TW200951178A - Polyimide material, polyimide film, method for producing the polyimide material and method for producing the polyimide film - Google Patents

Abstract

Disclosed is a low-cost polyimide film having excellent heat resistance, colorless transparency, formability and optical characteristics. The film contains a polyamic acid and/or a polyimide which is obtained by reacting (A) at least one acyl compound selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic acid, 2,3,5-tricarboxycyclopentylacetic acid dianhydride and reactive derivatives of those, and (B) a specific aromatic imino-forming compound in such a manner that the molar ratio between (A) the acyl compound and (B) the aromatic imino-forming compound is within the range from 1.000:0.960 to 1.000:0.995.

Description

200951178 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polyimide-based material, a polyimide film, and a method for producing the same. [Prior Art] In general, a wholly aromatic polyimine obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine has a molecular rigidity, a molecular resonance stability, a strong chemical bond, and the like. Excellent heat resistance, mechanical properties, electrical properties, acid resistance and hydrolysis, it is widely used as a film, coating agent, molded part, and insulating material in the fields of electric, battery, automotive, and aerospace industries. On the other hand, materials used in optical members require excellent colorless transparency, easy molding (forming) properties, and optical properties in addition to excellent heat resistance and mechanical properties. In particular, the wholly aromatic polyimide film represented by Kapton (manufactured by Toray Dupont Co., Ltd.) has excellent heat resistance and the like as described above, and is suitable for use in fields such as machinery and electrical, but has high colorability or The formability is low, so there is a problem in that it is limited when used as an optical material. That is, the above film absorbs the visible light field due to the charge-transfer interaction originating from the intermolecular or intramolecular - and has a problem of coloring yellow to color to brown. Further, since the film is formed into a film shape, heat treatment at a high temperature or the like is required, and the process load is high and the moldability is low. Specifically, the polyimine which forms the above film has low solubility in an organic solvent, and it is not possible to form a film directly by using polyimide. Therefore, it is necessary to use the polyaminic acid solution of the above polyimine precursor to coat the substrate to form a film-like coating film, and then heat-treat the coating film at a high temperature of about 400 ° C. The imide of the polyamidite in the coating film is imidized to obtain a film composed of polyimine. In order to solve such problems, non-coloring property and transparency are improved, and thus various polyimides which can impart solubility to an organic solvent and improve formability can be proposed. For example, a (all aromatic) polyimine copolymer composed of a specific repetitive structure having a perfluoroalkyl group is proposed (Patent Document 1). Further, it has been proposed to be obtained from an aromatic diamine such as cyclobutane tetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. Polyimine (Non-Patent Document 1). The polyamidene-based fluorene is a semi-aromatic polyimine composed of an aromatic and an aliphatic dianhydride. Further, proposals have been made from a group selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and the like. A polyimine resin obtained by reacting at least one compound containing a mercapto group with an aromatic diamine represented by a specific formula (Patent Documents 2 and 3). Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-1999. 2007) [Problems to be Solved by the Invention] The polyimine copolymer described in Patent Document 1 is excellent in heat resistance, -6 - 200951178, and transparency or solubility in an organic solvent is improved, but The problem of low light resistance and high cost. The polyimine described in Non-Patent Document 1 is excellent in heat resistance, and is improved in transparency compared with the conventional polyimine. However, when it is used as an optical material, there is still a problem of insufficient transparency. Further, since the polyfluorene* imine has low solubility in an organic solvent, when it is formed into a film form, the polyimine acid using the precursor must be subjected to heat treatment at a high temperature (thermally imidized) and left. The problem of large process load and poor formability. Patent Publications The polyimine resins described in Documents 2 and 3 have improved transparency, but the oxidation of the diamine monomers used causes problems in the initial or temporal coloration of the film. In this regard, any of the films composed of the polyimide resin or the like described in the above documents has a problem that the non-coloring property is insufficient when used as an optical member. Further, a common problem when using polyimine as a material for an optical member is a problem of causing initial or temporal coloration of the film due to oxidation of the diamine monomer used. In this regard, the film composed of the polyimide resin or the like described in the above documents has a problem that the color is insufficient when used as an optical member. On the other hand, although the material having excellent optical properties is exemplified by polyarylate or polycarbonate, the glass transition point of these materials is 200 ° C or less, and there is a limit in heat resistance, and solder resistance cannot be expected. Charges the performance of materials used as printed circuit boards. Further, a material other than the aromatic polymer is a polyacrylic resin, an epoxy resin or a fluorene resin, but none of the above properties required for the optical member can be satisfied. The polyacrylic resin or the epoxy resin is excellent in transparency and optical properties, but has a problem of low heat resistance. In particular, in recent years, with the development of light-emitting diodes, solar cells, flat-panel displays, etc., the development of high-intensity 200951178 brightness or short-wavelength of light-emitting devices has made optical components higher in temperature and higher in energy. These resins do not meet these requirements. On the other hand, the lanthanoid resin is excellent in heat resistance, but has low adhesion to other members, and the reliability of the device is lowered due to peeling from the substrate, and the light extraction efficiency is caused by the low refractive index. Low problem. The present invention has been made in view of the above problems, and an object of the present invention is to provide heat resistance, colorless transparency (non-coloring property, transparency), moldability (easily formed when formed into a film form, and low process load), and excellent optical characteristics and low. A polyimine-based material comprising a polyimine-based material, a polyimine film composed of the poly-imine-based material, and the polyimide-based material and the film. method. [Means for Solving the Problems] The present inventors have found out that the compound (polyamine and/or diisocyanate) is formed by containing a specific mercapto compound and a specific aromatic imine group in order to solve the above problems. The polyimine film of polyaminic acid and/or polyimine can reach the above object of the invention, and thus the present invention has been completed. That is, the present invention provides the following [1] to [14]. [1] A polyimine-based material characterized by comprising a polyamic acid and/or a polyimine obtained by the following reaction: (A) is selected from the group consisting of the following formula (1): , 5-tricarboxycyclopentylacetic acid, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride represented by the following formula (2), and at least one mercapto group of the group consisting of such reactive derivatives -8 - 200951178 The compound ' and (B) form an aromatic imine group represented by the following formula (3), [Chemical Formula 1]

(1) ❹

(2)

(In the formula (3), X is -NH2 or -N = C = 0, -Krjj (3) NHSl(R25)(R26)(R27), and 丫 is selected from a direct bond, -ch2-, -0-, -S-, , LH3) 2_ one base,

Z is selected from the group consisting of a direct bond, -CH2-, -Ο-, -S-, -C(CH,, 3j2~ ' > C = 0 ' -S〇2-, and R1 to R16 are independently selected. From the hydrogen, alkyl, vinyl, aryl, halogen group, R25 to R27 are each independently a carbon number of 1 to 15 & [2] The polyimine-based material μ dan as described in the above [1], wherein the (Β) aromatic imine group-forming compound is the above formula (3) +

