JP5749714B2 - Hybrid material and manufacturing method thereof - Google Patents

Description

  The present invention relates to a hybrid material and a method for producing the same, and more particularly, a hybrid material composed of an organic-inorganic polymer hybrid composed of a polybenzoazole phase and an inorganic oxide phase, and advantageously producing such a hybrid material. It relates to a method that can be performed.

Since polybenzoazole having an atomic group represented by the following chemical formulas (1) to (3) is excellent in heat resistance, electrical insulation, mechanical properties, etc., conventionally, for example, as an insulating film in electronic devices. The use of is studied.

  Among such polybenzoazoles, polybenzoxazole, which is particularly excellent in heat resistance and the like, has been conventionally produced by dehydrating and cyclizing a polyamide resin obtained by a reaction between a diamine compound and a dicarboxylic acid halide. Yes. However, in such a production method, the polymerization degree of the polybenzoxazole finally obtained is governed by the polymerization degree of the polyamide resin as a precursor, and the reactivity of the diamine compound and the dicarboxylic acid halide is such that the reactivity of the diamine is low. Therefore, it is difficult to obtain a high molecular weight polybenzoxazole because the degree of polymerization of the polyamide resin as a precursor, and thus the degree of polymerization of polybenzoxazole, is low. Therefore, there exists a problem that film forming property is scarce. In order to solve such problems, there has been proposed a method for producing a high molecular weight polybenzoxazole by controlling (improving) the reactivity by using a silylated aromatic diamine as a monomer (patent) Reference 1).

  On the other hand, in order to develop excellent heat resistance, it is generally known that it is useful to use a monomer having a rigid molecular structure having a benzene ring or the like as a monomer. When a monomer having a structure is used, the resulting polymer is poor in intermolecular cohesion and becomes brittle although it is strong. Therefore, there exists a problem that film forming property is scarce (refer patent document 2).

In addition, it has been proposed to further improve the inherent properties of polybenzoazole by introducing an inorganic oxide phase into polybenzoazole. For example, SiO ₂ is a structural unit by a sol-gel reaction using a silane coupling agent and an alkoxysilane compound on a side chain portion of polybenzoxazole (polybenzimidazole) or a benzene ring having a reactive substituent. Non-Patent Documents 1 and 2 propose a polybenzoxazole (polybenzimidazole) -silica hybrid material obtained by introducing a silica phase.

  However, the present inventors have examined the hybrid materials described in Non-Patent Documents 1 and 2 described above, and the techniques disclosed therein have sufficient film forming properties and excellent heat resistance. It has proved difficult to produce silica-containing hybrid materials. Specifically, a reactive substituent is introduced into the benzene ring constituting polybenzoxazole (polybenzimidazole) obtained according to the production methods described in Non-Patent Documents 1 and 2, and then a silane coupling agent or the like is used. In the hybrid material in which the silica phase is introduced by the sol-gel reaction, the bonding site between the polybenzoxazole (polybenzimidazole) and the coupling agent is not sufficient in heat resistance. Therefore, it is difficult to say that it has sufficient heat resistance.

Japanese Patent Publication No. 4-58808 JP-A-2005-97365

J. Premachandra et al., "Polymer-Silica Hybrid Materials Prepared from Some Functionalized Polybenzoxazoles and Polybenzobisthiazoles", Journal of Sol-Gel Science and Technology, Kluwer Academic Publishers, Netherlands, 1996, Vol. 7, p.163-175 Shih-Wei Chuang et al., `` Syntethis and properties of fluorine-containing polybenzoimidazole / silica nanocomposite membranes for proton change membrane fuel cells '', Journal of Membrane Science, USA, 2007, 305, p.353-363

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is a hybrid material excellent in heat resistance and film formability (thin film formability) and its production It is to provide a method.

In order to solve such a problem, the present invention provides a polymer phase composed of polybenzoazole having any of the atomic groups represented by the following chemical formulas (1) to (3) in a repeating unit, and an inorganic oxidation. The gist is a hybrid material composed of an organic-inorganic polymer hybrid in which the physical phase is integrated through any of the organic groups represented by the following chemical formulas (4) to (6).

In the hybrid material according to the present invention, a first preferred embodiment is one in which the inorganic oxide phase is a silica phase having SiO ₂ as a structural unit.

Moreover, the hybrid material of the present invention is, in a second preferred embodiment, from a linear polybenzoxazole in which the polymer phase has any one of atomic groups represented by the following chemical formulas (7) to (9) in a repeating unit. In the third preferred embodiment, the polymer phase is composed of a linear polybenzoxazole having an atomic group represented by the following chemical formula (10) in the repeating unit.

Furthermore, the hybrid material of the present invention is, in the fourth preferred embodiment, characterized in that the organic-inorganic polymer hybrid comprises I) a silylated product of aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, and the following chemical formulas (11) to (13) A linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end, obtained by using any one or more of the compounds represented by formula (II) and an aromatic tetracarboxylic dianhydride; II ) A sol-gel reaction is performed with at least one alkoxysilane compound in the presence of water, and the resulting reaction product is oxazolated.

In the hybrid material of the present invention, in the fifth preferred embodiment, the organic-inorganic polymer hybrid comprises I) a silylated product of aromatic dihydroxydiamine, an aromatic dicarboxylic acid chloride, and the following chemical formulas (11) to (13): A linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end, obtained by using any one or more of the compounds represented by formula (II) and an aromatic tetracarboxylic dianhydride; II ) A mixture with silica fine particles is oxazolized.

On the other hand, the hybrid material of the present invention is, in a sixth preferred embodiment, the polymer phase is composed of a branched polybenzoxazole having any one of atomic groups represented by the following chemical formulas (7) to (9).

Moreover, the hybrid material of the present invention, in a seventh preferred embodiment, is characterized in that the organic-inorganic polymer hybrid is: I) aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, aromatic tricarboxylic acid chloride, and the following chemical formula (11): A branched polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at least at a part of a plurality of terminals obtained by using at least one of the compounds represented by (13) to (13). II) A sol-gel reaction of at least one of alkoxysilane compounds in the presence of water and oxazolization of the resulting reaction product.

Furthermore, the hybrid material of the present invention, in an eighth preferred embodiment, is characterized in that the organic-inorganic polymer hybrid is: I) an aromatic dihydroxydiamine, an aromatic dicarboxylic acid chloride, an aromatic tricarboxylic acid chloride, the following chemical formula (11): A branched polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at least at a part of a plurality of terminals obtained by using at least one of the compounds represented by (13) to (13). II) A mixture with silica fine particles is formed by oxazolation.

On the other hand, in the hybrid material according to the ninth aspect of the present invention, in the ninth preferred embodiment, the polymer phase has a linear polymer having any of atomic groups represented by the following chemical formulas (14) to (16) in the repeating unit. It consists of benzimidazole. In a tenth preferred embodiment, the polymer phase consists of linear polybenzimidazole having an atomic group represented by the following chemical formula (17) in the repeating unit.

In addition, in an eleventh preferred embodiment of the hybrid material according to the present invention, the organic-inorganic polymer hybrid is represented by I) an aromatic tetraamine, an aromatic dicarboxylic acid chloride, and the following chemical formulas (11) to (13): A linear polybenzimidazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end, obtained by using any one or more of the compounds represented and an aromatic tetracarboxylic dianhydride; and II) alkoxy A sol-gel reaction is carried out with at least one silane compound in the presence of water, and the resulting reaction product is converted into an imidazole.

  Furthermore, in the hybrid material according to the present invention, in the first to eleventh preferred embodiments described above, the silica content of the organic-inorganic polymer hybrid is preferably 1 to 40% by weight, and 20 to 40 is preferable. More preferably, it is% by weight.

On the other hand, the gist of the present invention is also a method capable of advantageously producing the hybrid material of the above-described aspect. Specifically, in the method for producing the hybrid material according to the first to third preferred embodiments described above, a silylated product of aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, and the following chemical formulas (11) to (13): A step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end using any one or more of the compounds represented by: and an aromatic tetracarboxylic dianhydride; A step of subjecting the linear polybenzoxazole precursor and at least one of the alkoxysilane compounds to a sol-gel reaction in the presence of water and oxazlating the resulting reaction product to form an organic-inorganic polymer hybrid; The gist of the method for producing a hybrid material characterized by comprising:

Moreover, this invention makes it the manufacturing method of the hybrid material which concerns on the 1st-3rd preferable aspect mentioned above, silylated thing of aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, and following Chemical formula (11)-(13 ) And a step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal using any one or more of the compounds represented by formula (1) and an aromatic tetracarboxylic dianhydride; And a method for producing a hybrid material characterized by comprising a step of converting the mixture of such a linear polybenzoxazole precursor and silica fine particles into an organic-inorganic polymer hybrid by oxazolation. It is.

Furthermore, the present invention provides a method for producing a hybrid material according to the first or sixth preferred embodiment described above, wherein aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride and aromatic tricarboxylic acid chloride are -20 to 0 ° C. A step of synthesizing a branched polybenzoxazole precursor I by polymerization in an organic solvent containing an oxirane compound under temperature conditions, the branched polybenzoxazole precursor I, and the following chemical formulas (11) to (13): A step of synthesizing a branched polybenzoxazole precursor II having a trimethoxysilyl group or a triethoxysilyl group at least at a part of a plurality of terminals using at least one of the compounds represented by At least one of a branched polybenzoxazole precursor II and an alkoxysilane compound; A sol-gel reaction in the presence of water, and oxazolizing the resulting reaction product to form an organic-inorganic polymer hybrid. To do.

Moreover, this invention makes the aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, and aromatic tricarboxylic acid chloride into -20-20 degreeC in the manufacturing method of the hybrid material which concerns on the 1st or 6th preferable aspect mentioned above. Under a temperature condition, polymerization is performed in an organic solvent containing an oxirane compound to synthesize a branched polybenzoxazole precursor I ′, the branched polybenzoxazole precursor I ′, and the following chemical formulas (11) to ( 13) a step of synthesizing a branched polybenzoxazole precursor II ′ having a trimethoxysilyl group or a triethoxysilyl group at least at a part of a plurality of terminals using at least one of the compounds represented by 13) And a mixture of the branched polybenzoxazole precursor II ′ and silica fine particles Organic by - a method for manufacturing a hybrid material, characterized by a step of the inorganic polymer hybrid is for its gist.

