TW201641497A - New tetracarboxylic dianhydride, and polyimide and polyimide copolymer that are obtained from the new tetracarboxylic dianhydride - Google Patents

Abstract

A tetracarboxylic dianhydride represented by formula (1), and a polyimide or polyimide copolymer produced from this tetracarboxylic dianhydride, are used. This makes it possible to provide a polyimide and a polyimide copolymer having exceptional solvent solubility (solvent processability) and heat resistance, as well as a polyimide film containing the same.

Description

Novel tetracarboxylic dianhydride and polyimine copolymer obtained from the tetracarboxylic dianhydride

The present invention relates to a novel tetracarboxylic dianhydride having a spiro ring configuration, and a polyimine and polyimine copolymer obtained from the novel tetracarboxylic dianhydride.

Conventionally, a polyimide having a high temperature resistant to a solder mounting temperature (260 ° C) or higher for a plastic material for microelectronics has been widely used as an insulating layer such as a semiconductor element or a flexible printed wiring board. However, polyethylenimine having high heat resistance is mostly inferior in processability, and polyimides are almost all self-polyimine precursors, that is, polylysine processing which is soluble in a solvent (Non-Patent Document 1) ).

In order to form a polyimine from polylysine, a high temperature of 300 ° C or higher is required, and the use thereof is limited depending on the hydrazine imidization temperature. At the same time, when a polyimine film is produced from a poly-proline film, there is a concern that the film is destroyed by hardening shrinkage or voids in the film depending on the conditions of the heat-imidization, so the imidization reaction Control is very difficult. Further, when the hydrazine imidization reaction is carried out, there is a disadvantage that a high-temperature furnace of 300 ° C or higher is required to increase the production cost.

Therefore, in recent years, polyimine (solvent-soluble polyimine) or melt-formable thermoplastic polyimide, which is soluble in a solvent in a state where ruthenium iodization has been completed, has been developed, and the like Compared with polyimine, the processability is improved. Most of such polyamidiamines have a structure in which a siloxane chain in a polyimine chain or a polymer backbone such as an ether group is bent, and a bond which is easy to undergo intramolecular rotational motion is introduced. In addition, a large-volume substituent is introduced into the side chain to inhibit aggregation of the polymer chain, and the concentration of the quinone imine group in the main chain is lowered, and the workability is improved (Non-Patent Documents 2 and 3). However, such molecular design has made the original heat resistance of polyimine significantly reduced without exception. Therefore, there is almost no polyimine which has both heat resistance and solvent solubility of 260 ° C or more, particularly 290 ° C or more.

Meanwhile, a polyimine obtained from an aromatic tetracarboxylic dianhydride (electron acceptability) and an aromatic diamine (electron donating) is a mutual dipole and a dipole of a carbonyl group by a ruthenium ring. The interaction between the action and the charge transfer between the molecules enhances the cohesive force between the polymer chains and limits the molecular motion, and the glass transition temperature is significantly higher than that of the general-purpose resin. The charge transfer interaction also occurs in the molecule, and the light transmittance in the visible light region of most polyimide films becomes very low by the interaction of intramolecular and intermolecular charge movement (Non-Patent Document 4) . At the same time, in the linear and rigid chemical structure of the polyimine, the coefficient of thermal expansion (CTE) of the film is as low as that of the inorganic material, and the system is excellent in heat display. A heat-resistant film material having dimensional stability (Non-Patent Document 5).

In general, the polyimide film is made of a polyimine precursor which is soluble in a solvent, that is, a polylysine solution (varnish) which is soluble in a solvent is cast on a support, and dried to obtain a poly After the proline film is subjected to a dehydration ring-closure reaction (thermal imidization) at a high temperature (Non-Patent Document 1). In general, since the enthalpy imidization reaction is accompanied by the detachment of residual solvent in water or a film as a by-product, a strong contraction force is generated along the surface direction of the film, and the film is fixed to the support or the like. In this case, the film is clearly extended. In the polyimine having a linear and rigid chemical structure, the polyimine chain is highly aligned along the film surface by such extension (Non-Patent Documents 6 and 7). By this action, the polyimide film exhibits low thermal expansion, that is, exhibits excellent dimensional stability of heat. At present, a polyimide having a high dimensional stability is widely used as an insulating layer such as a semiconductor element or a flexible printed wiring board. However, polyimine which is excellent in heat resistance and dimensional stability of heat generally lacks processability because of its insoluble and insoluble characteristics, so it is necessary to dissolve in a precursor of a solvent (polyglycine). It is selected to be processed into a film and subjected to a thermal imidization process. Since the high temperature of 300 ° C or higher is required for the thermal imidization process, such a high temperature film formation process is disadvantageous for the use of a polyimide film having no coloring and transparency (especially an optical device). . Therefore, as described above, although a polyimide film having a solution ‧ hot workability is sought, once a polyimide film having a solution ‧ hot workability is obtained by a known method, there is almost no exception The polyimide film has a decrease in heat resistance and a linear thermal expansion coefficient (deterioration of dimensional stability of heat) (Non-Patent Document 7).

Therefore, in theory, it is extremely difficult to obtain a polyimide film having high heat resistance and low thermal expansion by coating and drying the polyimide varnish only (without applying a hot hydrazine imidization process). According to such a situation, there is no method for obtaining a polyimine which maintains coloration-free transparency in addition to solution processing property, heat resistance and low thermal expansion property, and is suitable for various optical applications. [Prior Technical Literature] [Patent Literature]

[Non-Patent Document 1] Prog. Polym. Sci., 16, 561 (1991). [Non-Patent Document 2] Polym. Eng. Sci., 29, 1413 (1989). [Non-Patent Document 3] Polym., 39, 1945 (1998). [Non-Patent Document 4] Prog. Polym. Sci., 26, 259 (2001). [Non-Patent Document 5] J. Appl. Polym. Sci., 31, 101 (1986). [Non-Patent Document 6] Polym., 30, 1170 (1989). [Non-Patent Document 7] Macromolecules, 29, 7897 (1996).

[Problem to be Solved by the Invention] An object of the present invention is to provide a tetracarboxylic dianhydride for a resin having excellent solvent solubility (solution processability) and high heat resistance, from the tetracarboxylic dianhydride A synthetic polyimide having excellent solution processability and a solution containing the polyimine, and a film having high heat resistance derived from the polyimide and the polyimide solution. Meanwhile, an object of the present invention is to provide a high heat resistance, a low linear thermal expansion coefficient, and a high transparency obtained by coating a ‧ dry polyimine copolymer with a solution containing the polyamidene copolymer Polyimide film. [Means for solving the problem]

In order to solve the problems described above, the inventors of the present invention have found that polytetraimine having excellent solution processability can be obtained by using a tetracarboxylic dianhydride represented by the following formula (1), and can be self-contained. The polyimine film having a heat resistance of 260 ° C or higher is obtained by the solution of the polyimine, and the present invention has been completed.

The present invention is as follows: [1] A tetracarboxylic dianhydride characterized by the following formula (1): The following formula (1):

[Chemical 1] .

[2] A polyimine characterized by having a repeating unit represented by the following formula (2): the following formula (2): [Chemical 2] (In the formula (2), X represents a divalent aromatic or aliphatic group).

Meanwhile, the present inventors have found that the polyimine containing the inducible structure derived from the tetracarboxylic dianhydride represented by the above formula (1) has a copolymer having a specific structure, that is, having the following a polyimine copolymer of a repeating unit represented by the formula (5) and a repeating unit represented by the following formula (6), which copolymer provides a stable polyimine solution at room temperature, and the solution Coating and drying, the polyimine film having high heat resistance, low linear thermal expansion coefficient, and high transparency can be obtained, and the present invention has been completed.

The present invention is as follows: [3] A polyimine copolymer having a repeating unit represented by the following formula (5) and the following formula (6): the following formula (5):

[Chemical 3] The following general formula (6):

[Chemical 4] (In the general formula (6), Y represents a tetravalent aromatic group selected from at least one of the group consisting of the following formulas (7) to (12))

[Chemical 5] .

[Effects of the Invention] According to the present invention, it is possible to provide a polyimine which has high heat resistance (high glass transition temperature) and solvent solubility, which is extremely difficult to coexist in the prior art, and which is produced from a solution containing the polyimine. A polyimide film, and a tetracarboxylic dianhydride having a fluorene structure and a spiro structure for the polyimine. Further, by selecting a copolymer having a specific structure from the polyimine, it is possible to provide a polyimide film having high heat resistance, high transparency, and low thermal expansion.

<Tetracarboxylic acid dianhydride> The tetracarboxylic dianhydride of the present invention has a structure represented by the following formula (1).