In the middle, the bonding groups X, Υ and Ζ are all compounds formed by para-bonding. [3] The polyethylenimine series material according to the above [1] or [2], the amount of the phthalic acid and/or the polyimine is converted into a polystyrene having an average molecular weight of 50,000 〜 The polyimide-based material according to any one of the above-mentioned items [1] to [3] wherein the poly (a) thiol compound and (or) a fluorenyl compound are B) The molar ratio of the aromatic imine group former ((A) mercapto compound: (B) aromatic imine group former) is obtained by a reaction of 1.000:0.960 to 1.000:0.995. [5] The polyimide-based material according to any one of the above-mentioned [1] to [4] wherein polylysine and/or polyimine are further obtained by Hammett's law The total σ of the substituent constants (wherein the total σ is based on the amine group, and the substituent constant of the amine-free body is not included) is an aromatic diamine compound in an amount of more than _ 0.11 and 2.0 or less as an aromatic The imine group forming compound is obtained by reacting. [6] A polyimine-based resin composition according to any one of the above [1] to [5], wherein the polyimine-based material and the organic solvent are contained. [7] A polyimine-based film according to any one of the above [1] to [5]. [8] The polyimide film according to the above [7], which is used for an optical member. [9] The polyimide film according to the above [7], which is used for a substrate for a printed circuit. [10] A method for producing a polyimine-based material, comprising the step of: (Α) selected from 2,3,5-tricarboxycyclopentyl acetic acid represented by the following formula (1), The above formula (2) represents at least one mercapto compound of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and a group of such reactive derivatives, and -10-200951178 (B) or less a step of reacting an aromatic imine group-forming compound represented by the formula (3) in an organic solvent to obtain a poly-proline, and a step of imidating at least a portion of the poly-proline ]

❹ (In the formula (3), X is -NH2 or -N = C = 0, -NHSi(R25)(R26)(R27), and 丫 is selected from a direct bond, -ch2-, -O-, -S- And one of -C(CH3)2-, Z is selected from the group consisting of a direct bond, -CH2-, -Ο-, -S-, -C(CH3)2-, >C = 0, _s〇2_- a group, rLr 16 is independently selected from the group consisting of hydrogen, alkyl, vinyl, aryl, and halogen, and R25 to R27 are each independently an alkyl group having 1 to 15 carbon atoms. [11] The method for producing a polyimide-based material according to the above [1], wherein at least a part of the polyamic acid is ruthenium imidized in the presence of an alicyclic tertiary monoamine. [12] The method for producing a polyfluorene-based material according to the above [11], wherein the alicyclic tertiary monoamine is a compound mi represented by the following formula (6) into h2c ch2 (〇) (6) (In the formula (6), R is an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom or a sulfur atom, and 1 is 〇 or 1' m and η are each independently an integer of 0 to 2). The method for producing a polyimide-based material according to the above [11] or [12], which further comprises an acid anhydride selected from the group consisting of acetic anhydride, propionic anhydride, and benzoic anhydride, and a chlorine equivalent to the acid anhydride. At least one dehydrating agent of the group consisting of: and a carbodiimide compound. [14] A method for producing a polyimide film, characterized by comprising any one of the above [10] to [13] The solution of the polyimide-based material and the organic solvent obtained by the method is coated on a substrate to form a coating film, and the organic solvent is removed by evaporation from the coating film to obtain a polyimide film. [Effect of the Invention] The polyglycine and/or polyimine (hereinafter also referred to as "polyimine, etc.") of the present invention are composed of the present invention. Since the quinone imine material is composed of a polyamic acid and/or a polyamidimide obtained by forming a compound of a specific mercapto compound and an aromatic imine group, it is excellent in heat resistance and transparency, and is colored (yellowed). In the present invention, since the polyimine obtained by the above specific -12-200951178 is excellent in solubility in an organic solvent, it can be directly dissolved in an organic solvent to form a film. In this case, a solution containing the above-mentioned polyimine or the like and an organic solvent is applied onto a substrate or the like to form a coating film, and then the solvent in the coating film is heated at a temperature of evaporation, and If heat treatment at a temperature exceeding 400 ° C is carried out by using a solution containing polyamic acid and an organic solvent, it is necessary to heat-treat at a high temperature of more than 400 ° C. Therefore, the process load can be reduced. The polyimide material of the present invention and The bismuth polyimide film can be used for the peripheral materials of the light-emitting diode, the peripheral materials of the solar cell, the peripheral material of the flat display, and the peripheral materials of the electronic circuit. Specifically, It is used as an optical member such as a heat-resistant transparent film or a conductive transparent film. The peripheral material of the flat-panel display is exemplified by a substrate for a transparent flexible display such as a liquid crystal display, a plasma display, an organic electroluminescence display, or an electronic paper. The electronic circuit peripheral material can be exemplified by a printed circuit board forming material and a printed circuit board. Specifically, it can be used for a flexible printed circuit board, a hard printed circuit board Φ, an optoelectronic printed circuit board, and COF (Crystal) The substrate for a film, the substrate for TAB (automatic bonding), and the like. [Embodiment] The polyimide-based material of the present invention is formed of (A) a specific mercapto compound and (B) a specific imine group. A compound of polyamine and/or polyimine obtained by the compound. First, the components (A) and (B) will be described. [Component (A)] The component (A) is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid represented by the following formula (1), and -13, 51, 517, 178, 3, represented by the following formula (2). 5. At least one enzyme-based compound of the group consisting of tricarboxycyclopentyl acetic acid and a reactive derivative thereof. By using these thiol-based compounds, a polyacrylonitrile or the like which is excellent in solubility in an organic solvent can be obtained, and a film having high heat resistance and little coloration can be obtained. [Chemical 4]

(1) [Chemical 5]

(2) The above reactive derivatives are exemplified by 2,3,5-trimethylcyclopentyl acetic acid monomethyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dimethyl ester, 2,3,5- Trimethyl tricarboxycyclopentyl acetic acid, tetramethyl 2,3,5-tricarboxycyclopentylacetate, monoethyl 2,3,5-tricarboxycyclopentyl acetate, 2,3,5-tricarboxyl Diethyl cyclopentyl acetate, triethyl 2,3,5-tricarboxycyclopentyl acetate, tetraethyl 2,3,5-tricarboxycyclopentylacetate, or the above alkyl ester is replaced by unsubstituted a phenyl ester or an esterified product of various para-substituted phenyl esters. Other reactive derivatives are exemplified by 2,3,5-tricarboxycyclopentyl acetic acid tetrachloro, 2,3,5-tricarboxycyclopentyl acetic acid dichlorodiester (the ester alcohol or phenol component is the same as above) Wait for chlorine. As for the (Α) component, it is preferred to use 2,3,5-tricarboxycyclopentyl acetic acid dianhydride. When 2,3,5-tricarboxycyclopentyl acetic acid dianhydride which is an acid anhydride is used as the (Α) component, the polyamine acid can be synthesized at a low temperature as compared with the case where no acid anhydride is used. Further, these mercapto compounds may be used singly or in combination of two or more. -14-200951178 [Component (B)] The component (B) contains an aromatic imine group-forming compound represented by the following formula (3) as the component (B-1). [Chemical 6] R1 R2 R3 R4 R5 R6 R7 R8