Furthermore, the present invention provides a method for producing a hybrid material according to the first, ninth, or tenth preferred embodiments described above, using an aromatic tetraamine, an aromatic dicarboxylic acid chloride, and the following chemical formulas (11) to (13): ) And a step of synthesizing a linear polybenzimidazole precursor having a trimethoxysilyl group or a triethoxysilyl group at a terminal using any one or more of the compounds represented by (II) and an aromatic tetracarboxylic dianhydride; , A step of making an organic-inorganic polymer hybrid by subjecting the linear polybenzimidazole precursor and at least one of the alkoxysilane compounds to sol-gel reaction in the presence of water and imidazolization of the obtained reaction product. The gist of the method for producing a hybrid material characterized by comprising:

  In addition, in the method for producing a hybrid material according to the present invention described above, the silica content of the organic-inorganic polymer hybrid is preferably 1 to 40% by weight, and more preferably 20 to 40% by weight.

  As described above, in the hybrid material according to the present invention, the polybenzoazole phase and the inorganic oxide phase are composed of an organic-inorganic polymer hybrid in which they are integrated through a predetermined atomic group. In addition, it has excellent film-formability (thin film moldability) and excellent heat resistance.

It is explanatory drawing which shows partially and typically an example of the organic-inorganic polymer hybrid which comprises the hybrid material of this invention.

  Hereinafter, the present invention will be specifically described with appropriate reference to the drawings.

FIG. 1 partially and schematically shows an example of an organic-inorganic polymer hybrid constituting a hybrid material according to the present invention. As is clear from FIG. 1, the organic-inorganic polymer hybrid shown therein is a repeating unit (constituent unit) having any one of atomic groups represented by the following chemical formulas (1) to (3): A A linear polybenzoazole phase composed of the above and a silica phase having SiO ₂ as a structural unit are integrally formed through a predetermined atomic group: α. In more detail, the predetermined atomic group: α is a divalent organic group, and one of the bonds is a repeating unit at the end of the linear polybenzoazole chain constituting the linear polybenzoazole phase (configuration Unit), and the other bond is bonded to the Si atom constituting the silica phase, thereby forming an integral organic-inorganic polymer hybrid. Such an organic-inorganic polymer hybrid of the present invention becomes a sufficient molecular weight body when the organic polymer chain is crosslinked by an inorganic polymer (silica) to form an organic-inorganic hybrid polymer chain. Furthermore, since the order of the molecular chain is disturbed by having a three-dimensional structure starting from the silica phase, the molecular weight is low only by the polymer phase, and the polymer chain is too rigid, resulting in poor film formation. Even if it is a case, it will have the outstanding film forming property.

  In the organic-inorganic polymer hybrid shown in FIG. 1, the inorganic oxide phase is a silica phase, but the inorganic oxide phase constituting the organic-inorganic polymer hybrid of the present invention is not limited to the silica phase. . For example, even in the case of an organic-inorganic polymer hybrid composed of an inorganic oxide phase having a structural unit of an inorganic oxide such as magnesium oxide, aluminum oxide, zirconium oxide or titanium oxide instead of the silica phase, It can be used as a constituent of a hybrid material.

In the present invention, the predetermined atomic group: α (divalent organic group) shown in FIG. 1 is any one of organic groups represented by the following chemical formulas (4) to (6). There is a big feature. That is, in the organic-inorganic polymer hybrid shown in FIG. 1, the silica phase is bonded to the end of the linear polybenzoazole phase via a predetermined organic group, in other words, the linear polybenzoazole phase. The terminal is modified with a silica phase, and a predetermined atomic group that binds the linear polybenzoazole phase and the silica phase: α (divalent organic group) has a benzene ring. Therefore, the organic-inorganic polymer hybrid constituting the hybrid material of the present invention has excellent film forming properties (thin film formability) and excellent heat resistance. The reason for the excellent heat resistance is that the end of the organic polymer, which is considered to start thermal decomposition, is crosslinked and integrated by the silica phase, so that the end of the organic polymer is substantially absent, and By using a coupling agent having a phenyl ring with high heat resistance, it is considered that decomposition at a predetermined atomic group: α (divalent organic group) portion hardly occurs, and thus excellent heat resistance is exhibited. In the present invention, excellent film forming property means that a flexible film (self-supporting thin film) is obtained without a support. For example, when the film is formed to a thickness of 30 μm, It means that a film without cracks can be produced.

Here, in the present invention, the polybenzoazole phase constituting the organic-inorganic polymer hybrid is preferably a polybenzoxazole phase. More specifically, the polybenzoazole phase is a linear polybenzoxazole having any of the atomic groups represented by the following chemical formulas (7) to (9) in the repeating unit, or the following chemical formulas (7) to ( It is preferable that it is comprised with the branched polybenzoxazole (polybenzoxazole which has a branched structure in a molecular chain) which has either of the atomic groups represented by 9).

The polybenzoazole phase is more preferably composed of linear polybenzoxazole having an atomic group represented by the following chemical formula (10) in the repeating unit, and more preferably, the following chemical formula (10). It is composed of a linear polybenzoxazole having a number average molecular weight of 5,000 to 500,000, more preferably 100,000 to 200,000, the atomic group represented as a repeating unit. If the molecular weight is lower than this range, the film-forming property is poor, and the number of ends increases, so that decomposition from the ends tends to occur, and the heat resistance also decreases. On the other hand, if the molecular weight is higher than this range, the viscosity becomes too high, and the handleability deteriorates. Further, in the synthesis of a high molecular weight polymer, only a slight difference in the molar ratio of charged monomers causes a large change in the molecular weight of the resulting polymer, making it difficult to produce a stable molecular weight polymer.

On the other hand, in the present invention, the polybenzoazole phase constituting the organic-inorganic polymer hybrid is also preferably a polybenzimidazole phase. Specifically, the polybenzoazole phase is composed of linear polybenzimidazole having any one of atomic groups represented by the following chemical formulas (14) to (16) in the repeating unit.

The polybenzoazole phase is more preferably composed of linear polybenzimidazole having an atomic group represented by the following chemical formula (17) in the repeating unit, and more preferably, the following chemical formula (17). It is composed of a linear polybenzimidazole having a number average molecular weight of 8000 to 12000 with the represented atomic group as a repeating unit. This is because the following chemical formula (17) has the highest heat resistance and is considered to be a structure that can ensure film forming properties.

  Furthermore, in the hybrid material of the present invention, the silica content of the organic-inorganic polymer hybrid is desirably 1 to 40% by weight, depending on the use of the material and the type of polybenzoazole constituting the polymer phase, It is more desirably 10 to 40% by weight, and further desirably 20 to 40% by weight. If the silica content is less than 1% by weight, a sufficient hybrid effect may not be obtained. On the other hand, if the silica content exceeds 40% by weight, the rigidity of the film becomes too high. This is because problems are likely to arise. Specifically, linear PBO (IPC-HAB) which is a kind of linear polybenzoxazole-silica hybrid composed of a polymer phase composed of linear polybenzoxazole and a silica phase formed according to a sol-gel method. ): In the PAPTMS-silica (sol-gel) hybrid, the silica content is preferably 1 to 30% by weight, more preferably 10 to 30% by weight, and 20 to 30% by weight. It is further desirable. If the silica content is less than 1% by weight, a sufficient hybrid effect may not be obtained. On the other hand, if the silica content exceeds 30% by weight, the rigidity of the film becomes too high. This is because problems are likely to arise. Moreover, in the linear PBO (OBC-6FAP): PAPTMS-silica (sol-gel) hybrid which is another kind of linear polybenzoxazole-silica hybrid, the silica content is 1 to 40% by weight. It is desirable that it is 10 to 40% by weight, more desirably 20 to 40% by weight. If the silica content is less than 1% by weight, a sufficient hybrid effect may not be obtained. On the other hand, if the silica content exceeds 40% by weight, the rigidity of the film becomes too high. This is because problems are likely to arise. Furthermore, linear PBI (IPC-DAB): PAPTMS-, which is a kind of linear polybenzimidazole-silica hybrid, composed of a polymer phase composed of linear polybenzimidazole and a silica phase formed according to the sol-gel method. In the case of a silica (sol-gel) hybrid, the silica content is desirably 1 to 30% by weight, more desirably 10 to 30% by weight, and further desirably 20 to 30% by weight. . If the silica content is less than 1% by weight, a sufficient hybrid effect may not be obtained. On the other hand, if the silica content exceeds 30% by weight, the rigidity of the film becomes too high. This is because problems are likely to arise. In addition, comparing linear PBO (IPC-HAB): PAPTMS-silica (sol-gel) hybrid with linear PBI (IPC-DAB): PAPTMS-silica (sol-gel) hybrid, linear PBO (IPC-HAB): -HAB): PAPTMS-silica (sol-gel) hybrid is more preferable because it has better heat resistance.

  By the way, the organic-inorganic polymer hybrid constituting the hybrid material according to the present invention can be synthesized (manufactured) by the following method, for example. In each of the following synthesis methods, various conditions and methods such as temperature conditions for reacting various compounds can be conventionally used, but the methods described below are particularly preferable. In addition, since the following reactions proceed effectively in an organic solvent, conventional reactions such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO) have been made. Among various solvents used in the organic synthesis, those according to the reaction are appropriately selected and used.

A. Synthesis of linear polybenzoxazole-silica hybrid An organic-inorganic polymer hybrid (linear polybenzoxazole-silica hybrid) in which the polymer phase is linear polybenzoxazole and the inorganic oxide phase is silica phase is advantageously Is synthesized by either of the following synthesis methods A1 or A2. Specifically, the synthesis method A1 includes an aromatic dihydroxydiamine silylated product, an aromatic dicarboxylic acid chloride, one or more compounds represented by the following chemical formulas (11) to (13), and an aromatic tetracarboxylic acid. A step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at a terminal using an acid dianhydride, and at least one of the linear polybenzoxazole precursor and an alkoxysilane compound; This is a technique including a step of subjecting the above to a sol-gel reaction in the presence of water and oxazolizing the obtained reaction product to obtain an organic-inorganic polymer hybrid. As synthesis method A2, silylated product of aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, any one or more of compounds represented by the following chemical formulas (11) to (13), and aromatic tetracarboxylic acid dihydrate A step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal using an anhydride, and a mixture of the linear polybenzoxazole precursor and silica fine particles are converted into oxazole. And a step of forming an organic-inorganic polymer hybrid. In any of these methods, first, the aromatic dihydroxydiamine is silylated using a silylating agent.