[Chemical 6]

The method for synthesizing the tetracarboxylic dianhydride represented by the formula (1) of the present invention is not particularly limited, and for example, a known esterification reaction is used and is represented by the following formula (3). a diol, that is, a spiro ring [芴-9,9'-(2',7'-dihydroxyxanthene)] or a diacetate thereof, and a benzotriene represented by the following formula (4) Trimellitic acid or its inducer is synthesized.

[Chemistry 7]

[化8]

As the trimellitic acid inducer, for example, trimellitic anhydride, trimellitic anhydride halide or the like is exemplified.

<Polyimide> The structural characteristics of the tetracarboxylic dianhydride represented by the formula (1) of the present invention are a spiro ring structure in which a xanthene structure and a ruthenium structure are perpendicularly intersected, and phthalic anhydride thereof Part of the bond is bonded to the xanthene via an ester bond.

In the polyimine which is represented by the formula (2) of the present invention, since the tetracarboxylic dianhydride represented by the above formula (1) is used as a raw material, a useful polyimine having the above specific physical properties can be obtained. The method for producing the polyimine is not particularly limited, and examples thereof include, for example, a tetracarboxylic dianhydride represented by the above formula (1) and an aromatic group having a divalent nucleophilic reactive functional group. After reacting with an aliphatic compound and obtaining a polyimine precursor having a repeating unit represented by the following formula (2), followed by a two-stage synthesis by a hydrazine imidization process, or in a high boiling solvent A one-stage synthesis method in which a tetracarboxylic dianhydride represented by the above formula (1) and an aromatic or aliphatic compound having a divalent nucleophilic reactive functional group are stirred and reacted at 150 to 220 ° C.

The polyimide of the present invention has a structure represented by the following formula (2).

[Chemistry 9] (In the formula (2), the X system represents a divalent aromatic or aliphatic group.)

In the above formula (2), the divalent aromatic or aliphatic group represented by X is a reaction mixture with a tetracarboxylic dianhydride represented by the above formula (1), and has a divalent nucleophilic reactive functional group. The skeleton structure of an aromatic or aliphatic compound. Further, in the present invention, an amine group, an isocyanate group or the like is exemplified as the divalent nucleophilic reactive functional group.

In the case of an aromatic or aliphatic compound having a divalent nucleophilic reactive functional group, specifically, for example, a diamine such as p-phenylenediamine, m-phenylenediamine, 4,4'-bis (4) -aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4- Aminophenyl)hexafluoropropane, p-terphenylene diamine, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, adjacent Tolylamine, m-toluidine, 4,4'-diamino-2,2'bis(trifluoromethyl)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 3,4'-diamine Diphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'- Diaminodiphenylphosphonium, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzimidamide, 4-amine Phenyl-4'-aminobenzoate 2,4-Diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminotetramethylene (2,4 diamino durene), 4,4' -diaminodiphenylmethane, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-ethylaniline), 4,4'-methylene An aromatic diamine such as bis(2,6-dimethylaniline) or 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylene double (ring) Hexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexane Bis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3,8- Bis(aminomethyl)tricyclo[5.2.1.0]decane, 1,3-diamine adamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4- Alicyclic diamines such as aminocyclohexyl)hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6- Chain of hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, diamine oxime Aliphatic diamine. Meanwhile, in the case of isocyanates, 1,5-phenylene diisocyanate, 1,3-diisocyanatobenzene, 3,3'-dichloro-4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenylmethane, 1,5-diisocyanatophthalene, methylphenyl-2,6-diisocyanate, isophthalic acid An aromatic diisocyanate such as m-xylylene diisocyanate or 2,2-bis(4-isocyanatophenyl)hexafluoropropane, or a lipid such as dicyclohexylmethyl 4,4'-diisocyanate A chain aliphatic diisocyanate such as a cyclodiisocyanate or a hexamethylene diisocyanate. At the same time, these can also be used in combination of two or more types.

In the range which does not significantly impair the polymerization reactivity at the time of polymerization of the polyimine of the present invention and the properties of the polyimine, an aromatic or fat other than the tetracarboxylic dianhydride represented by the above formula (1) may be used in combination. A tetracarboxylic dianhydride is used as a copolymerization component. As the aromatic tetracarboxylic dianhydride which can be used at this time, for example, pyromellitic dianhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride, 2,3, 3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, hydroquinone-bis(trimellitic anhydride), methyl pair Hydroquinone-bis(trimellitic anhydride), 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,4,3',4'-di Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 3 ,4,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,4,2',3'-diphenyl ether tetracarboxylic dianhydride, 2,3,2',3'-diphenyl ether Tetracarboxylic dianhydride, 3,4,3',4'-diphenylfluorene tetracarboxylic dianhydride, 3,4,2',3'-diphenylfluorene tetracarboxylic dianhydride, 2,3,2' , 3'-diphenylfluorene tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid phenyl)hexafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxylic acid Phenyl) propane dianhydride and the like. The aliphatic tetracarboxylic dianhydride is not particularly limited, but, for example, as an alicyclic group, for example, bicyclo [2.2.2] oct-7-ene-2, 3, 5, 6 -tetracarboxylic dianhydride, 5-(dioxotetrahydrofuranyl-3-methyl)-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl) - tetrahydronaphthalene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3,3',4,4'-tetracarboxylic dianhydride, 1,2 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like. At the same time, these can also be used in combination of two or more types.

For the solvent for synthesizing the polyimine or polylysine of the present invention, although N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2 are used. An aprotic solvent such as pyrrolidone or dimethyl hydrazine is preferred, but the reaction raw material, the produced polyimine precursor, and the ruthenium iodide can be dissolved. Further, the solvent which does not react with the reaction raw material or the product, that is, can be used without any problem, and the kind of the solvent is not particularly limited.

Specifically, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone can be used, and γ-butane can be used. Ester, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, etc. An ester solvent, a carbonate solvent such as ethyl carbonate or propylene carbonate, a glycol solvent such as diethylene glycol dimethyl ether, triethylene glycol or triethylene glycol dimethyl ether; Phenolic solvents such as cresol, p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol, etc., cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl a ketone solvent such as isobutyl ketone, an ether solvent such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or dibutyl ether; Acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutyl hydrazine, dimethyl hydrazine, propylene glycol methyl acetate, ethyl cellosolve, butyl cellulide can be used. Sodium, 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone acetate , Butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha solvents and the like, and these can also be in two or more categories.

The method for synthesizing the tetracarboxylic dianhydride represented by the formula (1) of the present invention is not particularly limited, and a known esterification reaction can be suitably used. Specifically, for example, the trimellitic anhydride chloride is dissolved in a dehydrated aprotic solvent, and then dissolved in the same temperature at a temperature of -78 ° C to 0 ° C, preferably -35 ° C to -5 ° C using a mechanical stirrer or the like. The solution containing the diol of the formula (3) and the deoxidizer is stirred for 0.5 to 48 hours, preferably 1 to 24 hours. Thereafter, the obtained reaction solution is heated to 0 to 100 ° C, preferably 10 to 50 ° C, and stirred for 0.5 to 48 hours, preferably 1 to 24 hours, to further complete the esterification. Next, the product is separated from the solution containing the product and appropriately washed, and then dried at 20 to 220 ° C, preferably 50 to 200 ° C using a vacuum dryer or the like, thereby obtaining the formula of the present invention ( 1) The tetracarboxylic dianhydride shown. When the purity of the tetracarboxylic dianhydride represented by the formula (1) of the present invention is low, it can be suitably purified by a known method such as a sublimation method or a recrystallization method.

The method for synthesizing the polyimine and the solution containing the polyimine represented by the formula (2) of the present invention is not particularly limited, and a known ruthenium amide reaction can be suitably used.

Specifically, for example, the following one-stage method can be used for the synthesis. In the case of a divalent nucleophilic reactive functional isocyanate group, an aromatic or aliphatic diisocyanate is dissolved in a solvent, and then a tetracarboxylic dianhydride powder represented by the formula (1) having a molar number such as an isocyanate group is used. , adding the solution slowly or in batches, and then stirring the solution for 0.5 to 168 hours, preferably 1 to 72, at a temperature of -20 to 100 ° C, preferably 0 to 50 ° C, using a mechanical stirrer or the like. In an hour, a solution containing the polyimine represented by the formula (2) can be obtained.