(In the formula (3), X is -NH2 or -N = C = 0, -NHSi(R25)(R26)(R27) φ , Υ is selected from a direct bond (single bond), -ch2-, -〇- , -s-, -c(ch3)2- one base 'z is selected from a direct bond, -ch2-, -〇-, -s-, -c(ch3)2-, >C = 0, - One of S02-, R1 to R16 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, a vinyl group, an aryl group, and a halogen group, and each of R25 to R27 is independently an alkyl group having 1 to 15 carbon atoms. By forming a compound using an aromatic imine having four benzene rings represented by the above specific formula, a film having little coloration can be obtained. Here, the term "imine forming compound" means a compound which is reacted with the component (A) to form an imine group. φ The above aromatic imine group-forming compound is exemplified by bis[4-(3-aminophenoxy)phenyl]millate, bis[4-(4-aminophenoxy)phenyl] maple, bis[4] -(3-Aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]one, 4,4'-bis(3-aminophenoxy) Benzene, 4,4,-bis(4-aminophenoxy)biphenyl, bis[4_(3-aminophenoxy)phenyl]propane, bis[4_(4.aminophenoxy)benzene Propane, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 2,2-bis[4-(3 -amino-α,α-dimethylbenzyl)phenyl]propane, 2,2-bis[4-(4-amino-α,α-dimethylbenzyl)phenyl]propane, 2, 2-bis[4-(3-Isocyanate dimethyl-15- 200951178 benzyl)phenyl]propane, 2,2-bis[4-(4-isocyanate-α,α-dimethylbenzyl) Phenyl]propane, 2,2-bis[4-(3·trimethyldecylalkylamino-α,α-dimethylbenzyl)phenyl]propane, 2,2·bis[4- (4- Trimethyldecylamino-α,α-dimethylbenzyl)phenyl]propane, and the like. Among these, it is preferred to use bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 4,4'-bis ( 3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]propane, 2,2 - bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-amino-α,α-dimethylbenzyl)phenyl]propane, 2, 2-bis[4-(4-amino-α,α-dimethylbenzyl)phenyl]propane. Further, the (Β-1) component is preferably a compound in which the bond group represented by X, Υ and Ζ in the above formula (3) is an aromatic imine group formed by para-bonding, that is, a formula The aromatic imine group forming compound represented by (4). By using these compounds, a film having higher heat resistance and less coloration can be obtained. Among the above aromatic imine group-forming compounds, bis[4-(4-aminophenoxy)phenyl]millate, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amino-α,α-dimethylbenzyl)phenyl]propane . [Chemical 7] R1 R2 R3 R4 R5 R6 R7 R8

(In the formula (4), R1 to R16, X, Y and an anthracene are the same as those in the above formula (3). Further, the imine forming compounds may be used alone or in combination of two or more. The polyimine-based material of the present invention may be obtained by a Hammert's rule, in addition to the compound ((B-1) component) represented by the above formula (3) as an aromatic imine group-forming compound. The total σ of the substituent constants (wherein the total σ is based on the amine group, and the substituent constant of the amine-free body is not included) is an aromatic aryl diamine compound in the range of -0.11 or less (( Β-2) Ingredients). The aromatic diamine compound preferably has an sigma of more than -0.11, and the aromatic diamine compound in the range of 1.6 or less is more preferably an aromatic two having a σ exceeding -〇_11 and being in the range of 〇.8 or less. Amine compound. In this case, the total σ of the substituent constants obtained by the Haman rule (wherein the total σ is based on the amine group and the substituent constant of the amine-free body is not included) is -0.70 or more and -0.11 or less. The aromatic diamine compound within the range is as the (Β-1) component. The difference between the total σ of the ( Β-1) component and the (Β·2) component is preferably 0.1 or more, more preferably 0.2 or more. A suitable example of the component (Β-2) is an aromatic diamine compound represented by the following formula (5). - [Chem. 8]

(In the formula (5), 'X is _Νη2, γ is selected from a direct bond, > C = 0, -S02-, -C(CF3)2-, and each of Rl7 to R24 is independently selected from a hydrogen atom. , alkyl, fluorinated alkyl, alkoxy, vinyl, aryl, halogen based). Preferred examples of the component of -17-200951178 (B-2) are, for example, selected from the group consisting of 2,2'-bis(trifluoromethyl)benzidine, 2,2'-dimethoxybenzidine, 2,2'- Dimethylbenzidine, 3,3'-diaminodiphenyl maple, 4,4'-diaminodiphenyl milling, 3,3'-diaminobenzophenone, 4,4,- At least one aromatic diamine compound of the group consisting of diaminobenzophenone and 1,1,3,3,3-hexafluoroisopropylidenebenilidine. The most preferred examples are, for example, 2,2'-bis(trifluoromethyl)benzidine, 2,2,-dimethylbenzidine, 3,3'-diaminodiphenyl maple, 4,4' - Diaminodiphenylphosphonium. The component (B-2) may be used singly or in combination of two or more. Next, a method for producing the polyimine of the present invention will be described. The method for producing a polyimine-based material of the present invention comprises the steps of: (a) reacting the above (A) mercapto compound with the above (B) aromatic imine forming compound in an organic solvent to obtain a polylysine Steps ' and (b) the step of imidizing at least a portion of the polyamic acid. [Step (a)] The step (a) is a step of reacting the above component (A) with the above component (B) in an organic solvent to obtain a poly-proline. The specific method for reacting the component (A) with the component (B) is to add at least one (A) mercapto compound to the resulting solution after dissolving at least one (B) aromatic imine group-forming compound in an organic solvent. And stirring at a temperature of 0 to 100 ° C for 1 to 60 hours. The above organic solvent is exemplified by, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, butyrolactone, N. An aprotic polar solvent such as N'-dimethylimidazolidinone or tetramethylurea; a phenolic solvent such as cresol, xylenol or halogenated phenol. Among them, N-methyl-2-azolopropanone and N,N-dimethylacetamide -18-200951178 are preferred. These solvents may be used alone or in combination of two or more. Further, the total amount of the aromatic imine group-forming compound and the mercapto compound in the reaction liquid is preferably from 5 to 30% by mass based on the total amount of the reaction liquid. The ratio of the (A) mercapto compound to the (B) aromatic imine group-forming compound is preferably an imine group or an isocyanate group per equivalent of the component (B), and the acid anhydride of the component (A) is in a ratio of 0.8 to 1.2 equivalents. More preferably, it is a ratio of 1.0 to 1.1 equivalents. More specifically, it can be reacted by making the molar ratio of the (A) mercapto compound and the (B) aromatic imine-based chelate compound 1.000:0.960 to 1.000:0.995, preferably 1.000- 0.970~1.000: 0.990 way of reaction. When the molar ratio of the (A) mercapto compound to the (B) aromatic imine group-forming compound is within the above range, the resulting polymer is particularly excellent in film formability, mechanical properties, and transparency. When the (B-1) component and the (B-2) component are used as the (B) aromatic imine group-forming compound, the (B-1) component and the (B-2) component are preferably blended into (B). -1) / ( B-2) >1. (B-1) : When the molar ratio of (B-2) is 1, the value is preferably 0.60:0·40 to 0.999:0.001 〇, more preferably 0·62:0·38~0· 99:0.01, preferably 0.65:0.35~0.96:0.〇4. When the amount of the (Β-1) component and the (Β-2) component are in the above range, the film formation property, the mechanical properties, and the transparency of the film are particularly excellent. Further, polylysine refers to an acid having a structure containing -CO-NH- and -CO-OH which is produced by reacting an acid anhydride group with an amine group, or a derivative thereof (specifically, for example, having CO-NH-containing) And -CO-OR (where R is an alkyl group, etc.). Polylysine is dehydrated from -CO-NH- and -CO-OH by heating to form a polyimine having a cyclic chemical structure (-CO-N-CO-). -19- 200951178