  Here, as aromatic dihydroxydiamine that can be used in the present invention, 2,4-diamino-1,5-benzenediol, 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB), 3, 3′-diamino-4,4′-dihydroxybiphenyl, 2,2′-bis (3-amino-4-hydroxyphenyl) ketone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfide, 2, 2-bis (3-amino-4-hydroxyphenyl) ether, 2,2-bis (3-amino-4-aminophenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2 , 2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) methane, 2,2-bis (3 -Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane (6FAP), 2,2-bis (3-amino-4-hydroxyphenyl) difluoro Methane, 2,4-diaminoresorcinol, 2,4-diamino-3-methylresorcinol, 4,6-diaminoresorcinol, 4,6-diamino-2-methylresorcinol, 9,9-bis (4- (4-amino -3-hydroxy) phenoxyphenyl) fluorene, 9,9-bis (4- (4-amino-3-hydroxy) phenoxy-3-methylphenyl) fluorene, 9,9-bis (4- (4-amino-3) -Hydroxy) phenoxy-3-phenylphenyl) fluorene, 9,9-bis (4- (3-amino-4-hydro) Xyl) phenoxyphenyl) fluorene, 9,9-bis (4- (3-amino-4-hydroxy) phenoxy-3-methylphenyl) fluorene, 9,9-bis (4- (3-amino-4-hydroxy) Phenoxy-3-phenylphenyl) fluorene, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis (2-methyl-5-cyclohexyl-4- (4-amino-3-hydroxy) ) Phenoxyphenyl) fluorene, 3,3′-diamino-4,4′-dihydroxybiphenyl ether, 3,3′-diamino-4,4′-dihydroxy-2,2′-dimethylbiphenyl ether, 4,4′- Diamino-3,3′-dihydroxy-2,2′-dimethylbiphenyl ether, 1,1 ′-(1,4-phenylenebis (1-mes Ruethylidene)) bis ((3-cyclohexyl-2-methyl) -4- (4-amino-3-hydroxy) phenoxyphenyl) propane, 2,2-bis (3-cyclohexyl-4- (4-amino-3- Hydroxyphenoxy) phenyl) propane, 1,1-bis (3-cyclohexyl-4- (4-amino-3-hydroxy) phenoxyphenyl) cyclohexane and the like can be exemplified. Moreover, even such trimethylsilylated products or hydrochlorides of aromatic dihydroxydiamines can be used.

  Examples of the silylating agent include hexamethyldisilazane, dimethyldichlorosilane, trimethylchlorosilane, N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide (BSA), N-methyl-N-trimethylsilylacetamide, N-methyl. -N-trimethylsilyltrifluoroacetamide, N-trimethylsilyldimethylamine, N-trimethylsilyldiethylamine, N, O-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylimidazole, tetramethyldisilazane, tert-butyldimethylchlorosilane, N -Methyl-N- (tert-butyldimethylsilyl) trifluoroacetamide, dichloromethyltetramethyldisilazane, chloromethyldimethylchlorosilane, bromomethyldi Chill chlorosilane, furo Fe mesyl amine, furo Fe mesyl chloride, furo Fe mesyl diethylamine, can be exemplified.

  Next, the resulting silylated product of aromatic dihydroxydiamine is reacted with aromatic dicarboxylic acid chloride. As such aromatic dicarboxylic acid chloride, the aromatic dicarboxylic acid described below is reacted with an excess amount of thionyl chloride in the presence of a catalyst such as N, N-dimethylformamide at room temperature to 75 ° C., and then Excess thionyl chloride is removed by heating and vacuum. The target aromatic dicarboxylic acid chloride can be obtained by recrystallizing the reaction product with a solvent such as hexane. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluorophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6 -Tetrafluoroisophthalic acid, 3,4,5,6-tetrafluorophthalic acid, 4,4'-hexafluoroisopropylidenediphenyl-1,1-dicarboxylic acid, 2,2'-bis (trifluoromethyl) -4 , 4′-diphenylenedicarboxylic acid, 4,4′-oxydiphenyl-1,1-dicarboxylic acid, 3,3′-dicarboxyldiphenyl ether, 3,4′-dicarboxydiphenyl ether, 4,4′-dicarboxydiphenyl ether 3,3′-dicarboxyldiphenylmethane, 3,4′-dicarboxyldiphenylmethane 4,4′-dicarboxyldiphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane, 3,4′-dicarboxyldiphenyldifluoromethane, 4,4′-dicarboxyldiphenyldifluoromethane, 3,3′-dioxymethane Carboxyl diphenyl sulfone, 3,4′-dicarboxyl diphenyl sulfone, 4,4′-dicarboxyl diphenyl sulfone, 3,3′-dicarboxyl diphenyl sulfide, 3,4′-dicarboxyl diphenyl sulfide, 4,4′-di Carboxyl diphenyl sulfide, 3,3′-dicarboxyl diphenyl ketone, 3,4′-dicarboxyl diphenyl ketone, 4,4′-dicarboxyl diphenyl ketone, 2,2-bis (3-carboxylphenyl) propane, 2,2 -(3,4 -Dicarboxyldiphenyl) propane, 2,2- (3,4'-dicarboxyldiphenyl) hexafluoropropane, 2,2-bis (3-carboxylphenyl) hexafluoropropane, 2,2-bis (4-carboxylphenyl) ) Hexafluoropropane, 1,3-bis (3-carboxylphenoxy) benzene, 1,4-bis (3-carboxylphenoxy) benzene, 1,4-bis (4-carboxylphenoxy) benzene, 3,3 ′-( 1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 4,4 ′-(1,4- Phenylenebis (1-methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxylphenoxy) phen Nyl) propane, 2,2-bis (4- (4-carboxylphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxylphenoxy) phenyl) hexanefluoropropane, 2,2-bis (4- (4-carboxylphenoxy) phenyl) hexafluoropropane, bis (4- (3-carboxylphenoxy) phenyl) sulfide, bis (4- (4-carboxylphenoxy) phenyl) sulfide, bis (4- (3-carboxylphenoxy) Examples thereof include phenyl) sulfone and bis (4- (4-carboxylphenoxy) phenyl) sulfonic acid.

  When the silylated product of aromatic dihydroxydiamine and aromatic dicarboxylic acid chloride are reacted, the amount of aromatic dicarboxylic acid chloride used is preferably slightly less than that of aromatic dihydroxydiamine. Specifically, aromatic dicarboxylic acid chloride is used in such a ratio that aromatic dihydroxydiamine: aromatic dicarboxylic acid chloride = 3.00: 2.50 to 3.00: 2.99 (molar ratio). By this, the film forming property of the obtained polybenzoxazole-silica hybrid becomes more excellent. A linear polybenzoxazole precursor having a hydroxyamine terminal (—NH—OH) is obtained by reacting a silylated product of aromatic dihydroxydiamine and an aromatic dicarboxylic acid chloride in such a ratio.

Next, a linear polybenzoxazole precursor having a hydroxyamine terminal (—NH—OH), one or more compounds represented by the following chemical formulas (11) to (13), and an aromatic tetracarboxylic dianhydride Is reacted to synthesize a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal.

  Here, the compound represented by the chemical formulas (11) to (13) is a silane coupling agent having a benzene ring (phenyl silane coupling agent), specifically, o-aminophenyltrimethoxysilane. , M-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane (PAPTMS), o-aminophenyltriethoxysilane, m-aminophenyltriethoxysilane, p-aminophenyltriethoxysilane, 1-isocyanate-4- Triethoxysilylbenzene, 1-isocyanate-3-triethoxysilylbenzene, 1-isocyanate-4-trimethoxysilylbenzene, and 1-isocyanate-3-trimethoxysilylbenzene. By reacting such a specific silane coupling agent and aromatic tetracarboxylic dianhydride with a linear polybenzoxazole precursor having a hydroxyamine terminal (—NH—OH), a linear polybenzoxazole is reacted. A linear polybenzoxazole-silica hybrid precursor obtained by integrating a precursor phase and a silica phase precursor via a unique organic group is obtained.

  In addition, as aromatic tetracarboxylic acid dihydrate, pyromellitic anhydride (PMDA), oxydiphthalic acid dianhydride (OPDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 2,2′-bis [ (Dicarboxyphenoxy) phenyl] propane dianhydride (BSAA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and the like can be exemplified.

  Using the linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end synthesized as described above, a silica phase as an inorganic oxide phase is introduced and oxazolated. However, as a method for introducing the silica phase, there are a sol-gel method (synthesis method A1) and a method using silica fine particles (synthesis method A2).

  In the method based on the sol-gel method (synthesis method A1), a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal and an alkoxysilane compound are subjected to a sol-gel reaction. A linear polybenzoxazole precursor having a silica phase at the end is obtained. Examples of the alkoxysilane compound used in the present invention include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, trimethoxysilane, triethoxysilane, and methyltrimethoxysilane. , Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoro Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxy silane, can be exemplified. In addition, since water is required in the reaction system in order to advance the sol-gel reaction, an amount of water necessary for the sol-gel reaction is appropriately used.

  On the other hand, in the technique using silica fine particles (Synthetic technique A2), for example, a linear polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal and silica fine particles are added in a predetermined solvent. Then, a linear polybenzoxazole precursor having a silica phase at the terminal is obtained by mixing.

  And the target linear polybenzoxazole-silica hybrid is obtained by making the linear polybenzoxazole precursor which has a silica phase in the terminal oxazole. As a method for oxazolation, a method such as heating is advantageously employed as in the prior art.

B. Synthesis of branched polybenzoxazole-silica hybrid An organic-inorganic polymer hybrid (branched polybenzoxazole-silica hybrid) in which the polymer phase is a branched polybenzoxazole and the inorganic oxide phase is a silica phase is advantageously Is synthesized by either of the synthesis methods B1 or B2. Specifically, the synthesis method B1 is a method in which an aromatic dihydroxydiamine, an aromatic dicarboxylic acid chloride, and an aromatic tricarboxylic acid chloride are polymerized in an organic solvent containing an oxirane compound under a temperature condition of −20 to 0 ° C. Using at least the step of synthesizing the branched polybenzoxazole precursor I, the branched polybenzoxazole precursor I, and any one or more of the compounds represented by the following chemical formulas (11) to (13). A step of synthesizing a branched polybenzoxazole precursor II having a trimethoxysilyl group or a triethoxysilyl group at least at a part of the ends of the branched polybenzoxazole precursor II and at least one of alkoxysilane compounds; Sol-gel reaction in the presence of water. And a step of forming an organic-inorganic polymer hybrid by forming the same. In addition, with synthesis method B2, aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride and aromatic tricarboxylic acid chloride are polymerized in an organic solvent containing an oxirane compound under a temperature condition of -20 to 0 ° C. The step of synthesizing the branched polybenzoxazole precursor I ′, the branched polybenzoxazole precursor I ′, and at least one of the compounds represented by the following chemical formulas (11) to (13) A step of synthesizing a branched polybenzoxazole precursor II ′ having a trimethoxysilyl group or a triethoxysilyl group at least at one of its ends, and a mixture of the branched polybenzoxazole precursor II ′ and silica fine particles. And an organic-inorganic polymer hybrid by oxazolation A.

