenol, bisphenol A, bisphenol F, allylphenol, etc., and one type may be used alone or two or more types may be mixed and used. The phenols are preferably phenol and cresol, and more preferably phenol. As the aldehyde, formaldehyde is usually used. As the formaldehyde, a commercially available product is generally used, and examples thereof include an aqueous formaldehyde solution (aqueous formalin solution), paraformaldehyde, trioxane, etc., but an inexpensive aqueous formalin solution is preferred. Formaldehyde forms a methylene group crosslink. As other aldehydes, o-hydroxybenzaldehyde and p-hydroxybenzaldehyde are used. As for o-hydroxybenzaldehyde and p-hydroxybenzaldehyde, commercially available products are used. These o-hydroxybenzaldehyde and p-hydroxybenzaldehyde may be used alone or in combination. In the present invention, formaldehyde is preferably used.

[0046] Other crosslinking agents include compounds represented by the following general formula (6).

[0047] [ka]

[0048] In formula (6), X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group. Specifically, 4,4'-di(halogenomethyl)biphenyl, 2,4'-di(halogenomethyl)biphenyl, 2,2'-di(halogenomethyl)biphenyl, 4,4'-di(alkoxymethyl)biphenyl, 2,4'-di(alkoxymethyl)biphenyl, 2,2'-di(alkoxymethyl)biphenyl, 4,4'-di(hydroxymethyl)biphenyl, 2,4'-di(hydroxymethyl)biphenyl, 2,2'-di(hydroxymethyl)biphenyl, o-xylylene Examples of the difluoride include m-xylylene difluoride, p-xylylene difluoride, o-xylylene dichloride, m-xylylene dichloride, p-xylylene dichloride, o-xylylene dibromide, m-xylylene dibromide, p-xylylene dibromide, o-xylylene diiodide, m-xylylene diiodide and p-xylylene diiodide, o-benzene dimethanol, m-benzene dimethanol and p-benzene dimethanol. These may be used alone or in combination of two or more. Examples of the preferred compound represented by the general formula (6) include 4,4'-di(chloromethyl)biphenyl, 4,4'-di(methoxymethyl)biphenyl, and 4,4'-di(ethoxymethyl)biphenyl. Examples of the 4,4'-di(chloromethyl)biphenyl, 4,4'-di(methoxymethyl)biphenyl, and 4,4'-di(ethoxymethyl)biphenyl include. As the halide derivative of the carboxylic acid compound, a commercially available product may be used. Specific examples include 10-undecenoyl chloride, diphenylcarbamoyl chloride, 2,2-dimethylbutyryl chloride, pentafluorobenzoyl chloride, 3,5,5-trimethylhexanoyl chloride, 1-adamantanecarbonyl chloride, 3,4,5-trimethoxybenzoyl chloride, heptafluorobutyryl chloride, and 3,5-bis(trifluoromethyl)benzoyl chloride. Alternatively, a halogenating agent may be applied to a carboxylic acid such as (meth)acrylic acid, propiolic acid, maleimidocarboxylic acid, or lauric acid to synthesize a halide derivative. Examples of the maleimidocarboxylic acid include the above-mentioned compounds No. 1 to 4. Examples of the halogenating agent used in the conversion to a halide derivative include thionyl chloride, oxalyl chloride, phosphoryl chloride, and phosphorus chloride, which are used in normal acid chloride reactions. The halide derivatives of carboxylic acid compounds may be used alone or in combination of two or more, but the total amount of the halide derivatives of carboxylic acid compounds added is preferably 1.0 to 1.2 mol per 1.0 mol of the precursor of the compound of the present invention. It is preferable to add the halide derivatives of maleimide carboxylic acid or (meth)acrylic acid before adding the halide derivatives of other carboxylic acid compounds.

[0049] The method for obtaining the precursor of the compound of the present invention is not particularly limited. Known catalysts, solvents, reaction temperatures, reaction times, etc. capable of polycondensing a compound having a phenolic hydroxyl group with an aldehyde or other crosslinking agent can be adopted. In addition, known methods such as neutralization, water washing, dehydration, and reduced pressure distillation can be adopted for post-treatment after the reaction is completed. As a preferred embodiment of the method for obtaining the precursor of the compound of the present invention, for example, a diaminodiphenol compound is reacted with a formaldehyde in water or an organic solvent without a catalyst or in the presence of an acid or base catalyst to obtain a precursor of the compound of the present invention. As the acid catalyst, organic acids such as hydrochloric acid, oxalic acid, formic acid, and acetic acid, as well as sulfuric acid, p-toluenesulfonic acid, and diethyl sulfate can be used, and as the base catalyst, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, etc. can be used. As the organic solvent, sulfolane, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, etc. can be used. The concentration of the reaction components in the entire reaction system including the solvent is not particularly limited, but is preferably 10 to 50% by mass, more preferably 20 to 40% by mass.