Step-I step by step so that at least a part of the proline acid obtained by the system b / IV stepping TJ \ly is subjected to dehydration ring closure and imidization to obtain a polyimine and an organic solvent. The step of the solution. Specifically, the method of imidization is a method using a dehydrating agent (chemical imidization), or at 160 ° C to 350 ° C (in the solution of about 160 to 220 ° C, the casting film is generally 300 ° ° C or higher) The method of heat treatment (thermal imidization). The dehydrating agent in the chemical imidization is exemplified by an acid anhydride such as acetic anhydride, propionic anhydride or benzoic anhydride, or a corresponding carbodiimide compound such as ruthenium chloride or dicyclohexylcarbodiimide. The amount of the dehydrating agent to be added may be appropriately changed depending on the target imidization ratio, but it is usually in the range of 1 to 10 moles per 1 mole of the mercapto compound, and is preferably in the range of 2 to 10 moles. Further, the chemical imidization can be carried out at a temperature of from 10 ° C to 120 ° C, and preferably at a temperature of from 25 ° C to 90 ° C. When the temperature exceeds 120 ° C, the coloring cannot be suppressed. When the temperature is lower than 10 ° C, the reaction rate is low, and there is a problem that the length of the amidation is long. In the case of thermal amide amination, it is preferred to remove water generated by the dehydration reaction from the outside of the system. In this case, it is preferred to use a method such as azeotropic removal of water, hydrazine, xylene or the like to azeotropically remove the hydrazine imidization at a lower temperature, and it is preferred to carry out the hydrazine imidization. Further, an alkaline catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N,N-dimethylaminopyridine, imidazole or alicyclic tertiary monoamine may be used as needed in the imidization. Among these, alicyclic tertiary monoamines are more suitable. The use of an alicyclic tertiary monoamine compound in the imidization of ruthenium promotes the quinone imine-20-200951178 reaction, which is considered to be an isolated electron pair on the nitrogen atom of the alicyclic tertiary monoamine. With high nucleophilicity. As the above alicyclic tertiary monoamine, a compound represented by the following formula (6) is preferably used. [Chemical 6]

(6) (In the formula (6), R is an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom or a sulfur atom, 1 is ruthenium or 1, and m and η are each independently an integer of 0 to 20). In the formula (6), R is preferably a methyl group or an ethyl group, and is preferably a methyl group. Further, m and η are preferably 0 or 1. Further, m + n is preferably from 1 to 3). Preferred examples of the compound represented by the above formula (6) are N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine and the like. By using an alicyclic tertiary monoamine as the ruthenium amide catalyst, even if an aliphatic compound is used as the component (A), ruthenium imidization can be carried out with high reactivity (醯 imidization reaction rate), and The time required for the imidization or shortening of the imidization at lower temperatures can be achieved. Thus, as a result, the coloration of the obtained polyimine can be reduced. Further, when a compound having a six-membered cyclic acid anhydride skeleton or at least two carbons constituting a bridged ring structure is used as a compound forming an acid anhydride skeleton, particularly a compound which is easily subjected to amide amination as a component (A), even at a low temperature It can also achieve the high imidization rate that could not be achieved in the past. The above base catalyst is preferably used in the range of -21 - 200951178 0.01 to 10 moles per mole of the 1 molar base compound, and is preferably used in the range of 〇·1 to 5 moles. Further, the ruthenium is imidized to at least a part of the polyamic acid, preferably 75 mol% or more, more preferably 85 mol% or more, and most preferably 90 mol% or more. The obtained solution containing polylysine and/or polyimine and an organic solvent may be used as it is, or may be obtained by separately separating the solid component such as polyimine and then dissolving it in an organic solvent. Further, the redissolved organic solvent is exemplified by the same as the above organic solvent. The method of separating the polyimine or the like is to pour a solution containing a polyimine or the like and an organic solvent into methanol or the like. The polyimine is precipitated in a weak solvent, and the polyimine or the like is precipitated and filtered. • A method of separating a polyimine or the like into a solid component, such as drying. By such operations, it is also possible to remove the dehydration catalyst (醯i-imidation catalyst) used in the oxime imidization process. The obtained polyaminic acid and/or polyimine is converted to polystyrene in a weight average molecular weight of 50,000 to 500,000, preferably 100, 〇〇〇 to 400, 〇〇〇. In the present invention, the total amount of polyaminic acid and polyamidene is 100 mol%, and the ratio of polyimine is 75 mol% or more, preferably 85 mol% or more, preferably 90 mol%. %the above. When the ratio of the polyimide to less than 75 mol%, the water absorption rate of the film becomes high and the durability is lowered. Hereinafter, the film production method of the present invention will be described. The method for producing a film of the present invention comprises applying a solution containing a polyamic acid and/or a polyamidimide obtained by reacting the above (indenyl)-based compound with the above-mentioned (indenyl) aromatic imine-forming compound and an organic solvent. The step (c) of forming a coating film on the substrate, and the step (d) of removing the organic solvent from the coating film to obtain a film. [Step (c)] The step (c) is a step of applying a solution containing the above polyimine -22-200951178 or the like and an organic solvent to a substrate to form a coating film. The above substrate is exemplified by a polyethylene terephthalate (PET) film, a SUS plate, a copper foil or the like. A method of applying a solution containing a polyimine or the like and an organic solvent to a substrate can be carried out by a roll coating method, a gravure coating method, a spin coating method, a method using a "squeegee", or the like. The thickness of the coating film is not particularly limited and may be, for example, 1 to 2 50 μm 0 [Step (d)] The step (d) is a step of removing the organic solvent from the coating film by evaporation to obtain a film. Specifically, the organic solvent in the coating film is removed by evaporation by heating the coating film. The heating conditions are not particularly limited as long as the organic solvent can be evaporated, and may be, for example, 1 to 5 hours at 60 to 25 °C. In addition, heating can also be carried out in two stages. For example, after heating at 100 ° C for 30 minutes, heating at 150 ° C for 1 hour or the like. Further, it may be dried under a nitrogen atmosphere or under reduced pressure as needed. In this step, if the organic solvent can be removed, it is not necessary to carry out the ruthenium imidization, so that the film can be obtained at a lower temperature than the prior art. Therefore, even if the other member forming the optical member has low heat resistance, a solution containing the above-mentioned polyimine or the like and an organic solvent may be directly applied to the member, and the organic solvent may be removed by evaporation to form a film. The resulting film is peeled off from the support substrate, or - it can be used without being peeled off. The film of the present invention is mainly composed of a polyimine obtained by reacting the above component (A) with component (B). In particular, the polyamic acid obtained by reacting the component (A) with the component (B) is, for example, at least one of repeating units represented by the following formulas (7) to (10). -23- (7) 200951178 [Chem. 16]

