TW201313781A - Polyamic acid resin composition, polyimide resin composition and polyimide oxazole resin composition and flexible substrate containing the same - Google Patents

Abstract

The present invention provide a polyamic acid resin composition, a polyimide resin composition and a polyimide oxazole resin composition, and a flexible substrate containing the same, which have excellent heat resistance, optical transparency, and low birefringence after treating film by heat. A polyamic acid resin composition is characterized by comprising the main component (a) a polyamic acid represented by general formula (1) as the structural unit, and (b) a solvent. (in general formula (1), X1 and X2 are each independently hydrogen or an monovalent organic group having carbon number of 1 to 10; R1 is an tetravalent organic group with carbon number of 4 to 40 having monocyclic or multicyclic alicyclic structure, or an tetravalent organic group with carbon number of 4 to 40 formed by an organic group having monocyclic alicyclic structure bonding each other directly or crosslinking each other; R2 is a divalent organic group with carbon number of 2 to 40 having at least two hydroxyl groups).

Description

Polylysine resin composition, polyimine resin composition, and polyamidiazole resin composition, and flexible substrate containing the same

The present invention relates to a polyaminic acid resin composition, a polyimide composition, and a polyimine The azole resin composition and the flexible substrate containing the same. More specifically, a polyamic acid resin composition suitable for use in a flexible display substrate such as a flat panel display, a touch panel, an electronic paper, a color filter substrate, a solar cell, or the like, a flexible printed circuit board, or the like Yttrium imine resin composition and polyimine The azole resin composition and the flexible substrate containing the same.

Compared with glass, organic film has the following advantages: rich in flexibility, difficult to break, and light in weight. Recently, by changing the substrate of the flat panel display to an organic film, the operation of the display can be made flexible.

When a display is produced on an organic film, it is generally a process in which an organic film is grown on a carrier substrate and then peeled off from the carrier substrate after the device is fabricated. There are the following methods for growing the substrate into an organic film. For example, there is a method of attaching an organic film to a glass substrate using an adhesive or the like (for example, Patent Document 1). Alternatively, a method of applying a solution containing a resin or the like as a raw material of a film onto a substrate to be carried and curing it by heat or the like (for example, Patent Document 2). The former must be provided with an adhesive between the substrate to be loaded and the film, and the subsequent process temperature is limited by the heat resistance of the adhesive. On the other hand, the latter is excellent in that the surface of the film to be formed is high in smoothness without using an adhesive.

As the resin which can be used for the organic film, for example, polyester, polyamide, polyimine, polycarbonate, polyether oxime, acrylic (acrylic acid), ring Oxygen resin, etc. Among them, the polyimide resin is suitable as a high heat resistant resin and is suitable for a display substrate. In particular, in addition to high heat resistance, the polyimide resin has excellent mechanical properties such as high mechanical strength, abrasion resistance, dimensional stability, and chemical resistance, and excellent electrical properties such as insulation properties. Characteristics are widely used in the field of electricity and electronics. In the case where the polyimine film is grown by the above-described coating method, a method in which a precursor containing polyamic acid solution is applied and hardened to be converted into a polyimide may be used. In general, polylysine can be easily synthesized by reacting an acid anhydride with a diamine.

Although all aromatic polyimines derived from aromatic acid dianhydrides and aromatic diamines have high heat resistance, they are absorbed by visible light wavelength regions derived from intramolecular and intermolecular charge transfer complexes. The resulting polyimine film will be colored yellow to brown. Also, it generally has a large birefringence. Therefore, it cannot be used as a display substrate requiring high transparency and low birefringence. When used as a substitute material for a glass substrate, generally, a light transmittance of 10 μm and 400 nm is required to be 80% or more, a glass transition temperature (Tg) or a thermal decomposition initiation temperature is 300° C. or more, and a visible light wavelength region (400 nm to The birefringence of 800 nm) is low birefringence of 0.01 or less.

As a method of suppressing the charge-transfer interaction of the polyimine and improving the light transmittance, a method of using the alicyclic monomer in at least one of the acid dianhydride and the diamine can be exemplified.

For example, Patent Document 3 discloses that a polyfluorene imide obtained from an alicyclic acid dianhydride and various aromatic or alicyclic diamines has high transparency and low birefringence.

Patent Document 4 discloses that a polyimide obtained from 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride and 2,2'-bis(trifluoromethyl)benzidine (TFMB) has High transparency and high Tg. Further, in Patent Document 4, it has been described that 2,2'-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (HFBAPP) is used in place of 2,2'-bis(trifluoromethyl). The polyimine film of phenylenebenzamide has high transparency.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-091822

[Patent Document 2] Japanese Patent Publication No. 2007-512568

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-080350

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-085992

However, the poly-imine group Tg described in Patent Document 3 is not sufficiently high. Further, in the polyamidene group described in Patent Document 4, Tg and birefringence do not conform to the general requirements.

In this manner, the current state of polyimine materials that meet all of the required properties of high transparency, high heat resistance, and low birefringence is not clear.

The present invention provides a polyamido resin composition, a polyimide resin composition, and a polyimine in view of the above problems. The azole resin composition and the flexible substrate containing the same have excellent heat resistance, light transmittance, and low birefringence as a film after heat treatment, which is a problem.

In order to solve the above problems and achieve the object, the polyaminic acid resin composition of the present invention is characterized in that it contains (a) a polyamic acid having a structural unit represented by the general formula (1) as a main component and (b) ) solvent; (In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; a tetravalent organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 4 to 40 carbon atoms which are interlinked by a crosslinked structure; R ₂ represents a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

Further, the polyimine resin composition of the present invention is characterized in that it contains a polyimine which has a structural unit represented by (a') general formula (2) as a main component and (b) a solvent; (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups.

Further, the polyimine of the present invention An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms.

According to the present invention, a polyamido resin composition, a polyimide composition, and a polyimine can be obtained. The azole resin composition and the flexible substrate containing the same have excellent heat resistance, high light transmittance in the visible light region, and low birefringence.

[Formation of the Invention]

Hereinafter, the form for carrying out the present invention will be described in detail together with the drawings. Further, the present invention is not limited by the following embodiments. Moreover, the drawings referred to in the following description are merely schematic to show the shape, size, and positional relationship to the extent that the content of the present invention can be understood. That is, the present invention is not limited to the shapes, sizes, and positional relationships illustrated in the respective drawings.

The first aspect of the present invention is a polyacetic acid resin composition comprising (a) a polyamic acid having a structural unit represented by the formula (1) as a main component and (b) a solvent. The second aspect of the present invention is a polyimine resin composition comprising a polyimine which has a structural unit represented by the formula (2) (a) as a main component and (b) a solvent. The third aspect of the present invention is a polyimine An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent.

In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulae (1) to (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or a monocyclic alicyclic structure. The organic group is a tetravalent organic group having 4 to 40 carbon atoms directly or in a crosslinked structure interposed therebetween. In the general formulae (1) and (2), R ₂ represents a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups. In the formula (3), R ₃ represents a tetravalent organic group having 2 to 40 carbon atoms.

When the polyglycolic acid of the present invention has a structural unit represented by the above formula (1) as a main component, it may contain other structural units. Other structural units may, for example, be a polyglycolic acid of a polycondensate of an acid dianhydride and a diamine compound, a polyhydroxyguanamine of a polycondensate of a dicarboxylic acid derivative and a hydroxydiamine, and a dehydration of polyglycine. Closed-loop polyimine, polyhydroxyimide, dehydration ring closure For example, the azole or the like may contain a structural unit represented by the general formula (2), a structural unit represented by the general formula (3), and a polyfluorene in which the R ₁ in the general formula (1) is an aromatic ring. An amino acid, a polyimine in which R ₁ in the formula (2) is an aromatic ring, and a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (1) are contained, more preferably 70% or more, and still more preferably 90% or more.