[0050] As a specific synthesis procedure, formaldehyde is dissolved in a solvent, and an acid catalyst and a diaminodiphenol compound are added. The temperature at which the acid catalyst and the diaminodiphenol compound are added is preferably -20 to 35°C, more preferably -10 to 30°C. The reaction temperature of the formaldehyde and the diaminodiphenol compound is preferably 0 to 80°C, more preferably 10 to 50°C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 5 hours. After the reaction is completed, the reaction solution obtained is neutralized and extracted with an organic solvent, and then reprecipitated with an organic solvent to obtain a precursor of the compound of the present invention. Then, the precursor of the compound of the present invention is dissolved, and a halide derivative of a carboxylic acid compound is added. The temperature at which the halide derivative of a carboxylic acid compound is added is preferably -20 to 20°C, more preferably -10 to 10°C. The subsequent reaction temperature is preferably 0 to 30°C, more preferably 0 to 10°C. The reaction time is preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours. After the reaction is completed, water is added to the resulting reaction solution to obtain the compound of the present invention having a crosslinked structure between aromatic rings.

[0051] Next, the composition of the present invention will be described. The composition according to the first aspect of the present invention contains at least one compound having an unsaturated double bond of the present invention represented by formula (1), and at least one photopolymerization initiator or at least one curing catalyst.

[0052] The photopolymerization initiator used in the composition of the first aspect of the present invention is not particularly limited as long as it is a conventionally known photopolymerization initiator used for photocuring a compound having an unsaturated double bond group. 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 isobutyl ether, benzoin n-butyl ether, benzil dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-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), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2,4-diethylthioxanthone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

[0053] 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 of enabling fine pattern formation using a reduction projection exposure machine (stepper, light source wavelength: 365 nm, 436 nm) that is standardly used in the manufacturing process of semiconductor protective films and the like. Preferred examples of the photopolymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione=2-(O-benzoyloxime) (manufactured by BASF Japan, "IRGACURE OXE-01"), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 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, "Omnirad 907"). The amount of the photopolymerization initiator used (if used) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 8 parts by mass, per 100 parts by mass of the compound represented by formula (1).

[0054] The composition of the first embodiment containing a 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 (when 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.

[0055] The curing catalyst used in the composition of the first aspect of the present invention is not particularly limited as long as it can promote the self-polymerization of the acrylic or methacrylic groups (hereinafter referred to as acrylic groups) at both ends of the compound represented by formula (1) of the present invention by heating, and conventionally used ones 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, and the like. 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).

[0056] The composition of the present invention may contain other components in addition to the compound represented by formula (1), which is an essential component, and an optional photopolymerization initiator and / or curing catalyst, or a compound capable of reacting with acrylic groups. Other components that can be used in combination with the composition of the present invention include various additives such as organic solvents, adhesion enhancers such as coupling agents, thermoplastic resins, colorants, thickeners, thermal polymerization inhibitors, defoamers, and leveling agents.

[0057] 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, 4-formylmorpholine, 1,3-dimethyl-2-imidazolidinone, 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 the handling of the composition is improved. There is no particular restriction on the content of the organic solvent in the composition of the present invention, but typically the content of the solvent in the composition (if used) is 95% by mass or less, preferably 20 to 90% by mass.

[0058] It is known that the addition of a compound containing a tertiary amine structure as an organic solvent promotes the reaction of acrylic groups. Therefore, among the above-mentioned organic solvents, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 4-formylmorpholine, and 1,3-dimethyl-2-imidazolidinone as compounds containing a tertiary amine structure, either alone or in combination with a compound that does not contain a tertiary amine structure. When used in combination with a compound not containing a tertiary amine structure, the addition ratio of each is not particularly limited. However, since compounds containing a tertiary amine structure generally have a high boiling point and therefore require a long drying time after spin coating, the compound containing a tertiary amine structure is preferably present in an amount of 50% or less in the solvent.

[0059] The coupling agent as the adhesion enhancer is not particularly limited, but may typically be a silane coupling agent. Examples of the silane coupling agent include, but are not limited to, 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. These may be used alone or in combination of two or more. Since the silane coupling agent is unreactive with the compounds of the present invention (compounds, self-polymerization products, polybenzoxazole), components other than those acting at the substrate interface may remain as residual components after curing. Therefore, when a large amount of the silane coupling agent is used as an adhesion enhancer, it may have undesirable effects such as a decrease in physical properties. Depending on the type of substrate, even a small amount can be effective, so it is appropriate to use it within a range that does not have undesirable effects. The proportion of the silane coupling agent used (if used) is usually 15% by mass or less, preferably more than 0% by mass and 5% by mass or less, based on the total mass of the composition, but the upper limit of the proportion used may vary depending on the type of substrate.