R1 R2 R3 R4 R5 R6 R7 R8

(8) R9 R10 R11 R12 R13 R14 R15 R16

R9 R10 R11 R12 R13 R14 R15 R16 R1 R2 R3 R4 R5 R6 R7 R8

(9)

R1. R2 R3 R4 R5 R6 R7 R8 々微2 发 Y' R9 R10 R^R14 R15 R16

(10) In the formulae (7) to (10), the RLR16, X, Y and Z systems are the same as those in the above formula (3), and R17 to R24 each independently represent a hydrogen atom or an alkyl group). Further, the polyimine which is obtained by reacting the component (A) with the component (B) is, for example, a repeating unit represented by the following formula (11) or (12). [Chem. 17]

R1 R2 R3 R4 R5 R6 R7 R8 *ζΛν-

(11) ', 〇 r9 > R13 R13 RU R15 R16 (In the formula (1 1 ), the RLr16, X, Y and Z systems are the same as in the above formula (3)). (12) 200951178 [化18] n 〇R1 R2 R3 R4 R5 R6 R8 " '0 r9 V0 R^R14 R15 R16 (in equation (12) 'R1~Ri6, X, γ and z are the above formula (3 ) the same). ❹ ❹ The film thickness of the present invention is from 1 to 2500 μm, preferably from 5 to 200 μm. Further, when the film of the present invention is used as a substrate, it is preferably 10 to 150 μm. When the film thickness of the present invention is 20 μί, it is preferably 80% or more, more preferably 85% or more, and still more preferably has a total light transmittance of 89% or more. When the film thickness of the present invention is 20 μm, the yttrium (yellow index) is preferably 2.5 or less, more preferably 1.4 or less. The film of the present invention preferably has a refractive index of from 1.58 to 1.66, more preferably from 1.60 to 1.64, with respect to light having a wavelength of 63 3 nm. The glass transition temperature (Tg) of the film of the present invention is preferably 250 ° C or higher, more preferably 280 ° C or higher. By having these glass transition temperatures, excellent heat resistance can be obtained. The tensile strength of the film of the present invention is preferably from 80 MPa to 300 MPa, more preferably from 100 MPa to 300 MPa. The tensile strength of the film of the present invention is preferably from 10% to 200%, more preferably from 20% to 150%. The tensile elastic modulus of the film of the present invention is preferably 2.2 GPa or more, more preferably 2.5 GPa or more. The film of the present invention can be used in the peripheral material of the light-emitting diode, the peripheral material of the solar cell, the peripheral material of the flat display, and the peripheral material of the electronic circuit. Specifically, an optical member such as a heat-resistant transparent film or a conductive transparent film can be used. In addition, the peripheral materials of the flat panel display are as follows: the electric side, the peripheral circuit, the electric indicator B, and the external 8 H.D adjustment. A plate and a base device are used to display the sensibility of the slurry. The liquid can be used as a substrate for a printed wiring board. For example, a substrate for a flexible printed circuit board or a hard type can be used as a substrate for a printed wiring board. A substrate for a printed circuit, a substrate for an optoelectronic printed circuit, a substrate for COF (Crystalline), and a substrate for TAB (with automatic bonding). When used as a printed circuit board, for example, a copper layer for wiring can be provided. The method for producing a substrate for a printed circuit in which a copper layer is provided on a film can be exemplified by a casting method, a lamination method, a wire method, and the like. The casting method can be achieved, for example, by changing the substrate used in the above step (b) into a copper foil. Specifically, a solution containing a polyimine or the like and an organic solvent is applied onto a copper foil to form a coating film, and then an organic solvent is removed from the coating film to produce a substrate for a printed circuit having a copper layer provided on the film. When the method of providing a copper layer on the film of the present invention is a lamination process, for example, a copper foil is heat-pressed on the obtained film of the present invention by lamination, and a substrate for a printed circuit provided with a copper layer can be produced. In the case of lamination, for example, a copper foil may be heat-pressed on the film of the present invention to produce a substrate for a printed circuit provided with a copper layer. In the case of the metal wire method, for example, after the surface of the film of the present invention is subjected to surface modification for exhibiting affinity with a metal, a Ni-based metal layer bonded to a polyamide bond and a wet film are formed by a vapor deposition method or a sputtering method. The sheet layer required for electroplating. Therefore, a substrate for a printed circuit provided with a copper layer can be produced by providing a copper layer having a predetermined film thickness by a wet plating method. Further, the polyimide-based solution containing the polyimine or the like and the organic solvent obtained in the steps (a) and (b) can be used as a polyimide composition for a peripheral material of a light-emitting diode, solar energy. The surrounding material of the battery, the surrounding material of the flat display, and the surrounding materials of the electronic circuit. Specifically, it can be used for a sealant, a lens material, a material for forming a printed circuit board, and the like. For example, when a material for forming a printed circuit board is used, a substrate for a printed circuit can be produced by casting the method of 200951178. Specifically, the polyimine-based resin composition can be applied to a copper flute, and then a substrate for a printed circuit provided with a copper layer can be produced by heat treatment. Further, an organic solvent having a boiling point of 150 or less can be used as a co-solvent in the above polyimine-based resin composition. The organic solvent is exemplified by, for example, methanol, ethanol, isopropanol, tetrahydrofuran, 1,3-dioxane 'i,4-dioxane, etc. 〇 〇 These solvents may be used alone or in combination of two or more. Further, the concentration of the polyamic acid and/or the polyamidene in the polyimine-based resin composition is preferably from 5 to 30% by mass based on the total amount of the reaction liquid. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. [Example 1] First, 9.88 g (22.8 〇 mmol) of bis[4-(3-aminophenoxy) was added to a 300 ml 4-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Base) phenyl] hydrazine. Then, after replacing the inside of the flask with nitrogen, N-methyl-2-pyrroledrone (hereinafter referred to as NMP) (60 ml) was added and stirred until homogeneous. 