Meanwhile, in the case of a divalent nucleophilic reactive functional group amine group, an aromatic or aliphatic diamine is dissolved in a high boiling point solvent, followed by a tetracarboxylic acid represented by the formula (1) having a Moir number such as a diamine. The acid dianhydride powder is added to the solution slowly or in portions, and then an azeotropic agent such as toluene is added, and while introducing an inert gas, a mechanical stirrer or the like is used, and the temperature is 150 to 220 ° C, preferably 160 °. The solution is stirred at 190 ° C for 0.5 to 10 hours, preferably 1 to 5 hours, and the water formed by the imidization of the hydrazine is removed together with the entraining agent to the outside of the reaction system, and the hydrazine can be imidized. A solution containing the polyimine represented by the formula (2) can be obtained by returning the temperature to room temperature. Further, when the water or the entrainer of the by-product of the hydrazine imidization reaction is removed, since the inside of the reaction vessel can be decompressed, the solid content concentration can be increased by this process.

Meanwhile, the polyimine of the above formula (2) of the present invention and a solution containing the polyimine can be synthesized by the following two-stage method. In the case of a divalent nucleophilic reactive functional group amine group, first, as a first stage, an aromatic or aliphatic diamine is dissolved in a solvent, followed by a formula (1) in which a molar number such as a diamine is used. The tetracarboxylic dianhydride powder is added to the solution slowly or in portions, and then the solution is stirred for 0.5 to 168 hours at a temperature of 0 to 100 ° C, preferably 5 to 50 ° C, using a mechanical stirrer or the like. Preferably, it is from 1 to 96 hours, and further, a poly-proline which is a precursor of polyimine is obtained. In order to maximize the molecular weight of the polylysine, the solid content concentration at this time is desirably such that the solution can be stirred to a uniform maximum concentration. That is, the solid content concentration is from 1 to 50% by weight, preferably from 5 to 40% by weight. As long as the concentration of the solid component is such, the degree of polymerization of the produced polyamic acid becomes extremely high. Meanwhile, in the case of using an aliphatic diamine, although the formation of a salt often occurs in the initial stage of polymerization to inhibit polymerization, in order to suppress the formation of a salt as much as possible to increase the degree of polymerization, it is preferred to control the concentration of the solid component during polymerization. The above appropriate concentration range.

Next, as a second stage, a method of performing the ruthenium imidization of the polyimine precursor obtained above, that is, poly-proline is described. In order to obtain the polyimine of the present invention, a known method such as a high-temperature solution hydrazine imidization method by heat dehydration ring closure, a chemical hydrazylation method using a dehydrating agent, or the like can be suitably used.

Specifically, for example, in the case of applying a high-temperature solution hydrazine imidation method, a polyamic acid solution obtained by the above method synthesized in a high-boiling solvent can be used by adding the above-mentioned polyamic acid. The solvent is added in the same manner as the solvent used in the production of the polyamic acid described above, and the viscosity is moderately easy to stir. Then, an azeotropic agent such as toluene is added, and an inert gas is introduced while using the machine. Agitator, etc., at a temperature of 150 to 220 ° C, preferably 160 to 190 ° C, the solution is stirred for 0.5 to 10 hours, preferably 1 to 5 hours, and then the water formed by the hydrazine imidization The boiling agent is removed to the outside of the reaction system, and can be easily imidized, and then the solution containing the polyimine represented by the formula (2) can be obtained by returning the temperature to room temperature. Further, when the water or the entrainer of the by-product of the hydrazine imidization reaction is removed, since the inside of the reaction vessel can be decompressed, the solid content concentration can be increased by this process.

Meanwhile, in the case of applying the chemical hydrazine imidation method, the poly-proline acid solution obtained by the above method is added with a solvent which can be used in the production of the poly-proline, and in particular, the addition of the polylysine which is produced as described above. The solvent used in the same solvent is used, and it becomes a moderate solution viscosity which is easy to stir, and then the anhydride of the organic acid is dripped, and the dehydration ring-closing agent which consists of a tertiary amine as a basic catalyst (chemical hydrazine imidation agent). The chemical oxime imidization can be completed by stirring the solution for 1 to 72 hours at a temperature of 0 to 100 ° C, preferably 10 to 50 ° C, using a mechanical stirrer or the like. The organic acid anhydride which can be used at this time is not particularly limited, but is, for example, acetic anhydride, propionic anhydride or the like. From the viewpoint of handling of the reagent and easy separation, it is appropriate to use acetic anhydride. Meanwhile, as the basic catalyst, although pyridine, triethylamine, quinoline or the like can be used, it is appropriate to use pyridine from the viewpoint of easy treatment and easy separation, and even if it is not limited to such a base. Catalyst. The content of the organic acid anhydride in the chemical hydrazine imidizing agent is in the range of 1 to 20 times the molar amount of the theoretical dehydration of polylysine, preferably 1 to 10 times the mole. Meanwhile, the content of the basic catalyst is in the range of 0.1 to 2 times moles relative to the organic acid anhydride, preferably in the range of 0.1 to 1 mole.

Since the reaction solution obtained by the above chemical ruthenium imidation method is mixed with a by-product of an alkali or unreacted chemical hydrazine imide, an organic acid or the like (hereinafter referred to as an impurity), in order to remove the same, Jia will be separated from polyimine and refined. The purification can be carried out by a known method. For example, in the simplest method, the following method can be applied: while stirring the ruthenium-imided reaction solution and dropping it into a large amount of a poor solvent, the polyimine is precipitated, and then The polyimine powder was recovered and repeatedly washed until the impurities were removed, followed by drying under reduced pressure to obtain a polyimide pigment powder. In this case, the solvent to be used may be a solvent which can precipitate the polyimine and can efficiently remove the impurities, and is easy to dry, and is not particularly limited, but is, for example, water. Initially, an alcohol solvent such as methanol, ethanol or isopropyl alcohol may be used as appropriate, and these may be used in combination. When the concentration of the solid component of the polyimine solution is too high when the polyimine is precipitated by dropping into the poor solvent, the precipitated polyimine becomes a granule, and the impurities remain in the coarse particles, or it takes a long time. The obtained polyiminoimine powder can be redissolved in a solvent. On the other hand, once the concentration of the polyimine solution is too thin, a large amount of lean solvent is required, so that the environmental load caused by the treatment of the waste solvent is increased or the manufacturing cost is increased. Therefore, the concentration (solid content concentration) of the polyimide reaction solution when it is dropped into a poor solvent is 20% by weight or less, preferably 10% by weight or less. The amount of the poor solvent used at this time can be suitably adjusted by those skilled in the art depending on the kind of the solvent or the polyimine in the polyimide reaction solution. The precipitated polyimine powder is recovered as described above, and the residual solvent is removed by vacuum drying or hot air drying or the like. The drying temperature and time are not limited as long as the temperature does not deteriorate the polyimine. It is preferably dried at a temperature of 30 to 150 ° C for 3 to 24 hours.

In order to form a polyimine solution, the polyimine powder represented by the above formula (2) must be dissolved in a solvent. The solvent which can be used can be suitably selected in accordance with the use and processing conditions of the polyamic acid. Specifically, a amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, γ-butyrolactone, Ester of γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, etc. a solvent, a carbonic acid solvent such as ethyl carbonate or propyl carbonate, a glycol solvent such as diethylene glycol dimethyl ether, triethylene glycol or triethylene glycol dimethyl ether, phenol or m-cresol. , phenolic solvents such as p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol, etc., cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl A ketone solvent such as a ketone or the like, an ether solvent such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or dibutyl ether, which can be used for other general-purpose solvents. Acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutyl hydrazine, dimethyl hydrazine, propylene glycol methyl acetate, ethyl cellosolve, butyl quercetin Butyl cellosolve), 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl Su acetate, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha solvents and the like, and these can also be in two or more categories.

In particular, in the case of continuous coating for a long period of time, in the case where the solvent in the polyimide absorbs moisture in the atmosphere and causes precipitation of the polyimine, it is preferred to use triethylene glycol dimethyl ether or γ. a low hygroscopic solvent such as butyrolactone or cyclopentanone. At the same time, even a guanamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone as a hygroscopic solvent It can be combined with the above-mentioned low hygroscopic solvent to suppress precipitation of polyimine. The method for dissolving the polyimine powder may be to dissolve the polyimine powder and form a polyimine solution in a temperature range of room temperature to the boiling point of the solvent in air or an inert gas for 1 to 48 hours. .

When the film toughness of the polyimide film is considered, the intrinsic viscosity of the polyimine represented by the formula (2) of the present invention is preferably 0.1 dL/g or more, and more preferably 0.2 dL/g or more. When the intrinsic viscosity is less than 0.1 dL/g, the film toughness of the polyimide film cannot be ensured, and it becomes a fragile film.