[0060] 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 the thickener include orben, bentone, and montmorillonite. Examples of the thermal polymerization inhibitor include hydroquinone and 2,6-di-tert-butyl-p-methylphenol. Examples of the defoaming agent include silicone-based, fluorine-based and polymer-based defoaming agents. The amount of these additives used (when used) in the composition of the present invention is preferably, for example, 30% by mass or less, as a rough guide, but can be increased or decreased as appropriate depending on the purpose of use.

[0061] 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.

[0062] The composition of the present invention may contain a thermal acid generator (thermal latent acid generator) or a thermal base generator (thermal latent base generator). The use of a thermal acid generator or a thermal base generator is preferable because it efficiently acts as a catalyst when the phenolic hydroxyl group-containing polyamide structure of formula (2), which is a polybenzoxazole precursor (non-phenolic hydroxyl group-containing polyamide structure when the benzene ring is hydrogenated to form a cyclohexane ring) undergoes an intramolecular dehydration ring-closing reaction to cyclize. In particular, the acid generated from the thermal acid generator can lower the temperature of the intramolecular dehydration ring-closing reaction, and the cured film obtained at that time has performance comparable to that of a film cured at a high temperature.

[0063] The acid generated from the thermal acid generator is preferably a strong acid.Specific examples of such strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as camphorsulfonic acid, trifluoromethylsulfonic acid, and nonafluorobutanesulfonic acid.These acids act efficiently as catalysts when the phenolic hydroxyl group-containing polyamide structure of formula (2), which is a polybenzoxazole precursor (non-phenolic hydroxyl group-containing polyamide structure when the benzene ring is hydrogenated to form a cyclohexane ring) undergoes intramolecular dehydration ring-closing reaction to cyclize.

[0064] The compound of the present invention and a composition containing the compound can also be used in the form of a dry film resist. That is, the compound and composition of the present invention can be applied to a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then dried in a drying oven set at 45 to 140 ° C. to remove a predetermined amount of solvent, and a cover film or the like can be laminated as necessary to form a dry film resist. In this case, the thickness of the resist on the base film is adjusted to 2 to 200 μm. The compound and composition of the present invention used to form a dry film resist may be any of those described above as long as they contain the compound, but the composition of the first aspect above is preferred. As the base film and cover film, for example, films of polyester, polypropylene, polyethylene, TAC, polyimide, etc. are used. These films may be treated with a silicone-based release treatment agent or a non-silicone-based release treatment agent as necessary. If supplied as a dry film resist, it is possible to omit the steps of application to a support and drying, and the composition of the present invention can be used more easily.

[0065] The polybenzoxazole of the present invention is an intramolecular dehydration ring-closure product of the above-mentioned polymer (self-polymer or copolymer) of the present invention. The conditions for intramolecular dehydration ring-closing of the polymer of the present invention are not particularly limited as long as they are the conditions usually used for converting a polybenzoxazole precursor into a polybenzoxazole by intramolecular dehydration ring-closing reaction. The intramolecular dehydration ring-closing reaction can be carried out using, for example, a hot plate, an oven, or a temperature-programmable heating oven. The intramolecular dehydration ring-closing reaction can be carried out in air or in an inert gas atmosphere such as nitrogen or argon.

[0066] The cured film containing the polybenzoxazole of the present invention can be used in electronic parts such as semiconductor devices and multilayer wiring boards, and organic EL display devices.Specifically, the cured film is suitably used for applications such as passivation films for semiconductors, surface protection films for semiconductor elements, interlayer insulating films, interlayer insulating films for multilayer wiring for high-density mounting, insulating films for rewiring layers, interlayer insulating films for electronic parts such as inductors and SAW filters, insulating films and flat layers for organic electroluminescent devices, but is not limited thereto and can have various structures. EXAMPLES