Polylysine can be synthesized by a reaction of a diamine compound with an acid dianhydride or a derivative thereof as described later. The derivative may, for example, be a tetracarboxylic acid of the acid dianhydride, one of the tetracarboxylic acids, a di-, tri- or tetra-ester, an acid chloride or the like.

When the polyimine of the present invention is a structural unit represented by the above formula (2) as a main component, other structural units may be contained. As other structural units, for example, polylysine, polyhydroxyguanamine, polyimine, polybenzo Oxazole and the like. For example, it may contain a structural unit represented by the general formula (1), a structural unit represented by the general formula (3), and a polyamic acid in which R ₁ in the general formula (1) is an aromatic ring, In the formula (2), R _{1 which} is an aromatic ring, a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (2) are contained, more preferably 70% or more, and still more preferably 90% or more.

Polyimine is described later by a diamine compound and acid dianhydride or The polyglycine synthesized by the reaction of the derivative can be synthesized by heating dehydration ring closure or chemical dehydration ring closure reaction.

Polyimine of the present invention When the azole is a structural unit represented by the above formula (3), it may contain other structural units. As other structural units, for example, polylysine, polyhydroxyguanamine, polyimine, polybenzo Oxazole and the like. For example, it may contain a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and a polyamic acid in which the R ₁ in the general formula (1) is an aromatic ring. In the formula (2), R _{1 which} is an aromatic ring, a polyimine in which the R ₁ in the formula (3) is an aromatic ring Oxazole. It is preferable that 50% or more of all the structural units represented by the above formula (3) are contained, more preferably 70% or more, and still more preferably 90% or more.

Polyimine The azole can be synthesized by a heating dehydration ring closure or a chemical dehydration ring closure reaction of polyglycine synthesized by a reaction of a hydroxyguanamine group-containing diamine compound with an acid dianhydride or a derivative thereof as described later. By having The polyamino acid synthesized by the reaction of the diamine compound of the azole ring with the acid dianhydride or its derivative can be synthesized by heating dehydration ring closure or chemical dehydration ring closure reaction.

R ₁ in the general formulae (1) to (3) represents a structure of an acid component, and represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or has a single The organic group of the cyclic alicyclic structure directly or crosslinks the interconnected structure with a carbon number of 4 to 40 tetravalent organic groups bonded to each other. Here, a part of the hydrogen atom of the alicyclic structure may be substituted by a halogen. Further, these acid components may be used singly or in combination as an acid component.

When an acid dianhydride which can be used in the alicyclic structure of the present invention is exemplified, examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentane IV. Carboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -Naphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid Dihydride, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]nonane-2,4,8,10-tetracarboxylic dianhydride, three Ring [6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane -5-carboxymethyl-2,3,6-tricarboxylic acid Dihydride, 7- Bicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2, 8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride , 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (above) Trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.) and derivatives of these.

Among the above structures, as the preferable ones of R ₁ in the general formulae (1) to (3), for example, the structures represented by the following general formulae (4) to (10) can be exemplified.

In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom. The alicyclic structure of the general formulae (4) to (6) may, for example, be cyclobutane, cyclopentane or cyclohexane. In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more The two-valent crosslinked structure. As such an alicyclic structure, bicyclo [2.2.1] heptane, bicyclo [2.2.1] oct-2-ene, 7- Bicyclo [2.2.1] heptane and the like. Examples of the alicyclic structure of the general formulae (8) and (9) include decalin and tetradecyl. In the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a hydrogen atom or a hydrogen atom having 1 to 3 carbon atoms or a hydrogen atom which may be substituted by a halogen atom. a aryl group having a carbon number of 1 to 3 and a hydrogen atom which may be substituted by a halogen atom or an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom may be substituted by a halogen atom or a halogen atom. A divalent crosslinked structure composed of two or more linked groups selected by the substituted aryl group. As such an alicyclic structure, 1,1-bicyclohexane, oxybicyclohexane, etc. are mentioned.

When the above acid dianhydride is exemplified, examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 3,4-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo [2.2.1] heptane tetracarboxylic dianhydride, 7- Bicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2, 8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic dianhydride Wait.

Among them, R ₁ in the general formula (1) is 1S, 2S, 4R represented by the following chemical formulas (11) to (13) from the viewpoint of being readily available in the market and from the viewpoint of reactivity with a diamine compound. 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride. These acid dianhydrides are commercially available from Iwatani Gas Co., Ltd. under the product names "PMDA-HH", "PMDA-HS", and "BPDA-H". Further, these acid dianhydrides can be used singly or in combination of two or more.

Moreover, it is possible to use one of the acid dianhydrides in place of other acid dianhydrides within a range that does not impair the effects of the present invention. As another acid dianhydride, an aromatic acid dianhydride or an aliphatic acid dianhydride can be exemplified. For example, as the aromatic acid dianhydride, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylate can be exemplified. Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' - Oxyphthalic acid dianhydride, 2,3,3',4'-oxyphthalic acid dianhydride, 2,3,2',3'-oxyphthalic dianhydride, diphenylphosphonium-3 , 3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-double ( 2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis (3,4- Dicarboxyphenyl)ether dianhydride, bis(1,3-di-oxo-1,3-dihydroisopropylfuran-5-carboxylic acid)-1,4-benzobenzene, 2,2-bis (4 -(4-Aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5 , 6-pyridine tetracarboxylic dianhydride, 3,4,9,10-decane tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2- Bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane Anhydride, 1,6-difluoropyroic acid dianhydride, 1-trifluoromethylpyramine dianhydride, 1,6-bis(trifluoromethyl)pyroic acid dianhydride, 2,2 - bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, "Rikacid" (registered trademark) TMEG-100 (trade name, New Japan Physical and Chemical Co., Ltd.) An aromatic tetracarboxylic dianhydride such as a company, and the like. Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like, but Not limited by these. Further, these other acid dianhydrides can be used singly or in combination of two or more.

R ₂ in the general formulae (1) and (2) has a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups. For example, a structure represented by the chemical formulas (14) to (23) can be exemplified.

Among these, from the viewpoint of transparency, the structure of the chemical formula (14) is preferred, and the diamine represented by the following formula (24) is more preferably used.

R ₃ in the general formula (3) represents a tetravalent organic group having 2 to 40 carbon atoms, and examples thereof include the structures represented by the chemical formulas (25) to (34). Among these, from the viewpoint of transparency, the structure of the chemical formula (25) is preferred.

Further, R ₃ in the formula (3) is a polyimine represented by the formula (25) The azole is a dehydrated ring-closing product of the polyaminic acid represented by the formula (1) and the polyimine represented by the formula (2) synthesized from the diamine represented by the above formula (24).

Further, one of the diamine compounds may be partially substituted with another diamine compound within a range that does not impair the effects of the present invention. As the other diamine compound, an aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound can be exemplified. For example, as the aromatic diamine compound, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenylmethane can be exemplified. , 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 2,2-bis(4-amino group Phenyl) hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Ether, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine , 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3,3'-tetramethylbenzidine, meta-phenylenediamine, p-phenylene Diamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis{4-(4-aminophenoxyphenyl)}indole, bis{4-(3-aminophenoxybenzene)碸, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenyl)benzene 9,9-bis(4-aminophenoxy)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 4,4-diaminobenzamide, 3,4-diaminobenzamide, 4,4-diaminobenzophenone And 3,3-diaminobenzophenone or a diamine compound substituted with an alkyl group, an alkoxy group, a halogen atom or the like on the aromatic ring, but is not limited thereto.

As the alicyclic diamine compound, for example, cyclobutanediamine, isophoronediamine, bicyclo[2.2.1]heptane dimethylamine, tricyclo[3.3.1.13,7]decane-1, 3-Diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3,3'- Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-four Methyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl -3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4' -diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4,4'- Diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminobicyclohexane Ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2 , 2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-di Methyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3' , 5'-Dimethyl-4,4'-diaminodicyclohexyl)propane, 2,2'-bis(4-aminocyclohexyl)hexafluoropropane, 2,2'-dimethyl-4 , 4'-diaminobicyclohexane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobicyclohexane, or an alkyl group or an alkane on the alicyclic ring A diamine compound substituted with an oxy group, a halogen atom or the like, but is not limited thereto.