From the viewpoint of the formability and usability of the polyimide, the molecular weight of the polyimine of the present invention is preferably 5,000 or more, and more preferably 10,000 or more. Further, the molecular weight of the polyimine can be determined using the viscosity of the polyimide solution.

Further, a method for producing a polyimine film comprising the polyamidene represented by the above formula (2) of the present invention and a method for producing a polyimide film obtained by molding the same will be described. The concentration of the solid component of the polyimine in the polyimine solution may be appropriately selected depending on the use of the solution, but for example, in the case of film formation, although the concentration of the solid component can also be based on polycondensation The molecular weight of the imine, the method of production, or the thickness of the desired film is selected, but is preferably 5% by weight or more, more preferably 5% by weight to 40% by weight. When the solid content concentration is too low, it becomes difficult to form a film having a sufficient film thickness. Conversely, when the solid content concentration is too high, the solution viscosity is too high and coating becomes difficult. Further, in the present invention, the solid content concentration of the polyimine is a solid component remaining after the solvent is removed from the polyimide reaction solution by a conventional method (mainly the polyfluorene represented by the above formula (2). The content of the amine).

At the same time, in the polyimine solution containing the polyamidiamine represented by the above formula (2) of the present invention, a mold release agent, a filler, a decane coupling agent, a crosslinking agent, and a chain seal may be added as necessary. Additives such as terminal agents, antioxidants, antifoaming agents, leveling agents, and the like.

Although the form of the film produced using the above polyimine solution is described, the method of producing the film is not particularly limited as long as it can produce a self-supporting film having film toughness.

Specifically, for example, a polyimine solution is applied onto a support such as a glass substrate by a doctor blade or the like by a known method, and then dried to prepare a polyimide film. Alternatively, for example, a polyimine solution is applied onto a metal foil such as a copper foil by a doctor blade or the like by a known method, and then dried to obtain a laminated film of a polyimide/metal foil. The laminated film can also be applied to a copper clad laminate for a flexible printed wiring board which is resistant to high-temperature processes during solder mounting. Further, in the case where the polyimine solution is applied to an insulating material for a semiconductor or a flexible printed wiring board, the polyimine solution can be directly applied to a device, and the solvent can be dried to easily form an insulating layer. Floor.

Since the glass transition temperature of the polyimide film produced as described above is usually 260 ° C or higher, particularly 290 ° C or higher, it is particularly suitable for use as a heat resistant film, for example, as a semiconductor or flexible printed wiring substrate. In the case of using an insulating material, since the glass transition temperature of the insulating layer is 260 ° C or more, even if it is 260 ° C of the lead-free solder mounting temperature, it can be sufficiently tolerated, and therefore it is suitable for use as an insulating material.

<Polyimine copolymer> The polyimine copolymer of the present invention (hereinafter also referred to as "polyimine of the present invention") has a repeating unit represented by the following formula (5) and a formula (6) ) The repeating unit shown. In the general formula (6), Y represents a tetravalent aromatic group selected from at least one of the group consisting of the following formulas (7) to (12).

[化10]

[11]

[化12]

The polyimine copolymer of the present invention is a tetracarboxylic dianhydride of at least one of the group consisting of the tetracarboxylic dianhydride represented by the following formula (13) and the group consisting of the following formulas (14) to (19); It is produced by a diamine represented by the following formula (20).

[Chemistry 13]

[Chemistry 14]

[化15]

[Chemistry 16]

[化17]

[化18]

[Chemistry 19]

[Chemistry 20]

The method for producing a polyimine copolymer according to the present invention is the tetracarboxylic acid of the tetracarboxylic dianhydride represented by the above formula (13) and at least one of the group consisting of the above formulas (14) to (19). a two-stage synthesis method in which a dianhydride is reacted with a diamine represented by the above formula (20) to obtain a polythenimine precursor (polyglycine) of the present invention, which is subjected to a ruthenium imidization process, or In the high boiling point solvent, the tetracarboxylic dianhydride represented by the above formula (13) and the tetracarboxylic dianhydride of at least one of the groups consisting of the above formulas (14) to (19), and the above formula (20) A one-stage synthesis method in which the diamine shown is reacted while stirring at 150 to 220 °C.

The diamine other than the diamine represented by the above formula (20) may be used in combination within the range which does not significantly impair the properties of the polyimine of the present invention. As the diamine which can be used, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-amine) Phenyloxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, p-terphenyltriamine ( P-terphenylene diamine), benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-toluidine, m-toluidine, 1,4-bis(4-amine Phenoxy group) benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodi Phenylhydrazine, 3,3'-diaminodiphenylanthracene, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diamine Benzobenzidine, 4-aminophenyl-4'-aminobenzoate, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene 2,4-diaminotetramethylene (2,4 diamino durene), 4, 4'-Diaminodiphenylmethane, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-ethylaniline), 4,4'- An aromatic diamine such as methylene bis(2,6-dimethylaniline) or 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylene double (cyclohexylamine), isophorone diamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-ring Hexane bis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3, 8-bis(aminomethyl)tricyclo[5.2.1.0]decane, 1,3-diamine adamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-dual ( An alicyclic diamine such as 4-aminocyclohexyl)hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1, 6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, diamine oxime, etc. A chain aliphatic diamine. At the same time, these can also be used in combination of two or more types.

The tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the above formulas (13) to (19) may be used in combination within the range which does not significantly impair the properties of the polyimine copolymer of the present invention. As the tetracarboxylic dianhydride which can be used, for example, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'- Benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride, 3 , 4,2',3'-diphenyl ether tetracarboxylic dianhydride, 2,3,2',3'-diphenyl ether tetracarboxylic dianhydride, 3,4,3',4'-diphenylhydrazine Tetracarboxylic dianhydride, 3,4,2',3'-diphenylfluorene tetracarboxylic dianhydride, 2,3,2',3'-diphenylfluorene tetracarboxylic dianhydride, 2,2'-double An aromatic tetracarboxylic dianhydride such as (3,4-dicarboxylic acid phenyl) hexafluoropropane dianhydride or 2,2'-bis(3,4-dicarboxylic acid phenyl)propane dianhydride, or a double ring [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(dioxotetrahydrofuranyl-3-methyl)-3-cyclohexene-1,2-di Carboxylic anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, bicyclo-3 , 3', 4, 4'-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, etc. Aliphatic tetracarboxylic dianhydride. At the same time, these can also be used in combination of two or more types.

For the solvent in the synthesis of the polyimine copolymer or polylysine of the present invention, the solvent described in the present invention regarding the polyimine can be used.

The method for producing the tetracarboxylic dianhydride represented by the above formulas (13) to (19) used in the present invention is not particularly limited. For example, the above formula (13) having an ester group in its structure and the tetracarboxylic dianhydride represented by the above formulas (17) to (19) can be produced by suitably using a known esterification reaction. . Specifically, for example, a solution in which trimellitic anhydride chloride is dissolved in a dehydrated aprotic solvent, and a solution in which a diol of the following formulas (21) to (24) and a deoxidizing agent are dissolved in a dehydrated aprotic solvent are separately prepared, and thereafter, a machine is used. The stirrer or the like is gradually cooled at a temperature of -78 ° C to 0 ° C, preferably -30 ° C to -5 ° C, and for 0.5 to 48 hours, preferably 1 to 24 hours. Mix ground. Thereafter, the obtained reaction solution is heated to 0 to 100 ° C, preferably 10 to 50 ° C, and stirred for 0.5 to 24 hours, preferably 1 to 12 hours, to complete the esterification, and after the esterification is completed, The product is separated from the solution containing the product and washed appropriately, and then dried at 100 to 220 ° C, preferably 120 to 200 ° C using a vacuum dryer or the like, thereby obtaining the formula used in the present invention ( 13) and tetracarboxylic dianhydride represented by formulas (17) to (19). When the purity of the tetracarboxylic dianhydride represented by the formula (13) and the formulas (17) to (19) of the present invention is low, a known method such as a sublimation method or a recrystallization method can be suitably used. refined.

[Chem. 21]

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[Chem. 24]

The method for synthesizing the polyimine copolymer of the present invention and the solution containing the polyimine copolymer is not particularly limited, and a known ruthenium amide reaction can be suitably used. In the hydrazine imidization reaction described later, the tetracarboxylic dianhydride represented by the above formula (13) and the tetracarboxylic dianhydride of at least one of the groups consisting of the above formulas (14) to (19) are used in combination. However, the mixing ratio is usually a tetracarboxylic dianhydride system in which at least one of the groups consisting of the above formulas (14) to (19) is one mole of the tetracarboxylic dianhydride represented by the above formula (13). It is used in an amount of from 1 to 99 mol%, preferably from 2 to 70 mol%. The content of the repeating unit represented by the above formula (5) and the repeating unit represented by the above formula (6) in the polyimine copolymer of the present invention can be adjusted by appropriately adjusting the mixing ratio.