  In any of the synthesis methods B1 and B2, first, aromatic dihydroxydiamine, aromatic dicarboxylic acid chloride, and aromatic tricarboxylic acid chloride are placed in an organic solvent containing an oxirane compound under a temperature condition of -20 to 0 ° C. The branched polybenzoxazole precursor is synthesized by polymerization. Polymerization of the monomer group consisting of aromatic dihydroxydiamine and the like effectively proceeds by removing hydrogen chloride generated during the polymerization of the monomer group consisting of aromatic dihydroxydiamine from the reaction system by reacting with the oxirane compound. To do.

  Here, as the oxirane compound used in the above-described polymerization, any oxirane compound having reactivity with hydrogen chloride can be used. Specifically, ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide and the like can be exemplified. Moreover, as aromatic dihydroxydiamine and aromatic dicarboxylic acid chloride, each compound enumerated in "A. Synthesis of linear polybenzoxazole-silica hybrid" can be used as long as the object of the present invention is not inhibited. Examples of the aromatic tricarboxylic acid chloride include benzene-1,3,5-tricarboxylic acid chloride (BTC), benzene-1,2,4-tricarboxylic acid chloride, 4,4 ′, 4 ″ -benzene-1,3. , 5-triyl-tris (benzoic acid) chloride and the like can be used.

  Specifically, a monomer group composed of aromatic dihydroxydiamine or the like is polymerized according to the following procedure. First, a predetermined amount of aromatic dihydroxydiamine is added to an organic solvent and dissolved to obtain a reaction solution. Next, propylene oxide is added to the reaction solution, and the reaction solution is cooled to −20 ° C. Then, a mixed solution obtained by dissolving aromatic dicarboxylic acid chloride and aromatic tricarboxylic acid chloride in an organic solvent in advance is dropped into the reaction solution and reacted at −20 ° C. for a predetermined time, and further room temperature (25 ° C.). The target branched polybenzoxazole precursor is synthesized by reacting for a predetermined period of time, and a branched polybenzoxazole precursor solution is obtained. By appropriately changing the amount of each component used, the resulting branched polybenzoxazole precursor has either a hydroxyamine terminal (—NH—OH) or a carboxylic acid terminal (—COOH). After the synthesis, the branched polybenzoxazole precursor solution is purified as necessary.

  When the first stage polymerization (polymerization at a low temperature) of the monomer group is carried out at a temperature lower than -20 ° C, the melting point of the solvent used (for example, NMP) may be lowered, and the organic solvent is solidified and homogenized. May pose problems in the synthesis of complex precursor solutions. On the other hand, when it is carried out at a temperature exceeding 0 ° C., the side reaction proceeds and an extra polymerization reaction occurs, so that the polymer is gelled.

Any of the hydroxyamine-terminated (—NH—OH) or carboxylic acid-terminated (—COOH) branched polybenzoxazole precursors obtained as described above, and the compounds represented by the following chemical formulas (11) to (13) A branched polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at least at a part of the plurality of terminals is synthesized using at least one of these. In addition, the compounds represented by the following chemical formulas (11) to (13) are as described in detail in “A. Synthesis of linear polybenzoxazole-silica hybrid”. By using a specific silane coupling agent such as a compound represented by the following chemical formulas (11) to (13), the branched polybenzoxazole precursor phase and the silica phase precursor are integrated through a unique organic group. The branched polybenzoxazole-silica hybrid precursor thus obtained is obtained.

  In addition, when using the branched polybenzoxazole precursor which has a hydroxylamine terminal (-NH-OH), together with the specific silane coupling agent represented by the above chemical formulas (11) to (13), an aromatic tetra Carboxylic dianhydrides are also used in combination. As the aromatic tetracarboxylic dianhydride that can be used, the same compounds as those listed in “A. Synthesis of linear polybenzoxazole-silica hybrid” can be used.

  Using the branched polybenzoxazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the end synthesized as described above, the silica phase as an inorganic oxide phase is introduced and oxazolated. There are two methods for introducing the silica phase, as in “A. Synthesis of linear polybenzoxazole-silica hybrid”, a method using a sol-gel method (synthesis method B1), and a method using silica fine particles (synthesis method). B2). Specific procedures of these methods, compounds used, and the like are the same as those described above in “A. Synthesis of linear polybenzoxazole-silica hybrid”. According to each method, a branched polybenzoxazole precursor having a silica phase at the terminal is obtained.

  And the target branched polybenzoxazole-silica hybrid is obtained by making the branched polybenzoxazole precursor which has a silica phase in the terminal oxazole. As a method for oxazolation, a method such as heating is advantageously employed as in the prior art.

C. Synthesis of linear polybenzimidazole-silica hybrid An organic-inorganic polymer hybrid (linear polybenzimidazole-silica hybrid) in which the polymer phase is linear polybenzimidazole and the inorganic oxide phase is silica phase is advantageously Is synthesized by the following method. Specifically, using aromatic tetraamine, aromatic dicarboxylic acid chloride, any one or more of compounds represented by the following chemical formulas (11) to (13), and aromatic tetracarboxylic dianhydride, A step of synthesizing a linear polybenzimidazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal, and at least one of the linear polybenzimidazole precursor and the alkoxysilane compound in the presence of water, And a step of forming an organic-inorganic polymer hybrid by sol-gel reaction and imidazolization of the obtained reaction product. In this method, first, an aromatic tetraamine and an aromatic dicarboxylic acid chloride are reacted to synthesize a linear polybenzimidazole precursor having an amine terminal (—NH ₂ ). The compounds used in the following reactions, which are also used in “A. Synthesis of polybenzoxazole-silica hybrid”, can be the same as those described above. is there.

  Examples of the aromatic tetraamine used in the present invention include 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalene, 2,3,6,7-tetraaminonaphthalene, 3,3. ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenylmethane, 3,3 ', 4,4'-tetraaminodiphenyldifluoromethane, 3,3', 4,4 ' -Tetraaminodiphenylditrifluoromethyl, 2,2-bis (3,4-diaminophenyl) hexafluoropropane, 9,9-bis (4- (3,4-diaminophenoxy) phenyl) fluorene, 3,3 ', 4,4′-tetraaminodiphenylethane, 3,3 ′, 4,4′-tetraamino-1,2-diphenylethane, 3,3 ′, 4,4′-tetra Mino-2,2-diphenylpropane, 3,3 ′, 4,4′-tetraaminodiphenylthioether, 3,3 ′, 4,4′-tetraaminodiphenylsulfone, 3,3 ′, 4,4′-tetra Examples include aminodiphenyl ketone, 3,3 ′, 4,4′-tetraaminodiphenyl sulfide 3,3 ′, 4,4′-tetraaminobiphenyl, and the like. Such trimethylsilylated aromatic tetraamines and hydrochlorides can also be used.

Next, the obtained linear polybenzimidazole precursor having an amine terminal (—NH ₂ ), one or more compounds represented by the following chemical formulas (11) to (13), and aromatic tetracarboxylic dianhydride By reacting the product, a linear polybenzimidazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal is synthesized.

  Then, using a linear polybenzimidazole precursor having a trimethoxysilyl group or a triethoxysilyl group at the terminal synthesized as described above, a silica phase as an inorganic oxide phase is introduced, and imidazolation is performed. As a result, the desired linear polybenzimidazole-silica hybrid can be obtained. As a method for introducing the silica phase, any of the above-described sol-gel method or the method using silica fine particles can be employed.

  Since the hybrid material according to the present invention is excellent not only in heat resistance but also in film forming properties (thin film moldability) during production, for example, by following the method described below, a film excellent in heat resistance It is possible to manufacture as.

  Specifically, a sol-gel reaction between a polybenzoxazole precursor (polybenzimidazole precursor) having a trimethoxysilyl group or a triethoxysilyl group at the terminal and an alkoxysilane compound is allowed to proceed in a predetermined solvent. The polybenzoxazole (polybenzimidazole) -silica hybrid with excellent heat resistance is obtained by casting the reaction solution onto a film and heating to dry the solvent and oxidize the precursor (imidazolide). Is advantageously obtained.

  The film made of the hybrid material of the present invention thus obtained has the highest level of extremely excellent heat resistance among the existing organic polymer films, and is used for semiconductor interlayer insulating films and protective films. It is expected to be used for applications such as flexible substrates for printed wiring boards and flexible substrates for solar cells.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements and the like can be added.

For the films obtained in the following Examples and Comparative Examples, 5% weight loss temperature: T _d ⁵ was measured using a thermogravimetric analyzer (trade name: TG-DTA6300) manufactured by SEIKO instruments. Inc. Then, by thermogravimetric analysis, it was determined from the measurement results under a temperature rising rate of 10 ° C./min under a nitrogen stream (200 ml / min). The 5% weight reduction temperature means a temperature when the weight is reduced by 5.0 wt% based on the weight at 200 ° C. Moreover, the film forming property of the obtained film was evaluated by evaluating the flexibility. Specifically, a film formed to a film thickness of 30 μm is cut into a size of length: 3 cm × width: 1 cm, and the cut film is wound around a rod having a diameter of 2 mm, and the film is cracked or cracked. It was confirmed visually. The case where no cracks or cracks occurred in the film was evaluated as “◯”, and the case where cracks or cracks occurred was evaluated as “X”. Table 1 below shows the measurement results of 5% weight loss temperature: T _d ⁵ and the evaluation results of flexibility in the following examples and comparative examples.