5·12 g (-22.8 mmol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride was added to the obtained solution at room temperature, and stirring was continued at this temperature for 12 hours to carry out the reaction. A solution of polylysine. After diluting with a solution of the obtained poly-proline acid, NMP (75 ml), pyridine (7.4 ml) of acetic anhydride (6.5 ml) was added, and at 110. (: stirring for 6 hours to carry out hydrazine imidization 'to obtain a polymer. Then, after cooling to room temperature, pour into a large amount of methanol', the polymer was isolated by filtration from -27 to 200951178. The obtained polymer was at 60 ° C. The mixture was vacuum dried overnight to give a white powder (yield: 13.4 g, yield: 94.5%). Then, the obtained polymer was redissolved in N,N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. The resin solution was coated on a substrate composed of polyethylene terephthalate (PET) using a squeegee (ΙΟΟμιη pitch), and dried at 100 ° C for 30 minutes and then dried at 150 ° C. After the film became a film, it was peeled off from the pet substrate. Then, the film was dried at 150 ° C for 3 hours under reduced pressure to obtain a film having a film thickness of 20 μm. The structure analysis, weight average molecular weight and enthalpy of the polymer were carried out by the following method. The imidization ratio was measured. As a result, the characteristic absorption of the carbonyl group was 1739 cm·1 and 1698 cm·1 (refer to Fig. 1), and the weight average molecular weight was 174,000. The yield of the obtained polymer was imidized (all the proline acids) Dehydration closed loop lysine ratio) 93%. Further, the solubility of the polymer in the organic solvent, the total light transmittance of the film, the YI 値, the refractive index, the glass transition point, and the YI 后 after the heat resistance test were evaluated by the following methods. The results are shown in Table 1. 1) The structural analysis was carried out by IR (KBr method), and (2) the weight average molecular weight weight average molecular weight was measured using a HCL-8 020 GPC apparatus manufactured by TOSOH. The solvent was N-methyl-2-added with lithium bromide and phosphoric acid. Pyrrolidinone (NMP), the temperature was measured at 40 ° C, and the molecular weight converted to polystyrene was determined. (3) The closed-loop ratio of the closed-loop ratio (醯i-imidization ratio) of polyimine was determined by 1H-NMR. The d-DMSO was used, and the closed-loop ratio was calculated from the ratio of the peak integral 値 (9.8~l〇.3ppm) of the guanidine imine moiety to the peak integral 値 (6.5 to 7.5 ppm) of the aromatic diamine. 4) Solubility to organic solvent The polymer was dissolved in hydrazine, Ν·dimethyl -28-200951178 acetamidine, adjusted to 20% by mass solution, and evaluated for solubility at room temperature. For "〇", the case of swelling or insoluble polymer is recorded as "X". (5) Full light The over-rate YI is determined by the JIS K7105 transparency test method. Specifically, the total light transmittance, YI 値 (yellow index) of the film is measured using the SC-3H type haze meter manufactured by SUGA Test Machine Co., Ltd. (6) Refractive index The refractive index of the obtained film at a wavelength of 6 33 nm was measured using a 20 10 type 稜鏡 illuminometer manufactured by Metricon Co., Ltd. Further, the measurement system was used at 23 ° C and 50% RH. The wafer substrate is processed. (7) The glass transition temperature (Tg) was measured at a temperature increase rate of 20 ° C / min using a Model 8230 DSC measuring apparatus manufactured by RJgaku Co., Ltd. (8) YI 后 after the heat resistance test The obtained film (side length 50 cm) was allowed to stand in a hot air dryer maintained at 150 ° C for 24 hours to carry out a heat resistance accelerated test. The YI 薄膜 of the film after the test was measured in the same manner as in the above (5). (9) Tensile properties The mechanical strength of the film was measured, and the tensile strength at room temperature, tensile strength and tensile modulus were measured in accordance with JIS K7 1 27 . 〇 [Example 2] Except that bis[4-(4-aminophenoxy)phenyl]roll was used instead of bis[4-(3-aminophenoxy)phenyl]fluorene, the same as in Example 1 In the same manner, a white powder polymer (yield 13.8 g, yield 97.3%) was obtained, and a film was obtained. The obtained polymer was subjected to structural analysis, weight average molecular weight, and oxime imidization ratio in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1739 cm·1 and 1696 cm·1 (refer to Fig. 2), and the weight average molecular weight was 3 3 9,000. The obtained imidization ratio of the polymer was 94%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. The results are shown in Table 1. -29- 200951178 [Example 3] except that 9.33 g (25.3 mmol) of bis(4-aminophenoxy)biphenyl was used instead of bis[4-(3-aminophenoxy)phenyl]indole, Further, the blending amounts of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, pyridine, and acetic anhydride were changed to 5.67 g (25.3 mmol), 8.2 ml, and 7.2 ml, respectively, and the remainder was the same as in Example 1. A white powder polymer (yield 13.2 g, yield 94.0%) was obtained, and a film was obtained. The obtained polymer was subjected to structural analysis, weight average molecular weight, and oxime imidization ratio in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1 73 8 cm·1 and 1 695 (refer to Fig. 3), and the weight average molecular weight was 292,000. The yield of the obtained polymer was 93%. Further, as in the examples The physical properties of the obtained polymer and film were evaluated in general. The results are shown in Table 1. [Example 4] Except that 9.70 g (23.6 mmol) of 2,2-bis[4-(4-aminophenoxy) group was used. Phenyl]propane replaces bis[4-(3-aminophenoxy)phenyl], and the amount of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, pyridine and acetic anhydride is changed to 5.30 g (23.6 mmol), 7.5 ml, 6.7 ml, and the same as in Example 1, a white powder polymer (yield: 13.5 g, yield: 95.3%) was obtained, and a film was obtained. In the method, the obtained polymer was subjected to structural analysis, weight average molecular weight, and ruthenium imidation rate. As a result, the characteristic absorption of the carbonyl group was 173 5 cm·1 and 1 682 (refer to FIG. 4), and the weight average molecular weight was determined. It was 320,000. The obtained imidization ratio of the obtained polymer was 93%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. Listed in Table 1 °