As the aliphatic diamine compound, for example, ethyl diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-di Alkyl hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, etc. Amines; ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether; and 1,3-bis(3) -aminopropyl)tetramethyldicyclohexane, 1,3-bis(4-aminobutyl)tetramethyldicyclohexane, α,ω-bis(3-aminopropyl)poly A cyclohexanediamine such as methylcyclohexane, but is not limited thereto.

These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used individually or in combination of 2 or more types.

Among these, it is preferred to use 9,9-(4-aminophenyl)phosphonium diamine represented by the following chemical formula (35), and it is found that the transparency or mechanical properties of the calcined film are maintained. The glass transition temperature rises and the birefringence is reduced.

The structural unit represented by the following general formula (36) or the following general formula (37) can be introduced into the molecular chain by using the diamine represented by the chemical formula (35).

(In the formula (36), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulae (36) and (37), R ₁ represents a single a tetravalent organic group having 4 to 40 carbon atoms of a cyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure, or a carbon having an interconnected structure interposed therebetween 4 to 40 of the 4 organic groups).

In general, coloring is often observed in a polyimide film using a diamine represented by the chemical formula (35). Polyimine and polyimine with the present invention As a comparison of the azole film, as described later (Comparative Example 8), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride used as a raw material monomer for transparent PI was used in the above chemical formula ( In the case of the polyimine film of the diamine or the like represented by 35), the transparency is deteriorated. Polyimine and polyimine of the present invention The azole film can suppress coloration by using an alicyclic acid dianhydride.

It is preferable to contain the diamine represented by the chemical formula (35) in a range of 10% or more and 50% or less of the total diamine residue, more preferably 30% or more and 50% or less, and still more preferably 40. % is included in the range of 50% or less. Thereby, the polyglycolic acid, the polyimine and the polyimine in the invention In the azole, the structural unit represented by the formula (36) or the formula (37) contains 10% to 50%.

In order to adjust the molecular weight to a preferred range, the polylysine, polyimine and polyimine of the present invention The azole can also seal both ends by an end sealant. As the terminal sealant to be reacted with the acid dianhydride, a monoamine or a monohydric alcohol or the like can be exemplified. Further, examples of the terminal sealant to be reacted with the diamine compound include an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a mono-active ester compound. Further, various organic groups as a terminal can be introduced by reacting the terminal sealant.

It can be used as an amine for one of the terminal sealants, and examples thereof include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, and 1-hydroxy-7-. Amino naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2- Amino naphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4- Aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6- Amino naphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7 -carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3- Amino naphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-amino group Salicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, monodecylamine cyanamide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2 -aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4- Aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-indolyl-8-aminonaphthalene, 1-indolyl-7-aminonaphthalene, 1-indenyl- 6-Aminonaphthalene, 1-indolyl-5-aminonaphthalene, 1-indolyl-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino group -7-decylnaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto- 3-aminonaphthalene, 1-amino-2-indenyl , 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline , 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl- 6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8 - amino naphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6 - Diacetylenyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-amine Naphthalene, 4,8-diethynyl-2-aminonaphthalene, etc., but are not limited by these.

Further, as the monohydric alcohol used for the terminal sealant, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3- Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-oxime Alcohol, 2-nonanol, 1-nonanol, 2-nonanol, 1-undecyl alcohol, 2-undecyl alcohol, 1-dodecanol, 2-dodecanol, 1-tridecane Alcohol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol , 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosyl alcohol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 3-methyl-1 -butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3 -heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isodecyl alcohol, 3,7- Dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptyl undecyl alcohol, ethylene glycol Ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl Ether, cyclopentanol, cyclohexanol, monomethylolcyclopentane, monomethylol dicyclopentane, monomethylol tricyclopentane, lower Alcohol, terpineol, etc., but are not limited by these.

As the terminal sealant, an acid anhydride, a monocarboxylic acid, a monoacid chlorine compound, and a single active ester compound can be exemplified by phthalic anhydride, maleic anhydride, nadic anhydride, and cyclohexane dicarboxylic anhydride. An anhydride such as 3-hydroxyphthalic anhydride; 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1 -hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3- Carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1- Mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynyl Benzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diacetylenebenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4 -diacetylenebenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4 -ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2 -ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7 a monocarboxylic acid such as ethynyl-2-naphthoic acid or 8-ethynyl-2-naphthoic acid and such a carboxyl group is an acid chlorided monoacid chlorine compound, and terephthalic acid, phthalic acid, and cis Butenedioic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-nor Aceene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 a dicarboxylic acid such as 7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene or 2,7-dicarboxynaphthalene Mono-acid chlorine compound, mono acid chlorine compound and N-hydroxybenzotriazole or N-hydroxy-5-lower An active ester compound obtained by the reaction of a ene-2,3-dicarboxy quinone imine.

The ratio of introduction of one of the amines and monohydric alcohol used in the terminal sealant is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the acid anhydride, the monocarboxylic acid, the monoacid chloride compound, and the mono-active ester compound used as the terminal sealant is preferably in the range of 0.1 to 100 mol%, particularly preferably 5 to 90 mol, based on the diamine component. ear%. A plurality of different terminal groups can also be introduced by reacting a plurality of terminal sealants.

In polylysine, polyimine and polyimine The terminal sealant introduced into the azole can be easily detected by the following method. For example, by dissolving the polymer into which the terminal sealant has been introduced in an acidic solution, the amine component and the acid anhydride component of the structural unit of the polymer are decomposed, and then can be easily detected by gas chromatography (GC) or NMR measurement. The end sealant is removed. Further, the polymer to which the terminal sealant has been introduced can be directly detected by thermal decomposition gas chromatography (PGC), infrared spectroscopy, and ¹³ C NMR spectroscopy, and can be easily detected.

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition contains (b) a solvent. As the solvent, it is possible to use two or more of the following solvents: N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamidine. A polar, aprotic solvent such as amine or dimethyl hydrazine, tetrahydrofuran, An ether such as an alkane or a propylene glycol monomethyl ether; a ketone such as acetone, methyl ethyl ketone, diisobutyl ketone or diacetone; ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate Esters such as esters; aromatic hydrocarbons such as toluene and xylene;

Relative to polylysine, polyimine and polyimine The content of the solvent (b) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, more preferably 2,000 parts by weight or less, still more preferably 1,500 parts by weight or less based on 100 parts by weight of the azole. When it is in the range of 50 to 2000 parts by weight, the viscosity suitable for coating can be made, and the film thickness after coating can be easily adjusted.

In the following, a method for producing polyacrylic acid having (a) a structural unit represented by the general formula (1) as a main component will be described. The reaction method of the polymerization reaction is not particularly limited as long as it is a polylysine which can be produced, and a known reaction method can be used.

For the specific reaction method, for example, after all the diamine components and the reaction solvent are fed into the reactor to be dissolved, the acid dianhydride component of the quantitative amount is fed, and the mixture is stirred at room temperature to 80 ° C. The method to 30 hours, etc.

From the diamine compound represented by the chemical formula (24) to 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3, The structural unit of the polyamic acid obtained from 3',4,4'-dicyclohexanetetracarboxylic dianhydride can be exemplified by the following chemical formulas (38) to (42).

In the following, a method for producing poly(imine) having (a') a structural unit represented by the formula (2) as a main component will be described. The method for producing polylysine represented by the formula (1) obtained by the above-described conventional reaction method can be used without any particular limitation, and a conventional reaction method can be used.

Specific examples of the reaction method include a method in which the polyamic acid solution obtained as described above is stirred at room temperature to 200 ° C for 0.5 to 30 hours.