-Examples 1-4
After the inside of a 100 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube was replaced with nitrogen, 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB): 2.59 g (12 mmol) was weighed out. N-methyl-2-pyrrolidone (NMP): 20 mL was added and completely dissolved. Thereafter, N, O-bis (trimethylsilyl) acetamide (BSA): 9.78 g (48 mmol) was added to the reaction solution and stirred at room temperature for 1 hour to effect silylation of HAB. The reaction solution is cooled with liquid nitrogen, and 2.13 g (11.4 mmol) of isophthalic acid chloride (IPC) is added, followed by reaction at −5 ° C. for 1 hour, and further at 25 ° C. for 24 hours. As a result, a hydroxyamine-terminated linear polybenzoxazole precursor solution [hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution] was obtained.

  Next, this hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio) to perform reprecipitation purification. The obtained solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then at 85 ° C. Vacuum drying was performed for 12 hours. The solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor thus obtained was redissolved in NMP and p-aminophenyltrimethoxysilane (PAPTMS): 0.26 g ( 1.2 mmol), and after complete dissolution, pyromellitic anhydride (PMDA): 0.26 g (1.2 mmol) is further added and reacted for 12 hours. Benzoxazole precursor solution [hereinafter referred to as a silane-terminated linear PBO (IPC-HAB): PAPTMS precursor solution. Was prepared.

The resulting silane-terminated linear PBO (IPC-HAB): PAPTMS precursor solution with an arbitrary amount of tetramethoxysilane (TMOS), water required for hydrolysis, and several drops of 1N hydrochloric acid aqueous solution as a catalyst The sol-gel reaction is allowed to proceed by adding and stirring at room temperature for 24 hours, and a linear polybenzoxazole precursor-silica hybrid solution [hereinafter, linear PBO (IPC-HAB): PAPTMS precursor-silica ( sol-gel) also called a hybrid solution. Was prepared. TMOS has a silica content in the film after oxazolation of 1% by weight in Example 1, 10% by weight in Example 2, 20% by weight in Example 3, and 30% in Example 4. Each was added in such a ratio as to be%. This linear polybenzoxazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 4 hours, whereby a linear polybenzoxazole precursor-silica hybrid film [hereinafter, linear PBO ( IPC-HAB): PAPTMS precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained linear PBO (IPC-HAB): PAPTMS precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then at 150 ° C. for 1 hour and at 500 ° C. for 3 hours in a nitrogen atmosphere. Then, it is oxazolated by heat treatment to form a linear polybenzoxazole-silica hybrid film [hereinafter also referred to as a linear PBO (IPC-HAB): PAPTMS-silica (sol-gel) hybrid film. ] Was obtained. The T _d ⁵ of each film in Examples 1-4, respectively, Example 1 626 ° C., Example 2 625 ° C. Example 3 641 ° C., Example 4 was 650 ° C.. In addition, the evaluation results of the flexibility were ○, with no cracks or cracks occurring in all the films.

-Example 5
As a silica component, a linear polybenzoxazole-silica hybrid film [hereinafter, referred to as the same as in Example 1 except that DMAc-dispersed colloidal silica particles (average particle size: 10 to 15 mm) manufactured by Nissan Chemical Co., Ltd. were used. Linear PBO (IPC-HAB): PAPTMS-silica (colloidal silica) hybrid film. ] Was obtained. The DMAc-dispersed colloidal silica particles were added in such a ratio that the silica content in the film after oxazolation was 20% by weight. The obtained film had a T _d ⁵ of 633 ° C., and the evaluation result of the flexibility was ○, with no cracks or cracks in the film.

-Examples 6 to 10
After replacing the inside of a 100 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube with nitrogen, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane (6FAP): 2.20 g (6 0.0 mmol), N-methyl-2-pyrrolidone (NMP): 39 mL was added and completely dissolved. Thereafter, N, O-bis (trimethylsilyl) acetamide (BSA): 5.72 g (28 mmol) was added to the reaction solution and stirred at room temperature for 1 hour to silylate 6FAP. The reaction solution was cooled with liquid nitrogen, 4,4′-oxydiphenyl-1,1-dicarboxylic acid chloride (OBC): 1.68 g (5.7 mmol) was added, and then at −5 ° C. for 1 hour. By reacting and further reacting at 25 ° C. for 24 hours, a hydroxyamine-terminated linear polybenzoxazole 6F precursor solution [hydroxyamine-terminated linear PBO (OBC-6FAP) precursor solution] was obtained.

  Subsequently, this hydroxyamine-terminated linear PBO (OBC-6FAP) precursor solution was dropped into ion-exchanged water, and reprecipitation purification was performed. The obtained solid hydroxyamine-terminated linear PBO (OBC-6FAP) precursor was recovered by filtration, thoroughly washed with ion-exchanged water, and then vacuum-dried at 50 ° C. for 12 hours. The solid hydroxyamine-terminated linear PBO (OBC-6FAP) precursor thus obtained was redissolved in NMP and p-aminophenyltrimethoxysilane (PAPTMS): 0.13 g (0.13 g) 0.6 mmol), and after complete dissolution, pyromellitic anhydride (PMDA): 0.13 g (0.6 mmol) is further added and reacted for 12 hours. Benzoxazole precursor solution [hereinafter referred to as silane-terminated linear PBO (OBC-6FAP): PAPTMS precursor solution. Was prepared.

The resulting silane-terminated linear PBO (OBC-6FAP): A few drops of tetramethoxysilane (TMOS), water required for hydrolysis, and 1N aqueous hydrochloric acid solution as catalyst in the PAPTMS precursor solution The sol-gel reaction is allowed to proceed by adding and stirring at room temperature for 24 hours, and a linear polybenzoxazole precursor-silica hybrid solution [hereinafter, linear PBO (OBC-6FAP): PAPTMS precursor-silica ( sol-gel) also called a hybrid solution. Was prepared. TMOS has a silica content in the film after oxazolation of 1 wt% in Example 6, 10 wt% in Example 7, 20 wt% in Example 8, and 30 wt% in Example 9. %, And in Example 10, the ratio was 40% by weight. This linear polybenzoxazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 4 hours, whereby a linear polybenzoxazole precursor-silica hybrid film [hereinafter, linear PBO ( OBC-6FAP): PAPTMS precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained linear PBO (OBC-6FAP): PAPTMS precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, at 150 ° C. for 1 hour and 420 ° C. for 3 hours in a nitrogen atmosphere. Then, it is oxazolated by heat treatment to form a linear polybenzoxazole-silica hybrid film [hereinafter also referred to as a linear PBO (OBC-6FAP): PAPTMS-silica (sol-gel) hybrid film. ] Was obtained. Table 1 shows the measurement results of T _d ⁵ .

-Example 11-
After replacing the inside of a 200 mL flask equipped with a stirrer, a nitrogen introducing tube and a calcium chloride tube with nitrogen, 4,73'-diamino-3,3'-dihydroxybiphenyl (HAB): 1.73 g (8 mmol) was weighed out. N-methylpyrrolidone (NMP): 100 mL was added and dissolved. Next, 3 mL of propylene oxide (PO) was added to the reaction solution, and the reaction solution was cooled to −20 ° C. Further, separately prepared benzene-1,3,5-tricarboxylic acid chloride (BTC): 0.27 g (1 mmol) and isophthalic acid chloride (IPC): 1.22 g (6 mmol) are dissolved in 30 mL of NMP. The mixed solution is gradually added to the reaction solution over 20 minutes, followed by reaction at −20 ° C. for 2 hours, and addition and reaction at 25 ° C. for 20 hours, whereby a hydroxyamine-terminated branched polybenzoxazole precursor is obtained. A body [branched PBO (BTC / IPC-HAB) precursor] solution was prepared.

  Subsequently, this hydroxyamine terminal branched polybenzoxazole precursor solution was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio), and reprecipitation purification was performed. The obtained solid hydroxyamine-end branched polybenzoxazole precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then vacuumed at 50 ° C. for 12 hours. Drying was performed. The solid hydroxyamine-terminated branched polybenzoxazole precursor thus obtained was redissolved in NMP and p-aminophenyltrimethoxysilane (PAPTMS): 0.22 g (1.0 mmol) was dissolved in this solution. And then completely dissolved, and then pyromellitic anhydride (PMDA): 0.22 g (1.0 mmol) is further added, reacted for 12 hours, and a branched polybenzoxazole precursor having a trimethoxysilyl group at the terminal Solution [Hereinafter referred to as silane terminal branched PBO (BTC / IPC-HAB): PAPTMS precursor solution. Was prepared.

The resulting silane-terminated PBO (BTC / IPC-HAB): Add several drops of tetramethoxysilane (TMOS), water required for hydrolysis, and 1N aqueous hydrochloric acid solution as catalyst to the PAPTMS precursor solution The sol-gel reaction is allowed to proceed by stirring at room temperature for 24 hours, and a branched polybenzoxazole precursor-silica hybrid solution [hereinafter, branched PBO (BTC / IPC-HAB): PAPTMS precursor-silica (sol- gel) Also called a hybrid solution. Was prepared. TMOS was added in such a ratio that the silica content in the film after oxazolation was 10% by weight. This branched polybenzoxazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 4 hours, whereby a branched polybenzoxazole precursor-silica hybrid film [hereinafter, branched PBO (BTC / IPC -HAB): PAPTMS precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained branched PBO (BTC / IPC-HAB): PAPTMS precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, under a nitrogen atmosphere, at 150 ° C. for 1 hour, and at 500 ° C. for 3 hours. Oxazolation is carried out by heat treatment for a time, and it is also called a branched polybenzoxazole-silica hybrid film [hereinafter referred to as a branched PBO (BTC / IPC-HAB): PAPTMS-silica (sol-gel) hybrid film. ] Was obtained. Table 1 shows the measurement results of T _d ⁵ .

-Example 12-
After replacing the inside of a 200 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube with nitrogen, benzene-1,3,5-tricarboxylic acid chloride (BTC): 0.27 g (1 mmol) and isophthalic acid chloride (IPC ): 1.62 g (8 mmol) was weighed, N-methylpyrrolidone (NMP): 100 mL was added and dissolved, and the reaction solution was cooled to -20 ° C. Next, 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) prepared separately: 1.95 g (9 mmol) was dissolved in NMP: 20 mL, and further propylene oxide (PO): 3 mL was added. The solution was gradually added to the reaction solution over 20 minutes, reacted at −20 ° C. for 2 hours, and then reacted at 25 ° C. for 20 hours, whereby a carboxylic acid-terminated branched polybenzoxazole precursor [branched PBO (BTC / IPC-HAB) Precursor] solution was prepared.