[0067] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "parts" means parts by mass, and "%" means mass%. The weight average molecular weight of the synthesized polymer was determined in terms of standard polystyrene using gel permeation chromatography (GPC, apparatus manufactured by Tosoh Corporation, column manufactured by Tosoh Corporation). Unless otherwise specified, commercially available reagents were used. Sodium hydroxide: Fujifilm Wako Pure Chemical Corporation Paraformaldehyde: Tokyo Chemical Industry Co., Ltd. 4,4'-(Hexafluoroisopropylidene)bis(2-aminophenol): Wakayama Seika Kogyo Co., Ltd. Sodium dihydrogen phosphate dihydrate: Kanto Chemical Co., Ltd. Methyl isobutyl ketone (MIBK): Tokyo Chemical Industry Co., Ltd. Dibutylhydroxytoluene (BHT): Kanto Chemical Co., Ltd. Hexane: Junsei Chemical Co., Ltd. N-Methylpyrrolidone (NMP): Fujifilm Wako Pure Chemical Corporation Picorin: Tokyo Chemical Industry Co., Ltd. Methacryloyl chloride: Tokyo Chemical Industry Co., Ltd. 3,5-Bis(trifluoromethyl)benzoyl chloride: Tokyo Chemical Industry Co., Ltd. 10-Undecenoyl Chloride: Tokyo Chemical Industry Co., Ltd. Cyclopentanone: Zeon Corporation 6-Maleimidohexanoic acid: Sigma-Aldrich Thionyl chloride: Junsei Chemical Co., Ltd. N,N-Dimethylformamide (DMF): Junsei Chemical Co., Ltd. Acetone: Junsei Chemical Co., Ltd. Sebacyl chloride: Tokyo Chemical Industry Co., Ltd. Heptafluorobutyryl chloride: Tokyo Chemical Industry Co., Ltd.

[0068] Synthesis Example 1 (Preparation of Maleimidocarboxylic Acid Chloride) In a 500 ml round bottom flask equipped with a Teflon coated stir bar, 8.44 parts (0.040 mol) of 6-maleimidohexanoic acid and 20 parts of DMF were added. After cooling the mixture on ice, 5.51 parts (0.046 mol) of thionyl chloride was slowly added and stirred at room temperature for 20 minutes.

[0069] Example 1 (Synthesis of precursors of the compounds of the present invention) In a 2000mL flask equipped with a stirrer and a thermometer, 130g of distilled water was charged while blowing nitrogen (200mL / min), 13.2g (330mmol) of sodium hydroxide and 6.0g (200mmol) of paraformaldehyde were added, and after stirring at room temperature for 10 minutes, 54.9g (150mmol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) was added, and the temperature was raised to 50°C, and stirring was continued for 3 hours at 50°C. After that, stirring was continued until the internal temperature reached room temperature, and 334g of 20% sodium dihydrogen phosphate aqueous solution (429mmol as sodium dihydrogen phosphate) was added. Then, 300g of MIBK and 0.2g of BHT were added, and the entire amount was transferred to a separatory funnel. After leaving it to stand, the aqueous layer was discarded (about 500g), and 350g of distilled water was added to wash the organic layer, and the aqueous layer was discarded. This operation was repeated three times in total. The obtained organic layer was divided into about 100 g portions and dropped into 1000 g of stirred hexane over 10 minutes, and the precipitated powder was collected by filtration and washed with about 200 g of hexane to obtain a white powder. The obtained powder was dried in an oven at 40°C for 20 hours and stored as a white powder. (Compound a) The weight average molecular weight (Mw) of compound a was 1,050. Compound a is a mixture containing the following formula (A). Formula (A) is a compound in which three structures of the above formula (1) are bonded together, but since compound a is a mixture, it may also include compounds in which two or four or more structures of formula (1) are bonded together.

[0070] [ka]

[0071] Hereinafter, the number of moles of compound a charged is calculated from the theoretical value of the amine group equivalent and shown. Hereinafter, compounds b-1 to b-4 and b-7 to b-11 are mixtures containing compounds in which an amide bond is formed by reacting an acid chloride with an amino group of (Formula A).

[0072] Example 2 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 71.3g (719mmol) of NMP, 10.2g (110mmol) of picoline, and 9.5g (50mmol) of compound a. The solution was cooled on ice, and 2.6g (25mmol) of methacryloyl chloride was added and stirred for 20 minutes. Then, 2.7g (10mmol) of 3,5-bis(trifluoromethyl)benzoyl chloride was added and stirred for 15 minutes. Furthermore, 4.1g (20mmol) of 10-undecenoyl chloride was added and stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 200g of cyclopentanone (CP) was added and dissolved. The operation of adding 100g of water and washing with liquid was performed three times. The organic layer was extracted, 0.01g of BHT was added, and the solution was concentrated under reduced pressure at 50°C and stored as a CP varnish. (Compound b-1) The weight average molecular weight (Mw) of compound b-1 was 1,050.