Specifically, the synthesis can be carried out using the following one-stage synthesis method. The diamine represented by the above formula (20) is dissolved in a solvent having a high boiling point, and then the tetracarboxylic acid represented by the above formula (13) is obtained in an amount of the total amount of the tetracarboxylic dianhydride and the molar amount of the diamine. The dianhydride and the tetracarboxylic dianhydride of at least one of the group consisting of the above formulas (14) to (19) are added to the solution slowly or in portions, and then an azeotropic agent such as toluene is added, and an inert gas is introduced thereto. While stirring at a temperature of 150 to 220 ° C, preferably 160 to 190 ° C, using a mechanical stirrer or the like, the solution is stirred for 0.5 to 10 hours, preferably 1 to 5 hours, and then produced by imidization. The water is removed together with the entrainer to the outside of the reaction system, and the ruthenium can be imidized, and then the solution containing the polyimine copolymer of the present invention can be obtained by returning the temperature to room temperature. Further, when the water or the entrainer of the by-product of the hydrazine imidization reaction is removed, since the inside of the reaction vessel can be decompressed, the solid content concentration can be increased by this process. The solvent to be used at this time is not particularly limited as long as it is a solvent which does not allow the polyimine copolymer to precipitate.

Meanwhile, the polyimine copolymer of the present invention and a solution containing the polyimine copolymer can be synthesized by the following two-stage synthesis method. First, as a first stage, the diamine represented by the above formula (20) is dissolved in a high boiling point solvent, and then the above formula (13) is obtained by the amount of all tetracarboxylic dianhydride and the amount of moiré such as diamine. The tetracarboxylic dianhydride shown in the above and the tetracarboxylic dianhydride of at least one of the group consisting of the above formulas (14) to (19) are added to the solution slowly or in portions, followed by using a mechanical stirrer or the like. The solution is stirred at a temperature of 0 to 100 ° C, preferably 5 to 50 ° C, for 0.5 to 168 hours, preferably 1 to 96 hours, to obtain a polyaminic acid as a polyimide precursor. In order to maximize the molecular weight of the polylysine, the solid content concentration at this time is desirably such that the solution can be stirred to a uniform maximum concentration. That is, the solid content concentration is from 1 to 50% by weight, preferably from 5 to 40% by weight. As long as the concentration of the solid component is such, the degree of polymerization of the produced polyamic acid becomes extremely high. Meanwhile, in the case of using an aliphatic diamine, although the formation of a salt often occurs in the initial stage of polymerization to inhibit polymerization, in order to suppress the formation of a salt as much as possible to increase the degree of polymerization, it is preferred to control the concentration of the solid component during polymerization. The above appropriate concentration range.

The second stage of the polyimine precursor obtained by the above method, that is, the method of carrying out the ruthenium imidization of polylysine, is as described above in relation to the polyimine of the present invention.

In order to form a polyimine solution containing the polyimine copolymer of the present invention, the polyimine copolymer powder thus obtained must be dissolved in a solvent. As the solvent which can be used, for example, the solvent described above in relation to the polyimine of the present invention. These can also be used in combination of two or more types.

In particular, even if it involves a long-term continuous coating, in the case where the solvent in the polyimide absorbs moisture in the atmosphere to cause precipitation of the polyimine, the solvent is selected as described above in relation to the present invention. Said in the amine.

In the polyimine copolymer of the present invention, the content of the repeating unit represented by the above formula (5) and the repeating unit represented by the above formula (6) is usually from 1 to 99 mol%, and the linear thermal expansion property is maintained low. From the viewpoint, it is preferably from 2 to 70 mol%.

The intrinsic viscosity of the polyimine copolymer of the present invention is as described above in relation to the polyimine of the present invention. In addition, in the present invention, the intrinsic viscosity means a value measured by a method described later.

The molecular weight of the polyimine copolymer of the present invention is as described above in relation to the polyimine of the present invention.

A method for producing a polyimine film comprising the polyimine of the present invention and a polyimine film obtained by applying the same to a support and drying it will be described. The solid content concentration in the polyimine solution containing the polyimine of the present invention can be appropriately selected depending on the use of the solution. For example, in the case of film formation, although the solid content concentration can be selected depending on the molecular weight of the polyimide, the production method, or the thickness of the desired film, it is preferably 5% by weight or more. When the solid content concentration is too low, it becomes difficult to form a film having a sufficient film thickness. Conversely, when the solid content concentration is too high, the solution viscosity is too high and coating becomes difficult. Further, the solid content concentration of the polyimine copolymer in the present invention means a solid component remaining after removal of the solvent from the polyimide solution by a conventional method (mainly the polymerization represented by the above formula (6) The content of quinone imine).

Meanwhile, the additive which can be added to the polyimine solution containing the polyimine copolymer of the present invention is as described above in relation to the polyimine of the present invention.

The form of the polyimine film of the present invention using the polyimine solution of the polyimine copolymer of the present invention is as described above in relation to the polyimine of the present invention.

Since the glass transition temperature of the polyimide film produced as described above is usually 260 ° C or higher, it is suitable for use as an insulating material for a semiconductor or flexible printed wiring board capable of sufficiently withstanding the mounting temperature of lead-free solder at 260 ° C. .

The polyimine film of the present invention is produced by using the polyimine solution of the polyimine copolymer of the present invention, which has a characteristic of high light transmittance and low linear thermal expansion, that is, usually, The light transmittance at a wavelength of 400 nm is 30% or more, and since the linear thermal expansion coefficient is 40 ppm/K or less, the polyimide film of the present invention has excellent transparency and thermal dimensional stability, and thus can be applied to various opticals. Use and optical devices.

The invention can also be expressed as follows:

[4] The polyimine copolymer according to [3], wherein the content of the repeating unit represented by the above formula (5) is 2~ based on all repeating units of the polyamidene copolymer. 70 mol% range.

[5] A polyimine solution, which comprises the polyimine according to [2], or a polyamidene copolymer according to [3] or [4], and aggregated The solid content concentration of the polyimine or the polyimine copolymer in the quinone imine solution is 5% by weight or more.

[6] A polyimine film comprising the polyimine of [2] or the polyimine copolymer according to [3] or [4].

[7] A heat-resistant film comprising the polyimine of [2] or the polyimine copolymer according to [3] or [4], and the heat-resistant film The glass transition temperature is 260 ° C or higher.

[8] A polyimine film according to [3] or [4] which has the following characteristics (A), (B) and (C): (A) a light transmittance of 30 nm at a wavelength of 300 nm (B) The linear thermal expansion coefficient is 40 ppm/K or less; and (C) The glass transition temperature (Tg) is 260 ° C or higher. The present invention is not limited to the above-described various embodiments, and various modifications may be made within the scope of the claims, and the technical means disclosed in the respective embodiments may be combined as appropriate, and the embodiments obtained after the combination are also included. It is within the technical scope of the present invention. Furthermore, novel technical features can be formed by combining the respective technical means disclosed in the various embodiments. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Further, the physical property values in the following examples were determined by the following methods.

(Evaluation method) <Infrared absorption spectrum> An infrared absorption spectrum of tetracarboxylic dianhydride was measured by a KBr method using a Fourier transform infrared spectrophotometer FI/IR-4100 (manufactured by JASCO Corporation). Meanwhile, in terms of the infrared absorption spectrum of the polyimine, after the polyimine solution is prepared, it is cast on a glass substrate, and dried at 100 ° C for 30 minutes, and then the polyimine formed. The film sample (about 5 μm thick) was peeled off from the glass substrate and measured for the polyimide film sample.

<Hydrogen nuclear magnetic resonance ( ¹ H-NMR, Nuclear Magnetic Resonance) spectrum> Fourier transform nuclear magnetic resonance JNM-ECP400 (manufactured by JEOL) was used, and in the deuterated dimethyl hydrazine, tetracarboxylic dianhydride and chemical quinone were used. The ¹ H-NMR spectrum of the aminated polyimide pigment was measured. Tetramethyl decane was used as a reference material.

<Differential Scanning Calorimetry (melting point)> The melting point of the tetracarboxylic dianhydride was measured using a differential scanning calorimeter DSC3100 (Netchi Japan Co., Ltd.) at a temperature elevation rate of 5 ° C/min in a nitrogen atmosphere. The higher the melting point, the steeper the melting peak, indicating high purity.