[Example 5] After the poly-proline was prepared as in Example 4, it was diluted with NMP-30-200951178 (75 ml), and xylene (12 ml) and isoporphyrin (1 drop; 7 ml) were added. The mixture was stirred at 180 ° C for 6 hours to carry out hydrazine imidation to obtain a polymer. Subsequently, the polymer was isolated as in Example 1 to obtain a white powder (yield: 13.2 g, yield: 93.3%), and the obtained polymer was used to obtain a film as in Example 1. The obtained polymer was subjected to measurement of a weight average molecular weight and a ruthenium imidation ratio in the same manner as in Example 1. As a result, the weight average molecular weight was 1 90,000, and the oxime imidization ratio was 89%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1 of φ. The results are shown in Table 1. [Example 6] First, bis[4-(4-aminophenoxy)phenyl]anthracene (9.75 g, 22.54) was added to a 300 ml 4-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Millions of ears). Next, after replacing the inside of the flask with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (60 ml) was added and stirred until homogeneous. 2,3,5-Tricarboxycyclopentyl acetic acid bis-anhydride (5.12 g, 22.84 mmol, anhydride: amine = 1:0.987) was added to the resulting solution at room temperature, and stirring was continued at this temperature. The reaction was carried out for 12 hours to obtain a solution containing polyamic acid. After diluting with a solution of the obtained poly-proline acid, the residue was diluted with NMP (75 ml), pyridine (7.4 ml), acetic anhydride (6.5 ml) was added, and stirred at 1 l ° C for 6 hours. Amination, obtaining a polymer. Subsequently, after cooling to room temperature, it was poured into a large amount of methanol, and the polymer was separated by filtration. The obtained polymer was vacuum dried overnight at 60 ° C to give a white powder (13.4 g, 95.0%). Next, the obtained polymer was redissolved in hydrazine, hydrazine-dimethylacetamide (DMAc) to obtain a resin solution of 20 mass - 31 - 200951178% by weight. The resin solution was applied onto a substrate composed of polyethylene terephthalate (PET) using a squeegee (ΙΟΟμιη pitch), and dried at 100 ° C for 30 minutes and then at 150 ° C for 60 minutes. After being a film, it is peeled off from the PET substrate. Subsequently, the film was dried at 150 ° C under reduced pressure for 3 hours to obtain a film having a film thickness of 20 μm. In the same manner as in Example 1, the polymer was subjected to structural analysis, weight average molecular weight, and oxime imidization ratio. Determination. As a result, the characteristic absorption of the carbonyl group was 1 740 CHT1 and 1 695 cm·1 (indenylene group), 1 892 CUT1 (end group) (refer to Fig. 5), and the weight average molecular weight was 149,000. The ruthenium imidation ratio of the obtained polymer (the ratio of lysine which was subjected to dehydration ring closure in all lysines) was 94%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. The results are shown in Table 1. [Example 7] Except that the amount of bis[4-(4-aminophenoxypurine)phenyl] was changed to 9.51 g (21.99 mmol; anhydride: amine = 1:0.963), In the same manner, a white powdery polymer was obtained (yield: 13.1 g, yield 94.6%), and a film was obtained. The obtained polymer was subjected to measurement of structure analysis, weight average molecular weight, and ruthenium imidation ratio in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1 740 CHT1 and 1 695 CHT1 (indenylene group), 189201^1 (end group) (refer to Fig. 6), the number of repeating units was 55, and the weight average molecular weight was 66,000. The obtained imidization ratio of the polymer was 93%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. The results are shown in Table 1. [Example 8] In addition to using 9.58 g (23-34 mmol, anhydride:amine = 1: 〇.987) - 2,2-bis[4-(4-aminophenoxy)phenyl]propane instead of double [ A polymer of a white powder (yield: 13.3 g, yield: 95.%) was obtained in the same manner as in Example 1 except for 4-(4-aminophenoxy)phenyl]indole, and a film was obtained. φ The structure of the obtained polymer was measured by the same method as in Example 1 to measure the weight average molecular weight and the ruthenium iodide ratio. As a result, the characteristic absorption of the carbonyl group was 1737 cm-1 and 1680 cm·1 (indenylene group), 1892 cm·1 (end group) (refer to Fig. 7), the number of repeating units was 160, and the weight average molecular weight was 183,000. The obtained imidization ratio of the polymer was 95%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. The results are shown in Table 1. 〇 [Example 9] First, 2,2-bis[4-(4-aminophenoxy). phenyl was added to a 300 ml 4-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Propane (9.24 g, 22-5 mmol; (B-1) component), 2,2'-bis(trifluoromethyl)benzidine (0.38 g, 1.2 mmol; (B-2) component). Next, after replacing the inside of the flask with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (135 g) was added and stirred until homogeneous. 2,3,5-Tricarboxycyclopentyl acetic acid dianhydride (5.38 g, 24.0 mmol; component (A)) was added to the resulting solution at room temperature, and stirring was continued at this temperature -33-200951178 The reaction was carried out for 24 hours to obtain a solution containing polyamic acid. N-methylpyrrolidine (2.7 ml) and acetic anhydride (6.7 ml) were added to the solution containing the obtained polyamic acid, and the mixture was stirred at 75 ° C for 3 hours to carry out hydrazine imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was separated by filtration. The obtained polymer was vacuum dried overnight at 60 ° C to become a white powder (13.1 g, 93%). Next, the obtained polymer was redissolved in N,N-dimethylacetamide (DM Ac ) to obtain a resin solution of 20% by mass. The resin solution was applied onto a substrate composed of polyethylene terephthalate (PET) using a squeegee (1 〇〇μηι pitch), dried at 100 ° C for 30 minutes, and dried at 150 ° C. After being used as a film for 60 minutes, it was peeled off from the PET substrate. Subsequently, the film was dried at 150 ° C under reduced pressure for 3 hours to obtain a film having a film thickness of 20 μm. The obtained polymer was subjected to measurement of a weight average molecular weight and a ruthenium iodide ratio in the same manner as in Example 1. The obtained polymer had a weight average molecular weight of 104,000, and the ruthenium iodide ratio (the ratio of lysine which was subjected to dehydration ring closure in all lysines) was 95%. The obtained film was subjected to structural analysis by IR (ATR method: film). As a result, the characteristic absorption of the carbonyl group was 1 73 5 cm·1 and 1 684 cm·1 (refer to Fig. 8). Further, as in Example 1, the solubility of the polymer in the organic solvent, the total light transmittance of the film, the YI 値, and the glass transition point were evaluated. The heat resistance test was carried out by subjecting the obtained film (side length 5 cm) to a hot air dryer maintained at 175 ° C for 12 hours, and performing a heat resistance accelerated test, and measuring the heat resistance test in the same manner as in the above (5). YI 値 of the film after. The results are shown in Table 1. -34- 200951178 [Example 〇] except that 9.36 g (22·8 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was used as the component (B_1)' 〇· 26 g (1.2 mmol) of 2,2,-dimethylbenzidine as (B.2) component, 5.38 g-(24.0 mmol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as The polymer (yield 13.2 g, yield 94%) and a film of a white powder were obtained