[0073] Example 3 (Synthesis of compounds of the present invention) A 500 ml flask equipped with a stirrer and a thermometer was charged with 197 g (1990 mmol) of NMP, 30.7 g (330 mmol) of picoline, and 28.4 g (150 mmol) of compound a. The solution was cooled on ice, and 20.7 g (90.0 mmol) of maleimide carboxylic acid chloride was added and stirred for 10 minutes. Then, 7.84 g (75.0 mmol) of methacryloyl chloride was added and stirred for 1 hour. 437 g of water was added to the reaction solution, the supernatant was discarded, and the precipitated solid was dissolved in 320 g of NMP. 535 g of water was added to this, and the precipitated solid was filtered and collected. The solid was dissolved in 550 g of CP, and water was added to wash the liquid, and this operation was repeated three times. The organic layer was extracted, concentrated with aeration at 60°C, and stored as CP varnish. (Compound b-2) The weight average molecular weight (Mw) of compound b-2 was 1,150.

[0074] Example 4 (Synthesis of compounds of the present invention) A 500 ml flask equipped with a stirrer and a thermometer was charged with 62.4 g (629 mmol) of NMP, 10.2 g (110 mmol) of picoline, and 9.5 g (50 mmol) of compound a. The solution was cooled on ice, 2.6 g (25 mmol) of methacryloyl chloride was added, and the mixture was stirred for 15 minutes. Then, 6.1 g (30 mmol) of 10-undecenoyl chloride was added, and the mixture was stirred for 1 hour. 240 g of water was added to the reaction solution, the supernatant was discarded, and the precipitated solid was dissolved in 70 g of acetone. After repeating this operation three times, the acetone solution was dropped into 1 L of water, and the precipitated solid was collected, dried in a 60°C oven, and stored in a can. (Compound b-3) The weight average molecular weight (Mw) of compound b-3 was 1,770.

[0075] Example 5 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 26.0g (262mmol) of NMP, 11.8g (126mmol) of picoline, and 10.0g (53mmol) of compound a. The solution was cooled on ice, and 13.4g (58mmol) of maleimide carboxylic acid chloride was added and stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 470g of cyclopentanone (CP) was added to dissolve it. The operation of adding 200g of water and washing with liquid was performed three times. The organic layer was extracted, 0.05g of BHT was added, and the mixture was concentrated under reduced pressure at 50°C and stored as CP varnish. (Compound b-4) The weight average molecular weight (Mw) of compound b-4 was 1,749.

[0076] Example 6 (Synthesis of compounds of the present invention) A 500 ml flask equipped with a stirrer and a thermometer was charged with 154.0 g (1.5 mol) of NMP, 10.2 g (110 mmol) of picoline, and 11.4 g (60 mmol) of compound a. The solution was cooled with ice, and 2.4 g (10 mmol) of sebacic acid chloride was added and stirred for 30 minutes. Then, 4.6 g (44 mmol) of methacryloyl chloride was added and stirred for 3 hours. 250 g of water was added to the solution obtained above, and the precipitate was collected. The precipitate was dissolved in 100 g of acetone, and then 250 g of water was added again, and the precipitate was collected. This operation was repeated three times in total. Then, the precipitate was dissolved in 100 g of acetone, and the mixture was dropped into 1 liter of water with stirring, and the precipitate was collected. Then, the mixture was dried in an oven at 60° C. for one day to obtain a compound of the present invention. (Compound b-5) The weight average molecular weight (Mw) of compound b-5 was 3,200. Compound b-5 is a mixture containing the following formula (B-1). Formula (B-1) is a compound in which six structures of the above formula (1) are bonded, but since compound b-5 is a mixture, it may also contain structures in which two or three or more structures of formula (1) are bonded.

[0077] [ka]

[0078] Example 7 (Synthesis of compounds of the present invention) A 500 ml flask equipped with a stirrer and a thermometer was charged with 154.0 g (1.5 mol) of NMP, 10.2 g (110 mmol) of picoline, and 11.4 g (60 mmol) of compound a. The solution was cooled with ice, and 2.4 g (10 mmol) of sebacic acid chloride was added and stirred for 30 minutes. Then, 1.2 g (6 mmol) of 10-undecenoyl chloride was added and stirred for 30 minutes. Then, 4.0 g (38 mmol) of methacryloyl chloride was added and stirred for 3 hours. 250 g of water was added to the solution obtained above, and the precipitate was collected. After dissolving the precipitate in 100 g of acetone, 250 g of water was added again, and the operation of collecting the precipitate was repeated three times in total. Then, the precipitate was dissolved in 100 g of acetone, dropped into 1 liter of stirred water, and the precipitate was collected. Then, the mixture was dried in an oven at 60° C. for one day to obtain the compound of the present invention. (Compound b-6) The weight average molecular weight (Mw) of compound b-6 was 3,200. Compound b-6 is a mixture containing the following formula (B-2). Formula (B-2) is a compound in which six structures of the above formula (1) are bonded, but since compound b-6 is a mixture, it may also contain structures in which two or three or more structures of formula (1) are bonded.