From the diamine compound represented by the chemical formula (24) to 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3, The structural unit of the polyimine obtained by 3',4,4'-dicyclohexanetetracarboxylic dianhydride can be exemplified by the following chemical formulas (43) to (45).

Next, (a") a polyimine which has a structural unit represented by the general formula (3) as a main component The method of producing the azole will be described. As the first method, for example, a polyfluorene ring represented by the formula (2) obtained by the above-described reaction method can be used for the dehydration ring closure. In the reaction method, it is not particularly limited, and a conventional reaction method can be utilized. As a specific reaction method, for example, a method of heat-treating a polyimide pigment at a temperature of 300 to 400 ° C for 0.5 to 30 hours; adding an acid catalyst such as a thermal acid generator to a polyimide solution at room temperature to The method of stirring at 250 ° C for 0.5 to 30 hours, and the like.

As the second method, for example, hydrazine imidation is represented by containing the following formula (46). Polylysine obtained from the diamine of the azole ring and the acid dianhydride. Specific examples of the reaction method include a method of feeding a predetermined amount of the acid dianhydride component, stirring at room temperature to 80 ° C for 0.5 to 30 hours, and then stirring at room temperature to 200 ° C for 0.5 to 30 hours.

(In the formula (46), R ₃ represents a tetravalent organic group having 2 to 40 carbon atoms).

A diamine compound represented by the chemical formula (24) and a 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3 a poly-proline acid obtained from 3', 4, 4'-dicyclohexane tetracarboxylic dianhydride, or a diamine compound represented by the chemical formula (47) and 1S, 2S, 4R, which is closed by dehydration. Aggregation of 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride Polyimine The structural unit of the azole can be exemplified by the following chemical formulas (48) to (50).

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a surfactant. Examples of the surfactants include fluorine-based surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Corporation), and Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.). . Further, for example, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Polyflow, GLANOL (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (for example) An organic oxoxane surfactant such as a trade name, manufactured by BYK Chieme Co., Ltd.). Further, an acrylic polymer surfactant such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be exemplified.

Relative to polylysine, polyimine and polyimine The surfactant preferably contains 0.01 to 10 parts by weight based on 100 parts by weight of the azole.

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain an internal mold release agent. As the internal mold release agent, long-chain fatty acids and the like can be exemplified.

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a thermal crosslinking agent. The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or a methylol group. By having at least two such groups, a condensation reaction can be carried out with a resin and a molecule of the same type to form a crosslinked structure, thereby improving mechanical strength or chemical resistance.

As preferred examples of the epoxy compound, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, polymethyl group can be exemplified. An epoxy group-containing polyoxyalkylene such as (glycidoxypropyl) or a decyl oxide; the present invention is not limited thereto. Specifically, for example: Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA- 1514, Epiclon EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 (above trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.); Rika Resin BEO- 60E, Rika Resin BPO-20E, Rika Resin HBE-100, Rika Resin DME-100 (above trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.); EP-4003S, EP-4000S (above trade name, manufactured by Adeka Co., Ltd.) ); PG-100, CG-500, EG-200 (above trade name, manufactured by Osaka Gas Chemical Co., Ltd.); NC-3000, NC-6000 (above Product name, manufactured by Nippon Kayaku Co., Ltd.; EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (above trade name, manufactured by Printech Co., Ltd.); Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085 (trade name, manufactured by Daicel Chemical Industry Co., Ltd.), and the like.

As the compound having at least 2 alkoxymethyl groups or hydroxymethyl groups, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML can be exemplified. -OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM -BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above trade name, manufactured by Honshu Chemical Industry Co., Ltd.); NIKALAC ( Registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade name, manufactured by Sanhe Chemical Co., Ltd.). It is also possible to contain two or more of these compounds.

The polyaminic acid resin composition of the present invention, the polyimine resin composition, the polyimine The azole resin composition can contain a colorant. Polyamine, polyimine, polyimine can be adjusted by adding a colorant The color of the azole film.

As the colorant, a dye, an organic pigment, an inorganic pigment or the like can be used, and from the viewpoint of heat resistance and transparency, an organic pigment is preferable. Among them, those having high transparency, excellent light resistance, heat resistance, and chemical resistance are preferred. When the color index (CI) number indicates a specific example of a representative organic pigment, it is preferred to use the following ones, but it is not limited by any of these coloring agents.

As an example of the yellow pigment, pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147 is used. , 148, 150, 153, 154, 166, 168, 185, and the like. Further, as an example of the orange pigment, pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71 and the like are used. Further, as an example of the red pigment, Pigment Red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217 is used. , 220, 223, 224, 226, 227, 228, 240, 254, and the like. Further, as an example of the violet pigment, pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50 or the like is used. Further, as an example of the blue pigment, Pigment Blue (hereinafter abbreviated as PB) 15, 15:3, 15:4, 15:6, 22, 60, 64 and the like are used. Further, as an example of the green pigment, pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58, and the like are used. If necessary, these pigments may also be subjected to surface treatment such as rosin treatment, acid-based treatment, alkaline treatment, and the like.

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain an inorganic filler. Examples of the inorganic filler include cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, and zirconia fine particles.

The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fibrous shape.

In order to prevent scattering of light, the inorganic filler contained is preferably small in particle diameter. The average particle diameter is from 0.5 to 100 nm, preferably from 0.5 to 30 nm.

Relative to polylysine, polyimine or polyimine In the case of azole, the content of the inorganic filler is preferably from 1 to 50% by weight, more preferably from 10 to 30% by weight. As the content increases, the flexibility or folding endurance will decrease.

As a polyamine resin composition, a polyimide resin composition or a polyimine The method of containing an inorganic filler in the azole resin composition is capable of utilizing various conventional methods. For example, it can be exemplified by making an organic inorganic filler with polyglycine, polyimine or polyimine The azole is mixed. The organic-inorganic filler is dispersed in an organic solvent at a ratio of about 30% by weight. Examples of the organic solvent include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, and methyl isobutyl. Ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1 , 3-dimethylimidazolidinone, γ-butyrolactone, and the like.

In order to make polyamic acid, polyimine or polyimine for inorganic fillers The dispersibility of the azole is improved, and the organic inorganic filler can also be treated with a decane coupling agent. When the terminal functional group of the decane coupling agent has an epoxy group or an amine group, it can be combined with polyglycine, polyimine, and polyimine by bonding with a carboxylic acid of polyphthalic acid. More effective dispersion is achieved by the affinity of the azole.

As the epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-epoxy Propoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and the like.

As the amine group, an example is: N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N -Phenyl-3-aminopropyltrimethoxydecane, and the like.

As a treatment method by a decane coupling agent of an organic inorganic filler sol, various conventional methods can be utilized. For example, by adding a decane coupling agent to the organic inorganic filler sol having a adjusted concentration, it can be treated by stirring at room temperature to 80 ° C for 0.5 to 2 hours.

Polyphthalic acid resin composition, polyimine resin composition and polyimine of the present invention The azole resin composition can contain a photoacid generator. When the photoreceptor for drawing the exposure pattern is irradiated with light, the acid is generated in the exposed portion to increase the solubility of the exposed portion in the aqueous alkali solution, and it can be used as a positive photosensitive resin. Use.

As the photoacid generator which can be used in the present invention, a quinonediazide compound, a phosphonium salt, a diazonium salt, a phosphonium salt or the like can be exemplified. Among them, a quinonediazide compound is preferably used from the viewpoint of obtaining an excellent dissolution inhibiting effect and obtaining a positive photosensitive resin composition having high sensitivity and low film reduction. Further, it may contain two or more kinds of photoacid generators. Thereby, the exposure can be increased Since the dissolution rate of the portion and the unexposed portion is higher, a positive photosensitive resin composition having a high sensitivity can be obtained.