  Subsequently, this carboxylic acid terminal branched polybenzoxazole precursor solution was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio) to perform reprecipitation purification. The obtained solid carboxylic acid terminally branched polybenzoxazole precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then vacuumed at 50 ° C. for 12 hours. Drying was performed. The solid carboxylic acid terminally branched polybenzoxazole precursor thus obtained was redissolved in NMP, and p-aminophenyltrimethoxysilane (PAPTMS): 0.22 g (1.0 mmol) was dissolved in this solution. Is added and completely dissolved to obtain a branched polybenzoxazole precursor solution having a trimethoxysilyl group at least part of a plurality of ends [hereinafter, silane-terminated branched PBO (BTC / IPC-HAB): PAPTMS precursor It is called body solution. Was prepared.

The resulting silane-terminated PBO (BTC / IPC-HAB): Add several drops of tetramethoxysilane (TMOS), water required for hydrolysis, and 1N aqueous hydrochloric acid solution as catalyst to the PAPTMS precursor solution The sol-gel reaction is allowed to proceed by stirring at room temperature for 24 hours, and a branched polybenzoxazole precursor-silica hybrid solution [hereinafter, branched PBO (BTC / IPC-HAB): PAPTMS precursor-silica (sol- gel) Also called a hybrid solution. Was prepared. TMOS was added in such a ratio that the silica content in the film after oxazolation was 10% by weight. This branched polybenzoxazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 4 hours, whereby a branched polybenzoxazole precursor-silica hybrid film [hereinafter, branched PBO (BTC / IPC -HAB): PAPTMS precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained branched PBO (BTC / IPC-HAB): PAPTMS precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, under a nitrogen atmosphere, at 150 ° C. for 1 hour, and at 500 ° C. for 3 hours. Oxazolation is carried out by heat treatment for a time, and it is also called a branched polybenzoxazole-silica hybrid film [hereinafter referred to as a branched PBO (BTC / IPC-HAB): PAPTMS-silica (sol-gel) hybrid film. ] Was obtained. Table 1 shows the measurement results of T _d ⁵ .

-Example 13-
A branched polybenzoxazole-silica hybrid film [hereinafter, branched] in the same manner as in Example 12 except that DMAc-dispersed colloidal silica particles (average particle size: 10 to 15 mm) manufactured by Nissan Chemical Co., Ltd. were used as the silica component. PBO (BTC / IPC-HAB): It is also called a PAPTMS-silica (colloidal silica) hybrid film. ] Was obtained. The DMAc-dispersed colloidal silica particles were added in such a ratio that the silica content in the film after oxazolation was 10% by weight. Table 1 shows the measurement results of T _d ⁵ .

-Examples 14 and 15-
After replacing the inside of a 100 mL flask equipped with a stirrer, a nitrogen introducing tube and a calcium chloride tube with nitrogen, 3,3 ′, 4,4′-tetraaminobiphenyl (DAB): 1.47 g (7.25 mmol) was weighed. N, N-dimethylacetamide (DMAc): 55 mL was added and completely dissolved. Thereafter, pyridine (py): 0.67 g (8.46 mmol) and triethylamine (TEA): 0.86 g (8.46 mmol) as base compounds were added to form a salt with hydrogen chloride generated during the polymerization. It was. The solution was ice-cooled to −5 ° C., and with stirring, isophthalic acid chloride (IPC): 1.40 g (6.89 mmol) previously dissolved in 6 mL of N, N-dimethylacetamide (DMAc) was added. By reacting at −5 ° C. for 1 hour and further at 25 ° C. for 24 hours, an amine-terminated linear polybenzimidazole precursor solution [amine-terminated linear PBI (IPC-DAB) precursor solution] is obtained. It was.

  Subsequently, this amine-terminated linear PBI (IPC-DAB) precursor solution was dropped into water to perform reprecipitation purification. The obtained solid amine-terminated linear PBI (IPC-DAB) precursor was recovered by filtration, thoroughly washed with methanol, and then vacuum-dried at 85 ° C. for 12 hours. The solid amine-terminated linear PBI (IPC-DAB) precursor thus obtained was redissolved in DMAc, and p-aminophenyltrimethoxysilane (PAPTMS): 0.16 g (0 .73 mmol) was added and completely dissolved, and then pyromellitic anhydride (PMDA): 0.16 g (0.73 mmol) was further added and reacted for 12 hours, followed by linear polybenzoic acid having a trimethoxysilyl group at the end. Imidazole precursor solution [hereinafter referred to as silane-terminated linear PBI (IPC-DAB): PAPTMS precursor solution. Was prepared.

The resulting silane-terminated linear PBI (IPC-DAB): PAPTMS precursor solution with an arbitrary amount of tetramethoxysilane (TMOS), water required for hydrolysis, and several drops of 1N hydrochloric acid aqueous solution as a catalyst The sol-gel reaction is allowed to proceed by adding and stirring at room temperature for 24 hours, and a linear polybenzimidazole precursor-silica hybrid solution [hereinafter, linear PBI (IPC-DAB): PAPTMS precursor-silica ( sol-gel) also called a hybrid solution. Was prepared. TMOS was added in such a proportion that the silica content in the film after oxazolation was 1% by weight in Example 14 and 20% by weight in Example 15. This linear polybenzimidazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 4 hours, whereby a linear polybenzimidazole precursor-silica hybrid film [hereinafter referred to as linear PBI ( IPC-DAB): PAPTMS precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained linear PBI (IPC-DAB): PAPTMS precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, in a nitrogen atmosphere, at 150 ° C. for 1 hour and at 410 ° C. for 3 hours. Then, imidazolation is carried out by heat treatment, and a linear polybenzimidazole-silica hybrid film [hereinafter also referred to as linear PBI (IPC-DAB): PAPTMS-silica hybrid film. ] Was obtained. The T _d ⁵ of each film in Examples 14 and 15 was 624 ° C. in Example 14 and 628 ° C. in Example 15. Moreover, the evaluation result of the flexibility was ◯ with no cracks or cracks in any of the films.

-Comparative Example 1-
After the inside of a 100 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube was replaced with nitrogen, 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB): 2.59 g (12 mmol) was weighed out. N-methyl-2-pyrrolidone (NMP): 20 mL was added and completely dissolved. Thereafter, N, O-bis (trimethylsilyl) acetamide (BSA): 9.78 g (48 mmol) was added to the reaction solution and stirred at room temperature for 1 hour to effect silylation of HAB. The reaction solution is cooled with liquid nitrogen, and 2.13 g (11.4 mmol) of isophthalic acid chloride (IPC) is added, followed by reaction at −5 ° C. for 1 hour, and further at 25 ° C. for 24 hours. As a result, a hydroxyamine-terminated linear polybenzoxazole precursor solution [hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution] was obtained.

Next, this hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio) to perform reprecipitation purification. The obtained solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then at 85 ° C. Vacuum drying was performed for 12 hours. The solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor thus obtained is redissolved in NMP, the solution is cast on a polyester film and dried at 85 ° C. for 4 hours. Attempts were made to produce a hydroxyamine-terminated linear PBO (IPC-HAB) precursor film. However, the film was not brittle and lacked film strength and flexibility because it did not grow to a sufficient high molecular weight. The resulting hydroxyamine-terminated linear PBO (IPC-HAB) precursor film piece is heat-treated at 150 ° C. for 1 hour and at 500 ° C. for 3 hours in a nitrogen atmosphere to effect oxazolation. A terminal linear PBO (IPC-HAB) film piece was obtained. T _d ⁵ of the obtained film was 603 ° C., and the evaluation result of flexibility was ○, with no cracks or cracks generated in the film.

-Comparative Examples 2, 3-
After the inside of a 100 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube was replaced with nitrogen, 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB): 2.59 g (12 mmol) was weighed out. N-methyl-2-pyrrolidone (NMP): 20 mL was added and completely dissolved. Thereafter, N, O-bis (trimethylsilyl) acetamide (BSA): 9.78 g (48 mmol) was added to the reaction solution and stirred at room temperature for 1 hour to effect silylation of HAB. The reaction solution is cooled with liquid nitrogen, and 2.13 g (11.4 mmol) of isophthalic acid chloride (IPC) is added, followed by reaction at −5 ° C. for 1 hour, and further at 25 ° C. for 24 hours. As a result, a hydroxyamine-terminated linear polybenzoxazole precursor solution [hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution] was obtained.

  Next, this hydroxyamine-terminated linear PBO (IPC-HAB) precursor solution was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio) to perform reprecipitation purification. The obtained solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then at 85 ° C. Vacuum drying was performed for 12 hours. The solid hydroxyamine-terminated linear PBO (IPC-HAB) precursor thus obtained was redissolved in NMP and 2- (3-triethoxysilylpropyl) succinic anhydride ( TEPSA): 0.36 g (1.2 mmol) was added, and a linear polybenzoxazole precursor solution having a triethoxysilyl group at the end [hereinafter referred to as silane-terminated linear PBO (IPC-HAB): TEPSA precursor solution]. Was prepared.

The resulting silane-terminated linear PBO (IPC-HAB): TEPSA precursor solution with an arbitrary amount of tetramethoxysilane (TMOS), water required for hydrolysis, and several drops of 1N hydrochloric acid aqueous solution as a catalyst The sol-gel reaction is allowed to proceed by adding and stirring at room temperature for 24 hours, and a linear polybenzoxazole precursor-silica hybrid solution [hereinafter, linear PBO (IPC-HAB): TEPSA precursor-silica ( sol-gel) also called a hybrid solution. Was prepared. TMOS was added in such a proportion that the silica content in the film after oxazolation was 1% by weight in Comparative Example 3 and 20% by weight in Comparative Example 4. The reaction solution was cast on a polyester film and dried at 85 ° C. for 4 hours to obtain a linear polybenzoxazole precursor-silica hybrid film [linear PBO (IPC-HAB): TEPSA precursor-silica ( sol-gel) also called a hybrid film. ] Was obtained. The obtained linear PBO (IPC-HAB): TEPSA precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, in a nitrogen atmosphere, 1 hour at 150 ° C. and 3 hours at 500 ° C. Then, oxazolation is carried out by heat treatment, and a linear polybenzoxazole-silica hybrid film [hereinafter also referred to as linear PBO (IPC-HAB): TEPSA-silica (sol-gel) hybrid film]. ] Was obtained. The T _d ⁵ of each film in Comparative Examples 2 and 3 is 521 ° C. in Comparative Example 2 and 535 ° C. in Comparative Example 3, and the evaluation result of the flexibility shows that no cracks or cracks occur in any film. It was ○.