[0079] [ka]

[0080] Example 8 (Synthesis of compounds of the present invention) A 500 ml flask equipped with a stirrer and a thermometer was charged with 71.3 g (719 mmol) of NMP, 10.2 g (110 mmol) of picoline, and 9.5 g (50 mmol) of compound a. The solution was cooled on ice, and 2.6 g (25 mmol) of methacryloyl chloride was added and stirred for 20 minutes. Then, 2.3 g (10 mmol) of heptafluorobutyryl chloride was added and stirred for 15 minutes. Furthermore, 2.8 g (10 mmol) of 3,5-bis(trifluoromethyl)benzoyl chloride was added and stirred for 15 minutes. Furthermore, 2.0 g (10 mmol) of 10-undecenoyl chloride was added and stirred for 1 hour. The reaction solution was dropped into 1 L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500 ml flask, and 200 g of cyclopentanone (CP) was added to dissolve it. The operation of adding 100 g of water and washing with liquid was performed three times. The organic layer was extracted, 0.01 g of BHT was added, and the mixture was concentrated under reduced pressure at 50° C. and stored as CP varnish. (Compound b-7) The weight average molecular weight (Mw) of compound b-7 was 1,692.

[0081] Example 9 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 71.3g (719mmol) of NMP, 10.2g (110mmol) of picoline, and 9.5g (50mmol) of compound a. The solution was cooled on ice, and 2.6g (25mmol) of methacryloyl chloride was added and stirred for 20 minutes. Then, 2.3g (10mmol) of maleimidocarboxylic acid chloride was added and stirred for 15 minutes. Furthermore, 4.1g (20mmol) of 10-undecenoyl chloride was added and stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 200g of cyclopentanone (CP) was added to dissolve it. The operation of adding 100g of water and washing the liquid was performed three times. The organic layer was extracted, 0.01g of BHT was added, and the solution was concentrated under reduced pressure at 50°C and stored as a CP varnish. (Compound b-8)

[0082] Example 10 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 71.3g (719mmol) of NMP, 10.2g (110mmol) of picoline, and 9.5g (50mmol) of compound a. The solution was cooled on ice, and 2.6g (25mmol) of methacryloyl chloride was added and stirred for 20 minutes. Then, 4.6g (20mmol) of maleimidocarboxylic acid chloride was added and stirred for 15 minutes. 2.0g (10mmol) of 10-undecenoyl chloride was added and stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 200g of cyclopentanone (CP) was added and dissolved. The operation of adding 100g of water and washing with liquid was performed three times. The organic layer was extracted, 0.01g of BHT was added, and the solution was concentrated under reduced pressure at 50°C and stored as a CP varnish. (Compound b-9)

[0083] Example 11 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 71.3g (719mmol) of NMP, 10.2g (110mmol) of picoline, and 9.5g (50mmol) of compound a. The solution was cooled on ice, 2.6g (25mmol) of methacryloyl chloride was added, and the mixture was stirred for 20 minutes. Then, 7.0g (30mmol) of heptafluorobutyryl chloride was added, and the mixture was stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 200g of cyclopentanone (CP) was added and dissolved. The operation of adding 100g of water and washing the liquid was performed three times. The organic layer was extracted, 0.01g of BHT was added, and the mixture was concentrated under reduced pressure at 50°C and stored as a CP varnish. (Compound b-10) The weight average molecular weight (Mw) of compound b-10 was 1,158.

[0084] Example 12 (Synthesis of compounds of the present invention) A 500ml flask equipped with a stirrer and a thermometer was charged with 71.3g (719mmol) of NMP, 10.2g (110mmol) of picoline, and 9.5g (50mmol) of compound a. The solution was cooled on ice, 2.6g (25mmol) of methacryloyl chloride was added, and the mixture was stirred for 20 minutes. Then, 8.3g (30mmol) of 3,5-bis(trifluoromethyl)benzoyl chloride was added, and the mixture was stirred for 1 hour. The reaction solution was dropped into 1L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500ml flask, and 200g of cyclopentanone (CP) was added and dissolved. The operation of adding 100g of water and washing the liquid was performed three times. The organic layer was extracted, 0.01g of BHT was added, and the mixture was concentrated under reduced pressure at 50°C and stored as a CP varnish. (Compound b-11) The weight average molecular weight (Mw) of compound b-1 was 1,030.

[0085] Comparative Example 1 8.4g (40mmol) of 6-maleimidohexanoic acid and 20g of DMF were added to a 500ml round bottom flask equipped with a Teflon coated stirring bar. After cooling the mixture on ice, 10.2g (80mmol) of oxalyl chloride was slowly added and stirred at room temperature for 2 hours. Then, 7.3g (20mmol) of 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) dissolved in 10g of DMF was added and stirred at 60°C for 3 hours. After cooling to room temperature, 300g of water was added and the precipitated solid was filtered. The solid obtained above and 100g of methanol were added to a flask and stirred and washed at 40°C, then cyclopentanone was added and concentrated under vacuum to obtain a compound c-1 solution.