As the quinonediazide compound, for example, a quinonediazide sulfonic acid is ester-bonded to a polyhydroxy compound, a quinonediazide sulfonic acid is sulfonamide bonded to a polyamine compound, and hydrazine is used. The diazonium sulfonic acid is bonded to the polyhydroxy polyamine compound by an ester bond and/or a sulfonamide. All of the functional groups of the polyhydroxy compound or the polyamino compound may not be substituted by quinonediazide, and it is preferred that 50 mol% or more of the entire functional group is substituted with quinonediazide. By using such a quinonediazide compound, it is possible to form a positive photosensitive resin composition which is a reaction of a general ultraviolet light mercury lamp i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm).

In the present invention, the quinonediazide compound is preferably any one of a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group. A compound having such a group may be used in the same molecule, and a compound having a different group may also be used in combination.

The quinonediazide compound which can be used in the present invention is synthesized from a specific phenol compound according to the following method. For example, a method of reacting 5-naphthoquinonediazidesulfonium chloride with a phenol compound in the presence of triethylamine can be exemplified. The method for synthesizing the phenol compound is, for example, a method of reacting an α-(hydroxyphenyl)styrene derivative with a polyhydric phenol compound under an acid catalyst.

Relative to polylysine, polyimine or polyimine The content of the photoacid generator is preferably from 3 to 40 parts by weight based on 100 parts by weight of the azole. By setting the content of the photo-acid generator to this range, it is possible to achieve higher sensitivity. Further, a sensitizer or the like may be further contained as necessary.

In the pattern in which the positive photosensitive resin is formed, a varnish of a positive photosensitive resin is applied onto the substrate, and after exposure, the exposed portion is removed using a developing solution. As the developer, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine is preferred. , dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. An aqueous solution of the compound. Further, depending on the case, a plurality of the following compounds may be added singly or in combination with the above aqueous alkali solution: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N , polar solvents such as N-dimethylacetamide, dimethyl hydrazine, γ-butyrolactone, dimethyl acrylamide; alcohols such as methanol, ethanol, isopropanol; ethyl lactate, propylene glycol An ester such as monomethyl ether acetate; a ketone such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone. After development, it is preferred to carry out a rinsing treatment with water. Here, an alcohol such as ethanol or isopropyl alcohol; an ester such as ethyl lactate or propylene glycol monomethyl ether acetate may be added to water and then rinsed.

Hereinafter, the polyphthalic acid resin composition, the polyimine resin composition, and the polyimine of the present invention are used. A method of producing a heat resistant resin film by using an azole resin composition will be described.

First, a polyamine resin composition, a polyimide composition, or a polyimine The azole resin composition is coated on the substrate. For example, a germanium wafer, a ceramic, a gallium arsenide, a soda lime glass, an alkali-free glass, or the like can be used as the substrate, but is not limited thereto. The coating method may be, for example, a method such as a slit die coating method, a spin coating method, a roll coating method, or a rod coating method, or may be applied by a combination of these methods.

Next, drying the coated polyamine resin composition, the polyimide component, or the polyimine a substrate of an azole resin composition, which is obtained as a polyphthalic acid resin composition, a polyimine resin composition or a polyimine The azole resin composition is coated with a film. The drying system uses a hot plate, an oven, an ultraviolet ray, a vacuum chamber, or the like. In the case of using a hot plate, it is heated directly on the plate, or the object to be heated is held on a jig provided by a close pin or the like provided on the plate. The material of the proximity pin may be a metal material such as aluminum or stainless steel, or a synthetic resin such as a polyimide resin or a "Teflon (registered trademark)", and may be used as a proximity pin of any of the materials. The height of the proximity pin is various depending on the size of the substrate, the type of the resin layer of the object to be heated, the purpose of heating, and the like, for example, heating the resin layer applied on a glass substrate of 300 mm × 350 mm × 0.7 mm, and the proximity of the needle The height is preferably about 2 to 12 mm. The heating temperature is in various forms depending on the kind or purpose of the object to be heated, and it is preferably from 1 minute to several hours from room temperature to 180 °C.

Then, the temperature is increased to a heat resistant resin film in a range of from 180 ° C to 400 ° C. The method of peeling the heat-resistant resin film from the substrate may be performed by any method such as a method of immersing in a chemical solution such as fluoric acid or a method of irradiating a laser to the interface between the heat-resistant resin coating film and the substrate.

Further, as described above, by the heat treatment of the polyglycolic acid or polyimine of the present invention having the structural unit represented by the general formulae (1) and (2) as a main component, the general formula (2) can be obtained. Polyimine which is a main component of the structural unit represented, or a polyimine which has a structural unit represented by the general formula (3) as a main component Oxazole.

The heat resistant resin film obtained as described above has high transparency, high heat resistance, low birefringence, and flexibility, and can be suitably used as a flexible substrate. Regarding the transparency, the transmittance at a wavelength of 400 nm is preferably 85% or more, more preferably 90% or more, still more preferably 95% or more. The glass transition temperature is preferably 250 ° C or higher, more preferably 300 C or higher, and still more preferably 350 ° C or higher. The birefringence is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.003 or less.

The flexible substrate containing the resin composition of the present invention can be used for displays such as liquid crystal displays, organic EL displays, touch panels, electronic papers, color filters, and the like, and flexible displays such as solar cells and CMOS. monitor.

In the manufacturing step of the flexible display, a step of forming a circuit necessary for the display element and the light receiving element on the heat resistant resin film formed on the substrate is included. For example, an amorphous germanium TFT can be formed on a flexible substrate. Further, it is also possible to form a configuration necessary for the element thereon by a conventional method. As described above, a solid heat-resistant resin film having a circuit or the like formed on the surface thereof can be peeled off from the substrate by a conventional method such as laser irradiation to obtain a flexible element.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples.

(1) Production of heat resistant resin film

On a 6-inch mirror-finished wafer, a coating development device Mark-7 manufactured by Tokyo Electron Co., Ltd. was used to pre-bake at 140 ° C for 4 minutes. The varnish was spin-coated so that the film thickness became 15±0.5 μm. Thereafter, a hot plate of Mark-7 was used in the same manner to perform a prebaking treatment at 140 ° C for 4 minutes. Using a inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and under a nitrogen stream (oxygen concentration of 20 ppm or less), the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes, and then 5 The heat resistant resin film was obtained by cooling to ° ° C / min until 50 ° C. Next, after immersing in fluoric acid for 1 to 4 minutes, the heat resistant resin film is peeled off from the substrate, and air-dried to obtain a heat resistant resin film.

(2) Production of heat-resistant resin film (on glass substrate)

On a 50 mm × 50 mm × 1.1 mm thick glass substrate (TEMPAX), a spin coater MS-A200 manufactured by Mikasa Co., Ltd. was used, and the film thickness after prebaking at 140 ° C for 4 minutes was 15 ± 0.5 μm. Rotating coated varnish. Thereafter, pre-baking treatment at 140 ° C for 4 minutes was carried out using a hot plate D-SPIN of Dainippon Screen Co., Ltd. Using a inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and under a nitrogen stream (oxygen concentration: 20 ppm or less), the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes at 5 ° C. /min was cooled until 50 ° C to prepare a heat resistant resin film (on a glass substrate).

(3) Production of heat-resistant resin film (on a substrate)

Spin coating was performed on a substrate of 1/4 of 1/4, using a spin coater MS-A200 manufactured by Mikasa Co., Ltd., and the film thickness after prebaking at 140 ° C for 4 minutes was 5 ± 0.5 μm. Varnish. Thereafter, pre-baking treatment at 140 ° C for 4 minutes was carried out using a hot plate D-SPIN of Dainippon Screen Co., Ltd. An inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) was used under a nitrogen stream (oxygen concentration: 20 ppm). Next, the prebaked film was heated at 3.5 ° C / min up to 300 ° C or 350 ° C for 30 minutes, and cooled at 5 ° C / min to 50 ° C to obtain a heat resistant resin film (on the substrate).

(4) Determination of light transmittance (T)

The light transmittance at 400 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). Further, in the measurement, the heat resistant resin film obtained in (2) was used.