-Comparative Example 4-
After replacing the inside of a 100 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube with nitrogen, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane (6FAP): 2.20 g (6 0.0 mmol), N-methyl-2-pyrrolidone (NMP): 39 mL was added and completely dissolved. Thereafter, N, O-bis (trimethylsilyl) acetamide (BSA): 5.72 g (28 mmol) was added to the reaction solution and stirred at room temperature for 1 hour to silylate 6FAP. The reaction solution was cooled with liquid nitrogen, 4,4′-oxydiphenyl-1,1-dicarboxylic acid chloride (OBC): 1.68 g (5.7 mmol) was added, and then at −5 ° C. for 1 hour. The reaction was further continued at 25 ° C. for 24 hours to obtain a hydroxyamine-terminated linear polybenzoxazole precursor solution [hydroxyamine-terminated linear PBO (OBC-6FAP) precursor solution].

Subsequently, this hydroxyamine-terminated linear PBO (OBC-6FAP) precursor solution was dropped into ion-exchanged water, and reprecipitation purification was performed. The obtained solid hydroxyamine-terminated linear PBO (OBC-6FAP) precursor was recovered by filtration, thoroughly washed with ion-exchanged water, and then vacuum-dried at 50 ° C. for 12 hours. The solid hydroxyamine-terminated linear PBO (OBC-6FAP) precursor thus obtained is redissolved in NMP and the solution is cast on a polyester film and dried at 85 ° C. for 4 hours. Attempts were made to produce a hydroxyamine-terminated linear PBO (OBC-6FAP) precursor film, but it was not fragile and lacked film strength and flexibility because it did not grow to a sufficient high molecular weight. The obtained hydroxyamine-terminated linear PBO (OBC-6FAP) precursor film piece was heat-treated in a nitrogen atmosphere at 150 ° C. for 1 hour and 420 ° C. for 3 hours to perform oxazolation. The measurement results of T _d ⁵ using the obtained hydroxyamine-terminated linear PBO (OBC-6FAP) film piece are shown in Table 2 below.

-Comparative Example 5-
After replacing the inside of a 200 mL flask equipped with a stirrer, a nitrogen introducing tube and a calcium chloride tube with nitrogen, 4,73'-diamino-3,3'-dihydroxybiphenyl (HAB): 1.73 g (8 mmol) was weighed out. N-methylpyrrolidone (NMP): 100 mL was added and dissolved. Next, 3 mL of propylene oxide (PO) was added to the reaction solution, and the reaction solution was cooled to −20 ° C. Further, separately prepared benzene-1,3,5-tricarboxylic acid chloride (BTC): 0.27 g (1 mmol) and isophthalic acid chloride (IPC): 1.22 g (6 mmol) are dissolved in 30 mL of NMP. The mixed solution is gradually added to the reaction solution over 20 minutes, followed by reaction at −20 ° C. for 2 hours, and addition and reaction at 25 ° C. for 20 hours, whereby a hydroxyamine-terminated branched polybenzoxazole precursor is obtained. A body [branched PBO (BTC / IPC-HAB) precursor] solution was prepared.

Subsequently, this hydroxyamine terminal branched polybenzoxazole precursor was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio), and reprecipitation purification was performed. The obtained solid hydroxyamine-end branched polybenzoxazole precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then vacuumed at 50 ° C. for 12 hours. Drying was performed. The solid hydroxyamine end-branched polybenzoxazole precursor thus obtained was redissolved in NMP, the solution was cast on a polyester film and dried at 85 ° C. for 4 hours to obtain a hydroxyamine. Terminal branched polybenzoxazole precursor film [hereinafter referred to as hydroxyamine terminal branched PBO (BTC / IPC-HAB) precursor film. ] Was obtained. By fixing the obtained hydroxyamine terminal-branched PBO (BTC / IPC-HAB) precursor film to a metal frame and then heat-treating it at 150 ° C. for 1 hour and at 500 ° C. for 3 hours in a nitrogen atmosphere. Oxazolation was performed to obtain a hydroxyamine terminal branched polybenzoxazole film [hydroxyamine terminal branched PBO (BTC / IPC-HAB) film]. Table 2 shows the T _d ⁵ measurement results.

-Comparative Example 6
After replacing the inside of a 200 mL flask equipped with a stirrer, a nitrogen introduction tube and a calcium chloride tube with nitrogen, benzene-1,3,5-tricarboxylic acid chloride (BTC): 0.27 g (1 mmol) and isophthalic acid chloride (IPC ): 1.62 g (8 mmol) was weighed, N-methylpyrrolidone (NMP): 100 mL was added and dissolved, and the reaction solution was cooled to -20 ° C. Subsequently, separately prepared 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB): 1.95 g (9 mmol) was dissolved in NMP: 20 mL, and 3 mL of propylene oxide (PO) was further added. The solution was gradually added to the reaction solution over 20 minutes, reacted at −20 ° C. for 2 hours, and then reacted at 25 ° C. for 20 hours, whereby a carboxylic acid terminal branched polybenzoxazole precursor [branched PBO (BTC / IPC-HAB) precursor] solution was prepared.

Subsequently, this carboxylic acid terminal branched polybenzoxazole precursor was dropped into a mixed solution of water: methanol = 4: 1 (weight ratio), and reprecipitation purification was performed. The obtained solid carboxylic acid terminal branched polybenzoxazole precursor was recovered by filtration, thoroughly washed with a mixed solution of water: methanol = 4: 1 (weight ratio), and then vacuumed at 85 ° C. for 12 hours. Drying was performed. The solid carboxylic acid end-branched polybenzoxazole precursor thus obtained was redissolved in NMP, the solution was cast on a polyester film and dried at 85 ° C. for 4 hours to obtain a carboxylic acid. Terminal branched polybenzoxazole precursor film [hereinafter referred to as carboxylic acid terminal branched PBO (BTC / IPC-HAB) film. ] Was obtained. Table 2 shows the T _d ⁵ measurement results.

-Comparative Example 7-
After replacing the inside of a 100 mL flask equipped with a stirrer, a nitrogen introducing tube and a calcium chloride tube with nitrogen, 3,3 ′, 4,4′-tetraaminobiphenyl (DAB): 1.47 g (7.25 mmol) was weighed. N, N, -dimethylacetamide (DMAc): 55 mL was added and completely dissolved. Thereafter, pyridine (py): 0.67 g (8.46 mmol) and triethylamine (TEA): 0.86 g (8.46 mmol) as base compounds were added to form a salt with hydrogen chloride generated during the polymerization. It was. The solution was ice-cooled to −5 ° C., and with stirring, isophthalic acid chloride (IPC): 1.40 g (6.89 mmol) previously dissolved in 6 mL of N, N-dimethylacetamide (DMAc) was added. By reacting at −5 ° C. for 1 hour and further at 25 ° C. for 24 hours, an amine-terminated linear polybenzimidazole precursor solution [amine-terminated linear PBI (IPC-DAB) precursor solution] is obtained. It was.

Subsequently, this amine-terminated linear PBI (IPC-DAB) precursor solution was dropped into water to perform reprecipitation purification. The obtained solid amine-terminated linear PBI (IPC-DAB) precursor was recovered by filtration, thoroughly washed with methanol, and then vacuum-dried at 85 ° C. for 12 hours. The solid amine-terminated linear PBI (IPC-DAB) precursor thus obtained was redissolved in DMAc, this solution was cast on a polyester film and dried at 85 ° C. for 3 hours. Although an attempt was made to produce an amine-terminated linear PBI (IPC-DAB) precursor film, the film formation was poor and the film could not be formed. When the flexibility was evaluated using a piece-like film, the sample (fragment-like film) was cracked or cracked. Further, T _d ⁵ was measured by using a sample piece generated in the evaluation of the flexibility, and it was 624 ° C.

-Comparative examples 8 and 9-
After replacing the inside of a 100 mL flask equipped with a stirrer, a nitrogen introducing tube and a calcium chloride tube with nitrogen, 3,3 ′, 4,4′-tetraaminobiphenyl (DAB): 1.47 g (7.25 mmol) was weighed. N, N-dimethylacetamide (DMAc): 55 mL was added and completely dissolved. Thereafter, pyridine (py): 0.67 g (8.46 mmol) and triethylamine (TEA): 0.86 g (8.46 mmol) as base compounds were added to form a salt with hydrogen chloride generated during the polymerization. It was. The solution was ice-cooled to −5 ° C., and with stirring, isophthalic acid chloride (IPC): 1.40 g (6.89 mmol) previously dissolved in 6 mL of N, N-dimethylacetamide (DMAc) was added. The mixture was reacted at −5 ° C. for 1 hour and further reacted at 25 ° C. for 24 hours to obtain an amine-terminated linear polybenzimidazole precursor solution [amine-terminated linear PBI (IPC-DAB) precursor solution]. .

  Subsequently, this amine-terminated linear PBI (IPC-DAB) precursor solution was dropped into water to perform reprecipitation purification. The obtained solid amine-terminated linear PBI (IPC-DAB) precursor was recovered by filtration, thoroughly washed with methanol, and then vacuum-dried at 85 ° C. for 12 hours. The solid amine-terminated linear PBI (IPC-DAB) precursor thus obtained was redissolved in DMAc, and 2- (3-triethoxysilylpropyl) succinic anhydride (TEPSA) was dissolved in this solution. ): 0.22 g (0.73 mmol) was added, and a linear polybenzimidazole precursor solution having a triethoxysilyl group at the end [hereinafter referred to as a silane-terminated linear PBI (IPC-DAB): TEPSA precursor solution. Was prepared.