<Intrinsic Viscosity> The reducing viscosity was measured at 30 ° C using an Ostwald viscometer using a 0.5 wt% polyimine precursor solution or a polyimine solution. This value is considered to be intrinsic viscosity.

<Solubility test of polyiminoimine powder against organic solvent> 0.1 g of polyimine powder and 9.9 g of organic solvent (solid content concentration: 1% by weight) were added to a sample tube, and stirred for 5 minutes using a test tube stirrer. The dissolution state was visually confirmed. The solvent used is chloroform (CF, chloroform), acetone, tetrahydrofuran (THF, tetrahydrofuran), 1,4-dioxane (DOX, 1,4-dioxane), ethyl acetate, cyclopentanone (CPN, cyclopentanone). ), cyclohexanone (CHN, cyclohexanone), N,N-dimethylformamide (DMF, N, N-dimethyl formamide), N,N-dimethylacetamide (DMAc, N, N-dimethyl) Acetamide), N-methyl-2-piperidone (NMP, N-methyl-2-piperidone), dimethyl sulfoxide, γ-butyrolactone (GBL, γ-butyrolactone), Tri-glycol (triethylene glycol dimethyl ether). The evaluation will be recorded as ++ at room temperature, and will be recorded as + by dissolving by heating and maintaining uniformity after cooling to room temperature, and the case of swelling or partial dissolution will be recorded as ±, and will be insoluble. The situation is recorded as -.

<Linear thermal expansion coefficient: CTE, and glass transition temperature: Tg> Using TMA4000 manufactured by Netchi Japan (sample size 5 mm long and 15 mm long), the load (static load) was set to film thickness (μm) × 0.5 g at 5 ° C /min temporarily raises the temperature to 150 ° C (the first temperature rise), immediately cools to 20 ° C, then raises the temperature at 5 ° C / min (the second temperature rise) and heats from the second temperature by the tangent method The mechanical analysis (TMA, Thermo Mechanical Analysis) curve was used to determine the glass transition temperature of the polyimide film. The coefficient of linear thermal expansion is obtained as an average value between 100 and 200 °C.

<Transmittance of Polyimine Film: T ₄₀₀ > Optical transmittance (T%) of a polyimide film having a wavelength of 200 to 800 nm measured using an ultraviolet-visible spectrophotometer V-530 (manufactured by JASCO Corporation) . The light transmittance of 400 nm was obtained as an index of transparency, and the transparency was evaluated.

<Yellowness (yellowness index): YI> Using an ultraviolet-visible spectrophotometer V-530 (manufactured by JASCO Corporation) and based on JIS K77373, the VWCT-615 color diagnostic program (manufactured by JASCO Corporation) The yellowness (YI) was calculated from the light transmittance (T%) of a polyimide film having a wavelength of 380 to 780 nm.

<Total Light Transmittance and Haze> Using Haze Meter NDH4000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance was determined based on JIS K7631, and the haze (turbidity) was determined based on JIS K7136.

<Synthesis Example 1> (Synthesis of tetracarboxylic dianhydride) A synthesis of tetracarboxylic dianhydride having no spiro structure was used as a comparative example. 8.4228 g (40.0 mmol) of trimellitic anhydride chloride was placed in an eggplant flask, and dissolved in 36 ml of dehydrated N,N-dimethylformamide (DMF) at room temperature, and sealed with a septum to prepare a solution A. (solute concentration 20 wt%). Next, 3.7242 g (20.0 mmol) of 4,4'-bisphenol was dissolved in 16 ml of dehydrated DMF (solute concentration: 20 wt%) in a separate flask at room temperature, and 120 mmol of pyridine was added to the solution. A membrane seal was prepared to prepare solution B. While cooling and stirring in an ice bath, the solution B was gradually dropped to the solution A using a syringe, followed by stirring at room temperature for 12 hours. After completion of the reaction, the yellow precipitate was separated by filtration and washed with DMF and ion-exchanged water. Removal of the pyridine hydrochloride was confirmed using an aqueous silver nitrate solution. The washed product was recovered and dried under vacuum at 180 ° C for 12 hours. The product obtained was a yellow powder with a yield of 4.8465 g and a yield of 38.5%. By a Fourier transform infrared spectrophotometer FI / IR-4100 (manufactured by Nippon Bunko), the obtained product was confirmed to have 1861cm ^{- 1} and 1782 cm ^{- 1} acid anhydride group of the C = O stretching vibration, and 1730cm ^{- 1} ester of The stretching vibration of the base C=O. At the same time, the results of proton NMR measurement using Fourier transform nuclear magnetic resonance JNM-ECP400 (manufactured by JEOL) confirmed that it can be attributed to DMSO- d ₆ , δ, ppm: 7.52 (d, 4H), 7.58 (d, 4H), 8.51. (d, 2H), 8.6 (m, 4H), 8.71 to 8.76 (m, 4H), and the target substance tetracarboxylic dianhydride was measured. At the same time, the melting point was measured by a differential scanning calorimeter DSC3100 (Netchi Japan Co., Ltd.), and since a steep melting peak was observed at 326 ° C, it was confirmed to be a product having a higher purity.

<Synthesis Example 2> (Synthesis of tetracarboxylic dianhydride) Synthesis of a tetracarboxylic dianhydride represented by the formula (18). 8.4228 g (40.0 mmol) of trimellitic anhydride chloride was placed in an eggplant flask, and dissolved in 36 ml of dehydrated N,N-dimethylformamide (DMF) at room temperature, and sealed with a septum to prepare a solution A. (solute concentration 20 wt%). Next, 3.7242 g (20.0 mmol) of 4,4'-bisphenol was dissolved in 16 ml of dehydrated DMF (solute concentration: 20 wt%) in a separate flask at room temperature, and 120 mmol of pyridine was added to the solution. A membrane seal was prepared to prepare solution B. While cooling and stirring in an ice bath, the solution B was gradually dropped to the solution A using a syringe, followed by stirring at room temperature for 12 hours. After completion of the reaction, the yellow precipitate was separated by filtration and washed with DMF and ion-exchanged water. Removal of the pyridine hydrochloride was confirmed using an aqueous silver nitrate solution. The washed product was recovered and dried under vacuum at 180 ° C for 12 hours. The product obtained was a yellow powder with a yield of 4.8465 g and a yield of 38.5%. The obtained crude product was recrystallized and purified using γ-butyrolactone (GBL). By a Fourier transform infrared spectrophotometer FI / IR-4100 (manufactured by Nippon Bunko), the obtained product was confirmed to have 1861cm ^{- 1} and 1782 cm ^{- 1} acid anhydride group of the C = O stretching vibration, and 1730cm ^{- 1} ester of The stretching vibration of the base C=O. At the same time, the results of proton NMR measurement using Fourier transform nuclear magnetic resonance JNM-ECP400 (manufactured by JEOL) confirmed that it can be attributed to DMSO- d ₆ , δ, ppm: 7.52 (d, 4H), 7.58 (d, 4H), 8.51. (d, 2H), 8.6 (m, 4H), 8.71 to 8.76 (m, 4H), and the target substance tetracarboxylic dianhydride was measured. At the same time, the melting point was measured by a differential scanning calorimeter DSC3100 (Netchi Japan Co., Ltd.), and since a steep melting peak was observed at 326 ° C, it was confirmed to be a product having a higher purity.

<Synthesis Example 3> (Synthesis of tetracarboxylic dianhydride) Synthesis of a tetracarboxylic dianhydride represented by the formula (19). Into the eggplant type flask, 4.3185 g (20.0 mmol) of trimellitic anhydride chloride was placed, and dissolved in 11 ml of dehydrated THF at room temperature, and sealed with a separator to prepare a solution A (solute concentration: 30% by weight). Next, 1.6019 g (10.0 mmol) of 2,6-dihydroxynaphthalene was dissolved in 4.2 ml of dehydrated THF (solute concentration: 30 wt%) in a separate flask at room temperature, and 60 mmol of pyridine was added to the solution. A membrane seal is then applied to prepare solution B. While cooling and stirring in an ice bath, the solution B was gradually dropped to the solution A using a syringe, followed by stirring at room temperature for 12 hours. After completion of the reaction, the yellow precipitate was separated by filtration and washed with THF and ion-exchanged water. Removal of the pyridine hydrochloride was confirmed using an aqueous silver nitrate solution. The washed product was recovered and dried under vacuum at 160 ° C for 12 hours. The product obtained was a yellow powder, and the yield was 4.4853 g, and the yield was 88.2%. The obtained crude product was recrystallized and purified using γ-butyrolactone (GBL). By a Fourier transform infrared spectrophotometer FI / IR-4100 (manufactured by Nippon Bunko), the obtained product was confirmed to have 1857cm ^{- 1} and 1780 cm ^{- 1} acid anhydride group of the C = O stretching vibration, and 1732cm ^{- 1} ester of The stretching vibration of the base C=O. It was confirmed that the target substance was tetracarboxylic dianhydride. At the same time, the melting point was measured by a differential scanning calorimeter DSC3100 (Netchi Japan Co., Ltd.), and since a steep melting peak was observed at 301 ° C, it was confirmed to be a product of high purity.