(5) Determination of total light transmittance (Tt)

The total light transmittance of the heat resistant resin film obtained in (1) was measured using a direct reading type haze (HGM2DP manufactured by Suga Test Machine Co., Ltd., C light source). Also, the value of one measurement was used as Tt. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(6) Determination of refractive index, in-plane/out-of-plane birefringence

The TE refractive index (n(TE)) and the TM refractive index (n(TM)) of a wavelength of 632.8 nm were measured using a 稜鏡 coupling (manufactured by METRICON Co., Ltd., PC2010). n (TE) and n (TM) are refractive indices in parallel and perpendicular directions with respect to the polyimide film surface. The average refractive index n (AV) is calculated from ((2 × n(TE) ² + n(TM) ² ) / 3) ^0.5 , and the in-plane/out-of-plane birefringence is set to n (TE) and n ( Calculated by the difference (n(TE)-n(TM)) of TM). Further, in the measurement, the heat resistant resin film obtained in (3) was used.

(7) Determination of glass transition temperature (Tg) and coefficient of linear expansion (CTE)

The measurement was carried out under a nitrogen flow using a thermomechanical analyzer (EXST AR6000 TMA/SS6000 manufactured by SII Nanotechnology Co., Ltd.). The heating method was carried out under the following conditions. In the first stage, the temperature is raised to 150 ° C at a heating rate of 5 ° C / min to remove the adsorbed water of the sample; in the second stage Cool to room temperature at a cooling rate of 5 ° C / min. The measurement was carried out in the third stage at a heating rate of 5 ° C/min to determine the glass transition temperature. Further, the linear expansion coefficient (CTE) was obtained from the average of the linear expansion coefficients of 50 to 200 ° C in the third stage. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(8) Determination of 1% thermal weight reduction temperature (Td1)

The measurement was carried out under a nitrogen flow using a thermogravimetric measuring apparatus (TGA-50 manufactured by Shimadzu Corporation). The heating method was carried out under the following conditions. In the first stage, the adsorbed water of the sample was removed by raising the temperature to 350 ° C at a heating rate of 3.5 ° C / min; in the second stage, it was cooled to room temperature at a cooling rate of 10 ° C / min. In the third stage, the measurement was carried out at a heating rate of 10 ° C/min, and a 1% thermogravimetric reduction temperature was determined. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(9) Determination of fracture stress, elongation at break, and Young's modulus

The measurement was carried out using Tensilon (Orientec Co., Ltd. RTM-100). For each sample, 10 samples or more were measured, and the JIS average value was calculated using JIS number average (JIS K-6301). Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(10) Determination of b ^* value

The b ^* value of CIELAB in the representative color space was measured using an SM color computer (Suga Test Machine Co., Ltd. SM-7-CH). A C light source was used in the light source, and the measurement was performed in a transmitted light mode. Also, in CIELAB, the b ^* value corresponds to the coordinates of yellow and blue, b ^* >0 is yellowish, and b ^* <0 is blueish. Further, in the measurement, the heat resistant resin film obtained in (1) was used.

(11) Production of relief pattern

The photosensitive resin composition (varnish) produced in the Example was spin-coated on an 8-inch wafer, and then hot plate (Marking and developing device Mark-7 manufactured by Tokyo Electron Co., Ltd.) was used at 120 ° C. Heat treatment (pre-bake) for 3 minutes to prepare a pre-baked film having a thickness of 2 to 4 μm. The obtained prebaked film was exposed by an i line stepper (manufactured by GCA Corporation, DSW-8000) at an exposure amount of 20 to 320 mJ/cm ² and in a step of 10 mJ/cm ² . The line & gap pattern for exposure is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, 100 μm. After the exposure, development was carried out for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D), followed by rinsing with pure water to obtain an undulating pattern. Further, the film thickness after prebaking and after development was measured using a light interferometric film thickness measuring device Lambda Ace SM-602 manufactured by Dainippon Screen Manufacturing Co., Ltd., and a refractive index of 1.63 was measured.

(12) Calculation of reduction amount of developing film

The amount of development film reduction was calculated according to the following formula.

Development film reduction (μm) = film thickness after pre-baking - film thickness after development

(13) Calculation of sensitivity

After the exposure and development, a line-and gap pattern of 10 μm and 20 μm (1L/1S) was formed to have a sensitivity of 1 to 1 as the minimum exposure amount.

Hereinafter, the abbreviations of the compounds used in the examples are described.

PMDA-HH: 1S, 2S, 4R, 5R-cyclohexane tetracarboxylic dianhydride

PMDA-HS: 1R, 2S, 4R, 5R-dicyclohexane tetracarboxylic dianhydride

BPDA-H: 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride

PMDA: pyrethic acid dianhydride

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

ODPA: 3,3',4,4'-oxydiphthalic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

HFHA: 2,2'-bis[3-(3-aminobenzylideneamino)-4-hydroxyphenyl]hexafluoropropane

FDA: 9,9-bis(4-aminophenyl)anthracene

CHDA: trans-1,4-diaminocyclohexane

PDA: p-phenylenediamine

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

TFMB: 2,2'-bis(trifluoromethyl)benzidine

m-BAPS: bis[4-(3-aminophenoxy)phenyl]indole

SiDA: 1,3-bis(3-aminopropyl)tetramethyldioxane

MAP: m-aminophenol

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

EL: ethyl lactate

DFA: dimethylformamide dimethyl acetal

Example 1

Under a nitrogen stream, 2.7704 g (12 mmol) of PMDA-HH, 7.4706 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

Example 2

Under a dry nitrogen stream, 2.7704 g (12 mmol) of PMDA-HS, 7.4706 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

Example 3

Under dry nitrogen flow, 3.4441 g (11 mmol) of BPDA-H, 6.7969 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 80 °C. After 8 hours, it was cooled to make a varnish.

Example 4

Under dry nitrogen flow, 2.7704 g (12 mmol) of PMDA-HH, 6.5286 g (10.8 mmol) of HFHA, 0.4181 g (1.2 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated and stirred at 80 ° C. . After 8 hours, it was cooled to make a varnish.

Example 5

Under a dry nitrogen stream, 1.0238 g (3.48 mmol) of BPDA, 1.9099 g (8.52 mmol) of PMDA-HH, 0.4110 g (3.60 mmol) of CHDA, 5.0778 g (8.40 mmol) of HFHA, 50 g of NMP were added to 100 mL of four. In a neck flask, the mixture was heated and stirred at 80 °C. After 8 hours, it was cooled to make a varnish.

Example 6

Under dry nitrogen flow, 3.4345 g (15.3 mmol) of PMDA-HS, 8.7985 g (14.5 mmol) of HFHA, 0.2669 g (0.8 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

Example 7

Under dry nitrogen flow, 3.4893 g (15.6 mmol) of PMDA-HS, 8.4683 g (14.0 mmol) of HFHA, 0.5424 g (1.6 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 8 hours, it was cooled to make a varnish.

Example 8

Under dry nitrogen flow, 3.6402 g (16.1 mmol) of PMDA-HS, 7.7753 g (12.9 mmol) of HFHA, 1.1204 g (3.2 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

Example 9

Under dry nitrogen flow, 3.7270 g (16.6 mmol) of PMDA-HS, 7.0351 g (11.6 mmol) of HFHA, 1.7379 g (5.0 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

Example 10

3.8584 g (17.2 mmol) of PMDA-HS, 6.2427 g (10.3 mmol) of HFHA, 2.3989 g (6.9 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask under a stream of dry nitrogen, and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

Example 11

Under dry nitrogen flow, 3.9994 g (17.8 mmol) of PMDA-HS, 5.3924 g (8.9 mmol) of HFHA, 3.1082 g (8.9 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

Comparative example 1

Under a dry nitrogen stream, 2.7154 g (12 mmol) of PMDA, 7.5255 g (12 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

Comparative example 2

Under a dry nitrogen stream, 3.3527 g (11 mmol) of BPDA, 6.8883 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

Comparative example 3

Under dry nitrogen flow, 3.4731 g (11 mmol) of ODPA, 6.7679 g (11 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

Comparative example 4

Under a nitrogen stream, 5.2599 g (23 mmol) of PMDA-HH, 4.9811 g (23 mmol) of m-TB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 2 hours, it was cooled to make a varnish.