[0086] Comparative Example 2 In a 500 ml flask equipped with a stirrer and a thermometer, 71.3 g (719 mmol) of NMP, 10.2 g (110 mmol) of picoline, and 9.5 g (50 mmol) of compound a were added. This solution was cooled on ice, and 15.2 g (55 mmol) of 3,5-bis(trifluoromethyl)benzoyl chloride was added and stirred for 1 hour. The reaction solution was dropped into 1 L of water, and the precipitated solid was collected by suction filtration. This was transferred to a 500 ml flask, and 200 g of cyclopentanone (CP) was added and dissolved. The operation of adding 100 g of water and washing with liquid was repeated three times. The organic layer was extracted, and 0.0116 g of BHT was added, followed by vacuum concentration at 50°C and storage as CP varnish. (Compound c-2)

[0087] Examples 13 to 21 (Preparation of compositions of the present invention) The components were mixed in the amounts shown in Table 1 to prepare compositions of the present invention. The components used in the compositions of Examples 13 to 21 are as follows: b-1 to b-11, c-1 to c-2: Compounds synthesized in Examples 1 to 12 and Comparative Examples Photopolymerization initiator: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (BASF Japan, "IRGACURE OXE-02") Silane coupling agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-503") Solvent: Cyclopentanone and 4-formylmorpholine

[0088] (Evaluation of Alkaline Solubility of Composition) Using a spin coater, each composition obtained in Examples 13 to 21 and Comparative Example was applied to a silicon substrate, and then dried to form a composition layer having a thickness of 10 μm on the silicon substrate. The composition layer obtained above was immersed in 100 g of a 2.38% aqueous solution of tetramethylammonium hydroxide (Tokusoh SD-1, manufactured by Tokuyama Corp.) for 5 minutes to confirm the solubility.

[0089] (Evaluation of photocurability of composition) Using a spin coater, each of the compositions obtained in Examples 13 to 21 and Comparative Example 1 was applied to a silicon substrate and dried to form a composition layer having a thickness of 10 μm on the silicon substrate. Then, 1000 mJ / cm 2 was applied through a photomask. 2 The resist was exposed to light with a pattern of 1:1 line and space width, and immersed in 100 parts of 2.38% tetramethylammonium hydroxide aqueous solution (Tokuyama Corp., Tokuso SD-1) for 1 minute, after which the surface of the composition layer was visually observed and the alkaline developability was evaluated according to the following evaluation criteria. The results are shown in Table 1. ◯: The unexposed area dissolved and the exposed area did not dissolve. ×: Both the unexposed and exposed areas were dissolved.

[0090] (Preparation of polymer film and benzoxazole film of the present invention) The compositions obtained in Examples 13 to 21 and Comparative Example 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 obtained above 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 a dose of 1000 mJ / cm. 2 Then, the copper foil was heated at 150° C. for 60 minutes to form a polymer film on the copper foil. The copper foil having the polymer film obtained above was heated at 225° C. for 120 minutes or at 300° C. for 1 hour to carry out an intramolecular dehydration ring-closing reaction of the polymer. The copper foil was then removed by etching to obtain the benzoxazole film of the present invention.

[0091] (Dielectric properties (dielectric constant: Dk, dielectric tangent: Df) evaluation) A plurality of benzoxazole films cut to a length of 60 mm and a width of 3 mm were laminated and then dried in a desiccator filled with silica gel for 12 hours to prepare test pieces with a thickness of 50 to 300 μm. The dielectric properties of the test pieces obtained above were measured by a cavity resonator perturbation method using an AET vector network analyzer ADMSO10c1 as a measuring instrument and a Kanto Electronics Application Development Co., Ltd. CP531 (10 GHz band resonator) as a cavity resonator. The measurement conditions were a frequency of 10 GHz and a temperature of 25° C. The results are shown in Table 1.

[0092] (Evaluation of glass transition temperature (Tg) of benzoxazole film) The dynamic viscoelasticity of the benzoxazole film prepared according to the above "Preparation of the benzoxazole film of the present invention" was measured using a dynamic viscoelasticity measuring device (DMA) (RSA-G2, manufactured by TA Instruments) (frequency 1 Hz, tension mode, heating rate 3°C / min), and the glass transition temperature was calculated from the maximum value of the loss tangent (tan δ). The results are shown in Table 1.

[0093] [Table 1]

[0094] [Table 2]

[0095] In Tables 1 and 2, "*" indicates that no membrane was obtained, and "-" indicates that no measurement was performed.