<Example 1> (Synthesis of tetracarboxylic dianhydride) The synthesis of the tetracarboxylic dianhydride represented by the formula (1) of the present invention. To the eggplant type flask, 6.4617 g (30.687 mmol) of trimellitic anhydride chloride was placed, and dissolved in 16.6 ml of dehydrated tetrahydrofuran (THF) at room temperature, and sealed with a septum to prepare a solution A (solute concentration: 30% by weight). Next, 3.6439 g (10.057 mmol) of spiro[芴-9,9'-(2',7'-dihydroxyanthracene)] was dissolved in 47.1 ml of dehydration in a separate flask at room temperature. In THF (solute concentration: 8 wt%), 4.85 ml (60.0 mmol) of pyridine was added to the solution, followed by membrane sealing to prepare a solution B. While cooling and stirring in an ice bath, the solution B was gradually dropped to the solution A using a syringe, followed by stirring at room temperature for 12 hours. After completion of the reaction, the white precipitate was separated by filtration and washed with THF and ion-exchanged water. After the silver nitrate aqueous solution was added to the washing liquid and the white precipitate was gradually not observed, the removal of the pyridine hydrochloride was confirmed. The washed product was recovered and dried under vacuum at 100 ° C for 12 hours. The product obtained was a white powder with a yield of 2.8336 g and a yield of 39.8%.

By a Fourier transform infrared spectrophotometer FI / IR-4100 (manufactured by Nippon Bunko), the obtained product was confirmed to have 1856cm ^{- 1} and 1781cm ^{- 1} acid anhydride group of C = O stretching vibration absorption band, and 1738cm ^{- 1} of A stretching vibration absorption band of an ester group C=O. At the same time, the results of proton NMR measurement using Fourier transform nuclear magnetic resonance JNM-ECP400 (manufactured by JEOL) confirmed that it can be attributed to DMSO- d ₆ , δ, ppm; 8.62 to 8.51 (m, 4H), 8.27 (dd, 2H, J = 8.0, 0.6 Hz), 8.15 (dd, 2H, J = 8.3, 1.8 Hz), 8.04 (d, 2H, J = 7.7 Hz), 7.49 to 7.46 (m, 4H), 7.32 (t, 2H, J) = 7.5 Hz), 6.94 (dd, 2H, J = 8.7, 2.4 Hz), 6.41 (d, 2H, J = 8.8 Hz), and for the elemental analysis value, the calculated value C: 72.47%, H: 2.83% The elemental analysis value was within 0.3% as compared with the tetracarboxylic dianhydride represented by the formula (1) having a measured value of C: 72.61% and H: 2.97%. At the same time, the melting point was measured by a differential scanning calorimeter DSC3100 (Netchi Japan Co., Ltd.), and since a steep melting peak was observed at 332 ° C, it was confirmed to be a product having a higher purity.

<Example 2> (Polymerization of polyproline; DABA) 0.6818 g (3 mmol) of 4,4'-diaminobenzoylanilide (4,4'-Diamino benzoyl-anilide (4,4') -DABA)) Dissolved in 6.57 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 2.1378 g (3 mmol) of the tetracarboxylic dianhydride powder represented by the formula (1) synthesized in Example 1 was gradually added and stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 15% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 1.41 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. The obtained precipitate was sufficiently washed with methanol and dried under vacuum at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.69 dL/g. The completion of the imidization was confirmed by ¹ H-NMR to detect the disappearance of protons of the carboxylic acid group in the poly-proline, and was confirmed by FT-IR (Fig. 1). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 1.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in DMAc at room temperature to prepare a 15% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 300 ° C for 1 hour. The film properties of the obtained film are shown in Table 2.

<Example 3> (Polymerization of polyproline; 4,4'-ODA system) 0.6007 g (3 mmol) of 4,4'-diaminodiphenyl ether (4,4'-ODA, 4, 4) '-oxydianiline) was dissolved in 6.39 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 2.1378 g (3 mmol) of the tetracarboxylic dianhydride powder represented by the formula (1) synthesized in Example 1 was gradually added and stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain polylysine (solid content concentration: 22.9% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 0.96 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 1.17 dL/g. The completion of the imidization was confirmed by ¹ H-NMR to confirm the disappearance of the proline proton in the poly-proline, and confirmed by FT-IR (Fig. 2). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 1.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in N-methyl-2-pyrrolidone (NMP) at room temperature to prepare 15 % by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 80 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 300 ° C for 1 hour. The film properties of the obtained film are shown in Table 2.

<Example 4> (Polymerization of polyproline; TFMB system) 0.9607 g (3 mmol) of 4,4'-diamino-2,2' bis(trifluoromethyl)biphenyl (TFMB, 2, 2'-bis(trifluoromethyl)-4,4'-diamino biphenyl) was dissolved in 7.2 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 2.1378 g (3 mmol) of the tetracarboxylic dianhydride powder represented by the formula (1) synthesized in Example 1 was gradually added and stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 23.6% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyamic acid was 0.94 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.81 dL/g. The completion of hydrazine imidation was confirmed by ¹ H-NMR to detect the disappearance of proline protons in polyglycine and by FT-IR (Fig. 3). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 1.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in cyclopentanone (CPN) at room temperature to prepare a 23% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. This polyimide film was again dried under reduced pressure at 280 ° C for 1 hour. The film properties of the obtained film are shown in Table 2.

<Example 5> (Polymerization of Polyproline) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.3 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 1.4965 g (2.1 mmol) of the tetracarboxylic dianhydride powder of the formula (1) and 0.2414 g (0.9 mmol) of the tetracarboxylic dianhydride powder of the formula (16) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain polylysine (solid content concentration: 22.9% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 1.52 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.99 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 4). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in cyclopentanone (CPN) at room temperature to prepare a 12% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. This polyimide film was again dried under reduced pressure at 280 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 6> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.0 g of dehydrated DMAc. Here, 1.2827 g (1.8 mmol) of the tetracarboxylic dianhydride powder of the formula (1), and 0.3218 g (1.2 mmol) of the tetracarboxylic dianhydride powder of the formula (16) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain polylysine (solid content concentration: 24.6% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 1.15 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 1.10 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 5). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in CPN at room temperature to prepare a 6 wt% solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. This polyimide film was again dried under reduced pressure at 280 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 7> The polyimine powder obtained in Example 6 was redissolved in DMAc at room temperature to prepare a 10% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. This polyimide film was again dried under reduced pressure at 280 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 8> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.9 g of dehydrated DMAc. Here, 1.4965 g (2.1 mmol) of the tetracarboxylic dianhydride powder of the formula (1), and 0.4810 g (0.9 mmol) of the tetracarboxylic dianhydride powder of the formula (18) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 21% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyamic acid was 1.36 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.76 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 6). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in CPN at room temperature to prepare a 20% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 9> The polyimine powder obtained in Example 8 was redissolved in DMAc at room temperature to prepare a 20% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 10> (Polymerization of Polyproline) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.7 g of dehydrated DMAc. Here, 1.2827 g (1.8 mmol) of the tetracarboxylic dianhydride powder of the formula (1), and 0.6413 g (1.2 mmol) of the tetracarboxylic dianhydride powder of the formula (18) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 25.1% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 1.30 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.87 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 7). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in CPN at room temperature to prepare a 20% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 11> The polyimine powder obtained in Example 10 was redissolved in DMAc at room temperature to prepare a 20% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 12> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.6 g of dehydrated DMAc. Here, 1.0689 g (1.5 mmol) of the tetracarboxylic dianhydride powder of the formula (1) and 0.8106 g (1.5 mmol) of the tetracarboxylic dianhydride powder of the formula (18) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 20.7 wt%) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 1.23 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.79 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 8). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

<Example 13> The polyimine powder obtained in Example 12 was redissolved in DMAc at room temperature to prepare a 12% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 14> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.6 g of dehydrated DMAc. Here, 1.2827 g (1.8 mmol) of the tetracarboxylic dianhydride powder of the formula (1) and 0.6101 g (1.2 mmol) of the tetracarboxylic dianhydride powder of the formula (19) were slowly added. It was stirred at a solid concentration of 30% by weight. Next, while diluting with DMAc as appropriate, it was stirred at room temperature for 72 hours to obtain a poly-proline which is a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 0.78 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.84 dL/g. The completion of the imidization was confirmed by FT-IR (Fig. 9). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

(Preparation of Polyimine Solution and Preparation of Polyimine Film) The obtained polyimine powder was redissolved in CPN at room temperature to prepare a 20% by weight solution. This polyimine solution was cast on a glass substrate and dried by a hot air dryer at 60 ° C for 2 hours. Thereafter, each of the glass substrates was dried under reduced pressure at 200 ° C for 1 hour, and then allowed to cool to room temperature, and the polyimide film was peeled off from the glass substrate. The polyimide film was dried again under reduced pressure at 250 ° C for 1 hour. The film properties of the obtained film are shown in Table 4.