Comparative Example 5

Under a dry nitrogen stream, 7.0599 g (15.9 mmol) of 6FDA, 9.6068 g (15.9 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 6

Under a dry nitrogen stream, 7.2639 g (16.4 mmol) of 6FDA, 5.2361 g (16.4 mmol) of TFMB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 7

8.4450 g (19.0 mmol) of 6FDA, 8.2216 g (19.0 mmol) of m-BAPS, and 50 g of NMP were added to 100 mL under a stream of dry nitrogen. In a four-necked flask, the mixture was heated and stirred at 30 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 8

Under a dry nitrogen stream, 7.824 g (17.6 mmol) of 6FDA, 2.4547 g (7.0 mmol) of FDA, 6.3879 g (10.6 mmol) of HFHA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 30 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 9

Under a dry nitrogen stream, 5.1472 g (23 mmol) of PMDA-HH, 7.3528 g (23 mmol) of TFMB, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 10

Under a nitrogen stream, 5.6897 g (25.4 mmol) of PMDA-HS, 10.9770 g (25.4 mmol) of m-BAPS, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 11

Under a dry nitrogen stream, 9.2384 g (30.2 mmol) of BPDA-H, 3.2616 g (30.2 mmol) of PDA, and 50 g of NMP were placed in a 100 mL four-necked flask, and the mixture was stirred under heating at 50 °C. After 6 hours, it was cooled to make a varnish.

Comparative Example 12

Under a dry nitrogen stream, 4.1511 g (18.5 mmol) of PMDA-HS, 4.4776 g (7.4 mmol) of HFHA, 3.8714 g (11.1 mmol) of FDA, and 50 g of NMP were placed in a 100 mL four-necked flask and heated at 30 ° C. Stir. After 6 hours, it was cooled to make a varnish.

The varnish compositions synthesized in Examples 1 to 11 and Comparative Examples 1 to 12 are shown in Table 1. Further, in Table 1, the light transmittance (T), the total light transmittance (Tt), and the TE refractive index (n (the light transmittance) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes. TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% heat The result of the weight reduction temperature (Td1).

Example 12

Under a dry nitrogen stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. 47.5 g of GBL was added to the obtained 15 g of the polyimine powder to obtain a polyimide pigment varnish.

Example 13

Under dry nitrogen flow, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. 47.5 g of GBL was added to the obtained 15 g of the polyimine powder to obtain a polyimide pigment varnish.

The light transmittance (T), total light transmittance (Tt), and TE refractive index of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 12 and 13 in Table 2. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transfer Temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight reduction temperature (Td1).

Example 14

Under a dry nitrogen stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. The heat treatment of the obtained polyimide pigment powder was carried out in an oven at 350 ° C for 30 minutes under a nitrogen stream to obtain a polyimine. Oxazole powder. 47.5 g of NMP was added to the obtained 15 g of polyimine Polyazole Azole varnish.

Example 15

Under dry nitrogen flow, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added together with 100 g of NMP, and stirred at 30 ° C for 6 hours. Thereafter, it was stirred at room temperature for 12 hours. Then, it was stirred at 180 ° C for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyimide pigment powder. Under the dry nitrogen flow, the obtained polyimine powder was heat-treated in an oven at 350 ° C for 30 minutes to obtain a polyimide. Oxazole powder. 47.5 g of NMP was added to the obtained 15 g of polyimine Polyazole Azole varnish.

The light transmittance (T), total light transmittance (Tt), and TE refractive index of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 14 and 15 in Table 3. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% The result of the thermogravimetric reduction temperature (Td1).

Example 16

The organic cerium sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight of the cerium oxide microparticles obtained in the first embodiment) 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

Example 17

The organic cerium sol (manufactured by Nissan Chemical Industries, Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight) of the cerium oxide particles obtained in the first embodiment. 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

Example 18

The organic cerium sol (manufactured by Nissan Chemical Industries, Ltd., trade name: PMA-ST, particle size 10 to 10 parts by weight) of the cerium sulphide granules obtained in the first embodiment. 30 nm) was added to the polyamic acid varnish to obtain a poly-proline-niobium oxide nanoparticle varnish.

The varnish compositions adjusted in Examples 16 to 18 are shown in Table 4. Moreover, in Table 4, the light transmittance (T), the total light transmittance (Tt), and the TE refractive index (n (TE)) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes. , TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermogravimetric reduction temperature The result of (Td1).

Example 19

0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 to obtain a polyimide pigment varnish.

Example 20

0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

Example 21

0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.4 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

Example 22

0.044 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.8 g of Epiclon 850-S (trade name, Dainippon Ink Chemical Co., Ltd.), and 13.47 g of GBL were added to 4 g of the polyimine powder obtained in Example 13 was used to obtain a polyimide pigment varnish.

The light transmittance (T), total light transmittance (Tt), and TE refractive index (n) of the heat resistant resin film obtained by calcination at 300 ° C were measured using the varnishes of Examples 19 to 22 in Table 5. (TE)), TM refractive index (n(TM)), average refractive index (n(AV)), in-plane/out-of-plane birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% Thermal weight reduction temperature (Td1), fracture stress, elongation at break, and Young's modulus.

Reference example 1

Stirring 117 g of PB15:6 (average primary particle size 30 nm), 140 g of Ajsper PB821 propylene glycol monomethyl ether acetate solution (30% by weight), 93 g of Daicel chemistry using a homogenizer Industrial Co., Ltd. "Cyclomer" ACA250 (45% by weight solution) and 627 g of propylene glycol monomethyl ether acetate were prepared to prepare a paste. The paste beaker was connected to a circulating bead mill disperser ("DYNO-MILL" KDL-A, manufactured by WAB A Bachofen Co., Ltd.), and a zirconia bead having a diameter of 0.3 mm was used as a medium at 3,200 rpm. After 3 hours of dispersion treatment, a blue pigment dispersion was obtained. 49.5833 g of GBL was added to the obtained 0.4167 g of the blue pigment dispersion to obtain a diluted solution.

Example 23

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 36.3 g of GBL were added to 13 g of the polyimine powder obtained in Example 13 to obtain a polyimide pigment varnish.

Example 24

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.325 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

Example 25

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.650 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

Example 26

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.975 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

Example 27

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.300 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

Example 28

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.625 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

Example 29

0.013 g of the surfactant Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 2.600 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL were added to 13 g of Example 13 Polyimine varnish is obtained by polyimine powder.

The light transmittance (T), b ^* value, and TE refractive index (n(TE)) of the heat resistant resin film obtained by calcination at 350 ° C were measured using the varnishes of Examples 23 to 29 in Table 6. , TM refractive index (n (TM)), average refractive index (n (AV)), in-plane / out-of-plane birefringence results.

Example 30

22.4 g of HFHA (0.037 mol) and 0.58 g of SiDA (0.0023 mol) were dissolved in 105 g of NMP under a stream of dry nitrogen. 5.75 g of ODPA (0.018 mol) was added together with 20 g of NMP, and stirred at 40 ° C for 1 hour. Thereafter, 6.23 g of PMDA-HH was added together with 20 g of NMP, and stirred at 80 ° C for 8 hours. Then, it was stirred at room temperature for 11 hours. Thereafter, 1.011 g of MAP was added together with 15 g of NMP, and stirred at 60 ° C for 1 hour. Thereafter, a solution of 4.60 g of DFA (0.038 mol) diluted with 10 g of NMP was added dropwise, and after dropwise addition, stirring was continued at 60 ° C for 1 hour. After that, the same operation was performed twice. Thereafter, 16.96 g of acetic acid was added at room temperature, and the mixture was stirred for 1 hour. After the completion of the stirring, the solution was poured into 2 L of water, and the precipitate of the polymer solid was filtered and collected. Further, the mixture was washed five times with 2 L of water, and the collected polymer solid was dried in a dryer at 50 ° C for 72 hours to obtain a polyphthalate powder.