The resulting silane-terminated linear PBI (IPC-DAB): TEPSA precursor solution with an arbitrary amount of tetramethoxysilane (TMOS), water required for hydrolysis, and several drops of 1N hydrochloric acid aqueous solution as a catalyst The sol-gel reaction is allowed to proceed by stirring at room temperature for 24 hours, and a linear polybenzimidazole precursor-silica hybrid solution [hereinafter, linear PBI (IPC-DAB): TEPSA precursor-silica ( sol-gel) also called a hybrid solution. Was prepared. TMOS was added in such a proportion that the silica content in the film after oxazolation was 1 wt% in Comparative Example 8 and 20 wt% in Comparative Example 9. This linear polybenzimidazole precursor-silica hybrid solution was cast on a polyester film and dried at 85 ° C. for 3 hours, whereby a linear polybenzimidazole precursor-silica hybrid film [hereinafter, linear PBI ( IPC-DAB): TEPSA precursor-silica (sol-gel) hybrid film. ] Was obtained. The obtained linear PBI (IPC-DAB): TEPSA precursor-silica (sol-gel) hybrid film was fixed to a metal frame, and then, in a nitrogen atmosphere, 1 hour at 150 ° C. and 4 hours at 410 ° C. Then, imidazolation is performed by heat treatment, and linear polybenzimidazole-silica hybrid film [hereinafter referred to as linear PBI (IPC-DAB): TEPSA-silica (sol-gel) hybrid film]. ] Was obtained. The T _d ⁵ of each film in Comparative Examples 8 and 9 was 588 ° C. in Comparative Example 8 and 618 ° C. in Comparative Example 9. Moreover, the evaluation result of the flexibility was ◯ without any cracks or cracks in any of the films.

As is clear from Table 1 and Table 2, it was confirmed that the film made of the hybrid material according to the present invention has high heat resistance and can be advantageously formed into a film.

Claims (12)

A polymer phase composed of polybenzoxazole or polybenzimidazole and a silica phase having SiO ₂ as a structural unit are integrated via any one of organic groups represented by the following chemical formulas (4) to (6). A hybrid material composed of an organic-inorganic polymer hybrid ,
The polymer phase is composed of a linear polybenzoxazole having any one of atomic groups represented by the following chemical formulas (7) to (9) in a repeating unit,
The organic-inorganic polymer hybrid is I) 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) silylated, isophthalic acid chloride (IPC), and p-aminophenyltrimethoxysilane (PAPTMS). And a linear polybenzoxazole precursor having a trimethoxysilyl group at the end, obtained using an aromatic tetracarboxylic dianhydride, and II) at least one of alkoxysilane compounds in the presence of water , Sol-gel reaction, and oxazolization of the resulting reaction product,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 30% by weight.
A hybrid material characterized by that.

A polymer phase composed of polybenzoxazole or polybenzimidazole, and SiO ₂  A hybrid material composed of an organic-inorganic polymer hybrid integrated with any of organic groups represented by the following chemical formulas (4) to (6):
The polymer phase is composed of a linear polybenzoxazole having any one of atomic groups represented by the following chemical formulas (7) to (9) in a repeating unit,
The organic-inorganic polymer hybrid is I) 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) silylated, isophthalic acid chloride (IPC), and p-aminophenyltrimethoxysilane (PAPTMS). And a mixture of a linear polybenzoxazole precursor having a trimethoxysilyl group at the end, obtained by using an aromatic tetracarboxylic dianhydride, and II) silica fine particles, oxazolated. Yes,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 40% by weight,
A hybrid material characterized by that.

A polymer phase composed of polybenzoxazole or polybenzimidazole, and SiO ₂  A hybrid material composed of an organic-inorganic polymer hybrid integrated with any of organic groups represented by the following chemical formulas (4) to (6):
The polymer phase is composed of a linear polybenzoxazole having any one of atomic groups represented by the following chemical formulas (7) to (9) in a repeating unit,
The organic-inorganic polymer hybrid comprises I) 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane (6FAP) silylated and 4,4′-oxydiphenyl-1,1-dicarboxylic acid A linear polybenzoxazole precursor having a trimethoxysilyl group at its end, obtained using chloride (OBC), p-aminophenyltrimethoxysilane (PAPTMS), and aromatic tetracarboxylic dianhydride; II) At least one kind of alkoxysilane compound is subjected to sol-gel reaction in the presence of water, and the resulting reaction product is oxazolated,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 40% by weight,
A hybrid material characterized by that.

A polymer phase composed of polybenzoxazole or polybenzimidazole, and SiO ₂  A hybrid material composed of an organic-inorganic polymer hybrid integrated with any of organic groups represented by the following chemical formulas (4) to (6):
The polymer phase is composed of a branched polybenzoxazole having any of the atomic groups represented by the following chemical formulas (7) to (9),
The organic-inorganic polymer hybrid comprises I) 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB), isophthalic acid chloride (IPC), and benzene-1,3,5-tricarboxylic acid chloride (BTC). ) And p-aminophenyltrimethoxysilane (PAPTMS), a branched polybenzoxazole precursor having a trimethoxysilyl group at least at a part of the plurality of terminals, and II) an alkoxysilane compound Sol-gel reaction with at least one kind in the presence of water, and the resulting reaction product is oxazolated,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 40% by weight,
A hybrid material characterized by that.

A polymer phase composed of polybenzoxazole or polybenzimidazole, and SiO ₂  A hybrid material composed of an organic-inorganic polymer hybrid integrated with any of organic groups represented by the following chemical formulas (4) to (6):
The polymer phase is composed of a branched polybenzoxazole having any of the atomic groups represented by the following chemical formulas (7) to (9),
The organic-inorganic polymer hybrid comprises I) 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB), isophthalic acid chloride (IPC), and benzene-1,3,5-tricarboxylic acid chloride (BTC). ) And p-aminophenyltrimethoxysilane (PAPTMS), and a branched polybenzoxazole precursor having a trimethoxysilyl group at least at a part of a plurality of ends, and II) silica fine particles The mixture is oxazolated,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 40% by weight,
A hybrid material characterized by that.

A polymer phase composed of polybenzoxazole or polybenzimidazole, and SiO ₂  A hybrid material composed of an organic-inorganic polymer hybrid integrated with any of organic groups represented by the following chemical formulas (4) to (6):
The polymer phase is composed of linear polybenzimidazole having any of the atomic groups represented by the following chemical formulas (14) to (16),
The organic-inorganic polymer hybrid comprises I) 3,3 ′, 4,4′-tetraaminobiphenyl (DAB), isophthalic acid chloride (IPC), p-aminophenyltrimethoxysilane (PAPTMS), aromatic A sol-gel obtained by using a tetracarboxylic dianhydride and a linear polybenzimidazole precursor having a trimethoxysilyl group at a terminal, and II) at least one alkoxysilane compound in the presence of water. Reaction, and the resulting reaction product is imidazoled,
The content of the silica phase in the organic-inorganic polymer hybrid is 1 to 30% by weight.
A hybrid material characterized by that.

A method for producing a hybrid material according to claim 1 ,
Silylated product of 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) , isophthalic acid chloride (IPC) , p-aminophenyltrimethoxysilane (PAPTMS) , and aromatic tetracarboxylic dianhydride A step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group at the end, and
A step of subjecting the linear polybenzoxazole precursor and at least one of the alkoxysilane compounds to a sol-gel reaction in the presence of water and oxazlating the resulting reaction product to form an organic-inorganic polymer hybrid; ,
A method for producing a hybrid material, comprising: A method for producing a hybrid material according to claim 2 ,
Silylated product of 4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) , isophthalic acid chloride (IPC) , p-aminophenyltrimethoxysilane (PAPTMS) , and aromatic tetracarboxylic dianhydride A step of synthesizing a linear polybenzoxazole precursor having a trimethoxysilyl group at the end, and
A step of converting the mixture of the linear polybenzoxazole precursor and the silica fine particles into an organic-inorganic polymer hybrid by oxazolation;
A method for producing a hybrid material, comprising: A method for producing a hybrid material according to claim 3 ,
2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane (6FAP) silylated, 4,4'- oxydiphenyl -1,1-dicarboxylic acid chloride (OBC) , p-aminophenyl Using trimethoxysilane (PAPTMS) and aromatic tetracarboxylic dianhydride to synthesize a linear polybenzoxazole precursor having a trimethoxysilyl group at the end;
A step of subjecting the linear polybenzoxazole precursor and at least one of the alkoxysilane compounds to a sol-gel reaction in the presence of water and oxazlating the resulting reaction product to form an organic-inorganic polymer hybrid; ,
A method for producing a hybrid material, comprising: A method for producing a hybrid material according to claim 4 ,
4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) , isophthalic acid chloride (IPC), and benzene-1,3,5-tricarboxylic acid chloride (BTC) under the temperature conditions of −20 to 0 ° C. A step of synthesizing a branched polybenzoxazole precursor I by polymerization in an organic solvent containing an oxirane compound;
Synthesis said branch polybenzoxazole precursor I, and have use of a p- aminophenyl trimethoxysilane (PAPTMS), a branch polybenzoxazole precursor II with at least a portion trimethoxysilyl group of the plurality of terminal And a process of
A step of subjecting the branched polybenzoxazole precursor II and at least one of alkoxysilane compounds to a sol-gel reaction in the presence of water and oxazolizing the resulting reaction product to form an organic-inorganic polymer hybrid; ,
A method for producing a hybrid material, comprising: In the hybrid material manufacturing method according to claim 5 ,
4,4′-diamino-3,3′-dihydroxybiphenyl (HAB) , isophthalic acid chloride (IPC), and benzene-1,3,5-tricarboxylic acid chloride (BTC) under the temperature conditions of −20 to 0 ° C. A step of synthesizing a branched polybenzoxazole precursor I ′ by polymerization in an organic solvent containing an oxirane compound;
The branch polybenzoxazole precursor I 'and, p- aminophenyl and have use the trimethoxysilane (PAPTMS), branched polybenzoxazole precursor II with at least a portion trimethoxysilyl group of the plurality of terminal' A step of synthesizing
A step of converting the mixture of the branched polybenzoxazole precursor II ′ and the silica fine particles into an organic-inorganic polymer hybrid by oxazolation;
A method for producing a hybrid material, comprising: A method for producing a hybrid material according to claim 6 ,
Using 3,3 ′, 4,4′- tetraaminobiphenyl (DAB) , isophthalic acid chloride (IPC) , p-aminophenyltrimethoxysilane (PAPTMS) , and aromatic tetracarboxylic dianhydride , Synthesizing a linear polybenzimidazole precursor having a trimethoxysilyl group at the terminal;
A step of subjecting the linear polybenzimidazole precursor and at least one of the alkoxysilane compounds to an organic-inorganic polymer hybrid by sol-gel reaction in the presence of water and imidazolization of the obtained reaction product; ,
A method for producing a hybrid material, comprising:

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