<Example 15> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.5 g of dehydrated DMAc. Here, 1.0689 g (1.5 mmol) of the tetracarboxylic dianhydride powder of the formula (1) and 0.7626 g (1.5 mmol) of the tetracarboxylic dianhydride powder of the formula (19) were slowly added. It was stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 28.5% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 0.83 dL/g.

(Synthesis of Polyimine by Chemical Iridization) The obtained polyamine solution was diluted to a solid concentration of 8 wt% using dehydrated DMAc, and then 3.0627 g (30 mmmol) at room temperature. A mixed solution of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, followed by stirring for 24 hours. Next, a large amount of deionized water was added to the obtained polyimine solution to precipitate a target product. Thereafter, the obtained precipitate was sufficiently washed with methanol, and vacuum-dried at 100 ° C for 12 hours to obtain a polyimide pigment powder. The intrinsic viscosity of the obtained polyimine was 0.74 dL/g. The completion of hydrazine imidation was confirmed by FT-IR (Fig. 10). The solubility evaluation of the obtained polyimine powder for various solvents is shown in Table 3.

<Comparative Example 1> (Polymerization of Polyamide; DABA) 0.6818 g (3 mmol) of 4,4'-diaminobenzimidamide (4,4'-DABA) was dissolved in 20.6 g of dehydrated NMP . Here, 1.6033 g (3 mmol) of the tetracarboxylic dianhydride powder containing no spiro structure synthesized in Synthesis Example 1 was gradually added and stirred at a solid concentration of 10% by weight. Then, the mixture was stirred at room temperature for 72 hours to obtain a viscous polyamine.

(Synthesis of Polyimine by Chemical Amidization) The obtained polyamine solution was diluted with a dehydrated NMP to a solid concentration of 8 wt%, and then 3.0627 g (30 mmmol) at room temperature. After the dropwise addition of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, gelation occurred to interrupt the reaction. I believe that this is because the polymer does not contain a spiro ring structure, so its solubility in a solvent is insufficient to cause gelation.

<Comparative Example 2> (Polymerization of polyproline; 4,4'-ODA system) 0.6007 g (3 mmol) of 4,4'-diaminodiphenyl ether (4,4'-ODA) was dissolved in 19.8 Dehydrated NMP of g. Here, 1.6033 g (3 mmol) of the tetracarboxylic dianhydride powder containing no spiro structure synthesized in Synthesis Example 1 was gradually added and stirred at a solid concentration of 10% by weight. Then, the mixture was stirred at room temperature for 72 hours to obtain a viscous polyamine.

(Synthesis of Polyimine by Chemical Amidization) The obtained polyglycine solution was diluted to a solid concentration of 3 wt% using dehydrated NMP, and then 3.0627 g (30 mmmol) at room temperature. After the dropwise addition of anhydrous acetic acid and 1.1865 g (15 mmol) of pyridine was slowly dropped, gelation occurred to interrupt the reaction. I believe that this is because the polymer does not contain a spiro ring structure, so its solubility in a solvent is insufficient to cause gelation.

<Comparative Example 3> (Polymerization of polyproline; TFMB) 0.9607 g (3 mmol) of 4,4'-diamino-2,2' bis(trifluoromethyl)biphenyl (TFMB) was dissolved in 6.0 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 1.6033 g (3 mmol) of the tetracarboxylic dianhydride powder containing no spiro structure synthesized in Synthesis Example 1 was gradually added and stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 18.1% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 2.26 dL/g.

(Synthesis of Polyimine Imine by Chemical Iridium) Using half of the obtained polyamic acid solution diluted with dehydrated DMAc to a solid concentration of 8 wt%, 1.5314 g (15 mmmol) at room temperature After the dropwise addition of the anhydrous acetic acid and 0.5932 g (7.5 mmol) of pyridine was slowly dropped, the gelation occurred due to the deterioration of the fluidity of the solution, and the reaction was interrupted. I believe that this is because the polymer does not contain a spiro ring structure, so its solubility in a solvent is insufficient to cause gelation.

<Comparative Example 4> (Polymerization of Polylysine) 0.9607 g (3 mmol) of the diamine represented by the formula (20) was dissolved in 6.0 g of dehydrated N,N-dimethylacetamide (DMAc). Here, 1.6033 g (3 mmol) of the tetracarboxylic dianhydride powder represented by the formula (18) was gradually added and stirred at a solid concentration of 30% by weight. Subsequently, while diluting with DMAc as appropriate, the mixture was stirred at room temperature for 72 hours to obtain a polyaminic acid (solid content concentration: 18.1% by weight) as a polyimide precursor. The intrinsic viscosity of the obtained polyglycolic acid was 2.26 dL/g.

(Synthesis of Polyimine Imine by Chemical Iridium) Using half of the obtained polyamic acid solution diluted with dehydrated DMAc to a solid concentration of 8 wt%, 1.5314 g (15 mmmol) at room temperature After the dropwise addition of the anhydrous acetic acid and 0.5932 g (7.5 mmol) of pyridine was slowly dropped, the gelation occurred due to the deterioration of the fluidity of the solution, and the reaction was interrupted. I believe that this is because the polymer does not contain a spiro ring structure, so its solubility in a solvent is insufficient to cause gelation.

[Table 1]

[Table 2]

[table 3]

[Table 4] In addition, in the above Table 4, the numerical values described in the brackets are the film thicknesses of the polyimide film when the values of the respective physical properties are measured.

no.

1 is a graph obtained by Fourier-Transform Infrared Spectrometer (FT-IR) measurement in Example 2. Fig. 2 is a view showing the FT-IR measurement in Example 3. Fig. 3 is a view showing the FT-IR measurement in Example 4. Fig. 4 is a view showing the FT-IR measurement in Example 5. Fig. 5 is a view showing the FT-IR measurement in Example 6. Fig. 6 is a view showing the FT-IR measurement in Example 8. Fig. 7 is a view showing the FT-IR measurement in Example 10. Fig. 8 is a view showing the FT-IR measurement in Example 12. Fig. 9 is a view showing the FT-IR measurement in Example 14. Fig. 10 is a view showing the FT-IR measurement in Example 15.

no.

Claims (8)

A tetracarboxylic dianhydride characterized by the following formula (1): Formula (1): [Chemical 1] . A polyimine characterized by having a repeating unit represented by the following formula (2): Formula (2): [Chemical 2] (In the formula (2), X represents a divalent aromatic or aliphatic group). A polyimine copolymer characterized by having a repeating unit represented by the following formula (5) and the following formula (6): Formula (5): [Chemical 3] General formula (6): [Chemical 4] (In the formula (6), Y represents a tetravalent aromatic group selected from at least one of the group consisting of the following formulas (7) to (12)) (7) to (12): 5] . The polyimine copolymer according to claim 3, wherein the content of the repeating unit represented by the above formula (5) is in the range of 2 to 70 mol% based on the total repeating unit of the polyamidene copolymer. . A polyimine solution, comprising the polyimine according to claim 2, or comprising the polyamidene copolymer according to claim 3 or 4, and in a polyimine solution The solid content concentration of the polyimine or the polyimine copolymer is 5% by weight or more. A polyimine film characterized by comprising the polyimine of claim 2 or the polyimine copolymer of claim 3 or 4. A heat-resistant film comprising the polyimine according to claim 2, or the polyimine copolymer according to claim 3 or claim 4, and the glass transition temperature of the heat-resistant film It is above 260 °C. A polyimine film comprising the polyimine copolymer according to claim 3 or 4, which has the following characteristics (A), (B) and (C): (A) light transmittance at a wavelength of 400 nm It is 30% or more; (B) the linear thermal expansion coefficient is 40 ppm/K or less; and (C) the glass transition temperature (Tg) is 260 ° C or more.