[0096] The polymer having the structural unit represented by formula (1) of the present invention is a photosensitive polybenzoxazole precursor, and an alkaline aqueous solution can be used for pattern formation. The polybenzoxazole film finally obtained has excellent electrical properties. Therefore, this cured film can be used for commonly used surface protection films for semiconductors, 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 its manufacturing method. These are based on completely new inventions, and it can be easily understood that they are unique and extremely excellent inventions. [Industrial Applicability]

[0097] By using the polybenzoxazole resin composition of the present invention, it is possible to provide a printed wiring board or the like having excellent adhesiveness and heat resistance.

Claims

1. A compound having a structural unit represented by the following general formula (1): 【Chemistry 1】 In formula (1), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (1), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to an aromatic ring, and when a plurality of Y's are present in a compound, the plurality of Y's may be the same or different from one another. R １ represents a monovalent substituent or a divalent or higher linking group; R １ When there are multiple R １ may be the same or different from each other. R ２ represents a monovalent substituent or a divalent or higher valent linking group containing a nitrogen atom directly bonded to an aromatic ring; R ２ When there are multiple R ２ may be the same or different.)

2. R ２ The compound of claim 1, wherein at least one of the groups contains an amide bond.

3. R １ The compound according to claim 1, wherein at least one of is a hydrogen atom.

4. 2. The compound according to claim 1, wherein at least one of Y's is a divalent linking group represented by the following formula (2): 【Chemistry 2】

5. The compound according to claim 1 , wherein X is a divalent linking group represented by (a) to (f). 【Chemistry 3】

6. The compound according to claim 5 , wherein X is a divalent linking group represented by (c).

7. In the following formula (3), R ２ A compound having a structural unit represented by the following formula (3), wherein at least one of the formulas (a) and (b) is (g) or (h). 【Chemistry 4】 In formula (3), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (3), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to an aromatic ring, and when a plurality of Y's are present in a compound, the plurality of Y's may be the same or different from one another. R １ represents a monovalent substituent or a divalent or higher linking group; R １ When there are multiple R １ may be the same or different from each other. R ２ R ′ represents a monovalent substituent or a divalent or higher linking group; ２ When multiple ' are present, multiple R ２ ' may be the same or different.)

8. R ２ A compound having a structural unit represented by formula (4), wherein at least one of the formulas (a) and (b) is (g) or (h). 【Chemistry 5】 (In formula (4), Z represents a monovalent substituent bonded to the ring, and when a plurality of Z's are present in formula (4), the plurality of Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when a plurality of L's are present in the compound, the plurality of L's may be the same as or different from each other, and when a plurality of M's are present in the compound, the plurality of M's may be the same as or different from each other. R ２ R ′ represents a monovalent substituent or a divalent or higher linking group; ２ When multiple ' are present, multiple R ２ ' may be the same or different.)

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

10. A composition comprising a compound capable of reacting with the compound according to any one of claims 1 to 8.

11. A polybenzoxazol, which is an intramolecular dehydration ring-closure product obtained by heating the compound according to any one of claims 1 to 8.

12. A dry film resist obtained by sandwiching a composition containing the compound according to claim 9 between substrates.

13. A dry film resist obtained by sandwiching a composition containing the compound according to claim 10 between substrates.

14. A dry film resist obtained by sandwiching a composition containing the compound according to claim 11 between substrates.

15. A semiconductor device comprising a surface protection film, an interlayer insulating film, or an insulating film of a redistribution layer, which contains the polybenzoxazole according to claim 11.

16. A compound having a structural unit represented by the following general formula (5): 【Chemistry 6】 In formula (5), X represents a direct bond or a divalent linking group, and when a plurality of X's are present in the compound, the plurality of X's may be the same or different. Z represents a monovalent substituent bonded to the ring, and when there are multiple Z's in formula (5), the multiple Z's may be the same as or different from each other. L and M represent the number of monovalent substituents Z, and L and M each independently represent an integer of 0 to 3, and when there are multiple L's in the compound, the multiple L's may be the same as or different from each other, and when there are multiple M's in the compound, the multiple M's may be the same as or different from each other. Y represents a direct bond or a divalent linking group bonded to an aromatic ring, and when a plurality of Y's are present in a compound, the plurality of Y's may be the same or different from one another. R １ represents a monovalent substituent or a divalent or higher linking group; R １ When there are multiple R １ may be the same or different.)

17. A mixture obtained by reacting a diaminodiphenol compound with an aldehyde or a crosslinking agent other than an aldehyde.

18. A mixture obtained by reacting a diaminodiphenol compound with an aldehyde or a crosslinking agent other than an aldehyde, and then reacting the resulting mixture with a carboxylic acid and / or a carboxylic acid chloride.

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