To 4 g of the obtained polyphthalate powder, 0.455 g of a quinonediazide compound TP-250 (manufactured by Toyo Seisakusho Co., Ltd.) and 0.455 g of HAP-170 (manufactured by Toyo Seisakusho Co., Ltd.), 0.421 were added. g dissolution accelerator Tris-HAP (manufactured by Honshu Chemical Co., Ltd.), 0.682 g of thermal crosslinking agent HMOM (manufactured by Honshu Chemical Co., Ltd.), and 0.182 g of surfactant Active Flow 77 (trade name, Kyoeisha Chemical Co., Ltd.) A varnish of a photosensitive resin composition was obtained by 9.3 g of EL and 6.9 g of GBL. Using the obtained varnish, the undulating pattern was produced by the method of the above (9), and after the photosensitivity evaluation, the amount of development film reduction was reduced to 0.17 μm, and the sensitivity was 300 mJ/cm ² .

Example 31

To 4.646 g of the polyimine powder obtained in Example 12, 0.929 g of a quinonediazide compound HAP-170 (manufactured by Toyo Seisakusho Co., Ltd.) and 0.664 g of a thermal crosslinking agent HMOM (Honzhou Chemical Co., Ltd.) were added. A varnish of a photosensitive resin composition was obtained by using 0.011 g of a surfactant, Polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and 18.75 g of GBL. Using the obtained varnish, the undulation pattern was produced by the method of the above (9), and after the photosensitivity evaluation, the amount of development film reduction was 1.27 μm, and the sensitivity was 125 mJ/cm ² .

[Industrial availability]

According to the present invention, it is possible to provide a polyamine resin composition, a polyimide composition, and a polyimine. The azole resin composition has excellent heat resistance, light transmittance, and low birefringence after heat treatment. The film after heat treatment can be applied to a flexible substrate such as a flat panel display, a touch panel, an electronic paper, a color filter substrate, a solar cell, a surface protective film of a semiconductor element, an interlayer insulating film, or an organic electroluminescence element (organic The insulating layer or the spacer layer of the EL element), the planarizing film of the thin film transistor substrate, the insulating layer of the organic transistor, the flexible printed circuit board, and the like.

Claims (17)

A polyaminic acid resin composition characterized by comprising (a) a polyamic acid having a structural unit represented by the general formula (1) as a main component and (b) a solvent; (In the formula (1), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; a tetravalent organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure, or a tetravalent organic group having 4 to 40 carbon atoms which are interlinked by a crosslinked structure; R ₂ represents a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups. The polyamino acid resin composition according to claim 1, wherein R ₁ in the formula (1) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more the divalent crosslinked structure; in the general formula (10), X ₄ based direct bond, an oxygen atom, a sulfur atom, a sulfonic acyl or a hydrogen atom may also be a halogen atom substituted with 1 to 3 carbon atoms of the divalent An organic group or a hydrogen atom may be substituted by a halogen atom, an aryl group or an oxygen atom, a sulfur atom, a sulfonyl group, or a hydrogen atom may be substituted by a halogen atom, and a carbon number of 1 to 3 may be substituted with a hydrogen atom and hydrogen. A divalent crosslinked structure composed of two or more bonds selected from an extended aryl group in which an atom is substituted by a halogen atom). The polyaminic acid resin composition of claim 1, wherein the R ₂ in the formula (1) is represented by the following formula (14), The polyaminic acid resin composition according to the first aspect of the invention, wherein the polyamic acid having the structural unit represented by the formula (1) (1) as a main component contains 10% to 50% of the formula ( 36) the structural unit represented; (In the formula (36), X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and R ₁ represents an alicyclic structure having a monocyclic or condensed polycyclic ring type; The tetravalent organic group having a carbon number of 4 to 40, or an organic group having a monocyclic alicyclic structure or a tetravalent organic group having a carbon number of 4 to 40 in which the crosslinked structure is interlinked therebetween. The polyphthalic acid resin composition according to any one of claims 1 to 4, wherein the in-plane/out-of-plane birefringence obtained by the heat treatment is 0.01 or less. A polyimine resin composition characterized by comprising a polyimine and (b) a solvent having (a') a structural unit represented by the general formula (2) as a main component; (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups. The polyimine resin composition of claim 6, wherein R ₁ in the formula (2) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more a two-valent crosslinked structure; in the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom which may be substituted by a halogen atom, an aryl group or an oxygen atom, sulfur a valent organic group having 1 to 3 carbon atoms or a hydrogen atom to which an atom, a sulfonyl group or a hydrogen atom may be substituted by a halogen atom may be substituted by a halogen atom, and a divalent organic group having 1 to 3 carbon atoms and a hydrogen atom. A divalent crosslinked structure composed of two or more linkages selected from an extended aryl group substituted by a halogen atom). The polyimine resin composition of claim 6, wherein the R ₂ in the formula (2) is represented by the following formula (14), The polyimine resin composition of claim 6, wherein the polyimine having the structural unit represented by the formula (2) (a) contains 10% to 50% of a general formula. (37) the structural unit represented; (In the formula (37), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. Or a tetravalent organic group having 4 to 40 carbon atoms in which the crosslinked structure is interlinked. The polyimine resin composition according to any one of claims 6 to 9, wherein the in-plane/out-of-plane birefringence obtained by the heat treatment is 0.01 or less. Polyimine An azole resin composition characterized by containing a polyimine which has a structural unit represented by the formula (3) (3) as a main component Oxazole and (b) solvent; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms. Such as the polyimine of claim 11 An azole resin composition in which R ₁ in the general formula (3) is one or more selected from the following general formulae (4) to (10); (In the general formulae (4) to (10), R ₄ to R ₇₉ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom; In the formula (7), the X ₃ -based oxygen atom, the sulfur atom, the sulfonyl group or the hydrogen atom may be substituted by a halogen atom, and the divalent organic group having 1 to 3 carbon atoms may be substituted or two or more a two-valent crosslinked structure; in the formula (10), X ₄ is a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group or a hydrogen atom which may be substituted by a halogen atom, an aryl group or an oxygen atom, sulfur A valent organic group having 1 to 3 carbon atoms which may be substituted by a halogen atom, or a hydrogen atom or a hydrogen atom may be substituted by a halogen atom, and a divalent organic group having 1 to 3 carbon atoms and hydrogen. A divalent crosslinked structure composed of two or more bonds selected from an extended aryl group in which an atom is substituted by a halogen atom). Such as the polyimine of claim 11 An azole resin composition in which R ₃ in the formula (3) is represented by the following formula (25), Such as the polyimine of claim 11 An azole resin composition in which a polyimine of (a") a structural unit represented by the formula (3) is used as a main component The azole contains 10% to 50% of the structural unit represented by the general formula (37); (In the formula (37), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure. Or a tetravalent organic group having 4 to 40 carbon atoms in which the crosslinked structure is interlinked. Polyimine, as claimed in any one of claims 11 to 14 The azole resin composition in which the in-plane/out-of-plane birefringence obtained by heat treatment is 0.01 or less. A flexible substrate characterized by containing a resin composition of a polyimine structure represented by the general formula (2); (In the formula (2), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in the intermediate structure; and R ₂ means a divalent organic group having 2 to 40 carbon atoms having at least 2 hydroxyl groups. A flexible substrate characterized by containing a polyimine represented by the general formula (3) a resin composition composed of azole; (In the formula (3), R ₁ represents a tetravalent organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure directly Or a tetravalent organic group having 4 to 40 carbon atoms bonded to each other in a crosslinked structure; R ₃ means a tetravalent organic group having 2 to 40 carbon atoms.