in the same manner as in Example 9 except for (A). The obtained polymer was subjected to structural analysis, weight average molecular weight, and oxime amination rate in the same manner as in Example 9. As a result, the characteristic absorption of the carbonyl group was 173 km·1 and 1683 cm_1 (refer to Fig. 9), and the weight average molecular weight was 183,000 Å, and the amination ratio was 97%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 9. The results are shown in Table 1. [Example 11] except that 9.32 g (22.7 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was used as the component (B-1), 0.25 g (1.2 mmol) Ear) 2,2'-dimethylbenzidine as component (B-2), 5.43 g (24.2 mmol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as (eight) The same procedure as in Example 9 was carried out to obtain a white powdery polymer (yield: 13.2 g, yield: 94%) and a film. The obtained polymer was subjected to structural analysis, weight average molecular weight, and measurement of amination rate in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 173 5 cm·1 and 1 683 (see Fig. 1A), the weight average molecular weight was 13 8,000, and the oxime imidization ratio was 93%. Further, evaluation was carried out as in Example 9. The physical properties of the obtained polymer and film were as follows. The results are shown in Table 1. [Example 12] except that 9.19 g (22.4 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl] was used. Propane as (Ed) component, 〇·25g (-35- 200951178 1.2 mM) 2,2'-dimethylbenzidine as component (B-2), 5.56 g (24.8 mmol) 2,3 5-methoxytricyclocyclopentyl acetic acid dianhydride was used as the (human) component, and the same as in Example 9 was used to obtain a white powder polymer (yield 12.8 g, yield 91%) and a film. The same as in Example 1. In the method, the obtained polymer was subjected to structural analysis, weight average molecular weight, and oxime imidization ratio. As a result, the characteristic absorption of the carbonyl group was 173 5 cm·1 and 1684 cm·1 (refer to FIG. 11), and the weight average molecular weight was 52,000. The oxime imidization ratio was 95%. Further, various physical properties of the obtained polymer and film were evaluated as in Example 9. The results are shown in Table 1. [Example 13] 2,2-bis[4-(4-aminophenoxy)phenyl]propane (6.47 g, 15.8 mmol) was added to a 300 ml 4-neck flask of a meter, a stirrer, a nitrogen inlet tube and a cooling tube. Next, after replacing the inside of the flask with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (90.0 g) was added and stirred until homogeneous. 2,3,5-tricarboxycyclopentyl group was allowed at room temperature. Acetic acid dianhydride (3.53 g, 15.8 mmol) was added to the obtained solution, and stirring was continued at this temperature for 24 hours to obtain a polyaminic acid solution. Next, N- was added to the obtained polyaminic acid solution. Methyl pyrrolidine (1-9 ml) and acetic anhydride (4.5 ml) were stirred for 5 hours at 75 ° C to carry out hydrazine imidization. After cooling to room temperature, pour into a large amount of methanol and separate by filtration. The polymer was vacuum dried overnight at 60 ° C to obtain a white powder (yield 9.20 g, yield: 97.5 mass%). Next, the obtained polymer was redissolved in N,N-dimethylacetamide ( In DMAc), a resin solution of 20% by mass was obtained. Next, the resin solution was applied using a squeegee 200951178 (ΙΟΟμηι pitch). The film was coated on a substrate made of polyethylene terephthalate (PET), dried at 1 ° C for 30 minutes, and then dried at 150 ° C for 60 minutes, and then peeled off from the PET substrate. The film was dried at 180 ° C for 8 hours under reduced pressure to obtain a film having a film thickness of 20 μm. 'The ring closure ratio (the imidization ratio) of the above polymer and the polyglycine and the above polymer were evaluated in the same manner as in Example 1. (weight average molecular weight of the polymer after hydrazide). The obtained imidization ratio of the polymer was φ 98%. Further, the weight average molecular weight of the polyamic acid was 4.0 Χ 105, and the weight average molecular weight of the obtained polymer (the polymer after hydrazide) was 5.2 χ 105. The total light transmittance and enthalpy (initial) of the film were evaluated in the same manner as in Example 1. Further, ΥΙ値 (after UV test) and water absorption were evaluated by the following methods. After the heat resistance test, the obtained film (side length 5 cm) was placed in a hot air dryer maintained at 150 ° C for 100 hours, and subjected to a heat resistance accelerated test, and measured in the same manner as in the above (5). Determine the YI値 of the film after the heat resistance test. The results are shown in Table 1. (10) YI 耐 after UV resistance test The obtained film (side length 5 cm) was placed in a QUV tester (accelerated weather resistance tester) using a UV fluorescent lamp UVA-.35 1 as a light source for 1 week. UV acceleration test. The YI 薄膜 of the film after the test was measured in the same manner as in the above (5). (1 1 ) Water absorption test The obtained film was cut into 3 pieces of 3 cm x 4 cm size 'under drying under reduced pressure at 18 (TC dried for 8 hours. After measuring the film quality, the film was immersed in distilled water of -37-200951178 at 25 ° C for 24 hours. The water droplets on the surface of the impregnated film are removed and the water absorption rate (% by mass) is calculated from the mass change before and after the impregnation. The water absorption rate is calculated as follows: Water absorption rate (%) = {[(mass after impregnation) + (impregnation) The former mass)]_1}χ100 [Example 14] A polymer composed of a white powder was obtained in the same manner as in Example 1 except that the amidation reaction temperature was 40 ° C and the reaction time was 48 hours (yield 9.20).克, yield: 97.5 mass%) and film. The ring closure ratio (醯imination rate) and weight average molecular weight of the obtained polymer were evaluated in the same manner as in Example 1. The yield of the obtained polymer was 95%. Further, the weight average molecular weight of the polyamic acid is 4. Ox 105, and the weight average molecular weight of the obtained polymer (the polymer after hydrazide) is 5.6 x 10 s. Further, the total light of the film is evaluated as in Example 13. Transmittance, YI 値 (initial The results after the heat resistance test, after the UV test, and the water absorption. The results are shown in Table 1. [Comparative Example 1] In addition to using 7.08 g (35_3 mmol) of 4,4'-diaminodiphenyl ether to replace the double [4] -(3-Aminophenoxy)phenyl]anthracene, and the amount of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, pyridine and acetic anhydride was changed to 7.92 g (35.3 mmol), respectively. The polymer obtained in a light brown powder (yield: 12.7 g, yield: 92.7%) and a film were obtained in the same manner as in Example 1 except for 11.4 ml and 10.0 ml. The structure of the obtained polymer was carried out in the same manner as in Example 1. The analysis and the measurement of the weight average molecular weight. As a result, the characteristic absorption of the carbonyl group was 1 739 cm·1 and 1 689 cnT1 (see Fig. 12 of 200951178), and the weight average molecular weight was 295,000. The yield of the obtained polymer was 92%. Further, the ruthenium iodization ratio was calculated from the ratio of the sulphonic acid NH signal of 1H-NMR to the aromatic ring hydrogen signal. Further, various physical properties of the obtained polymer and film were evaluated as in Example 1. The results are shown in Table 1. - [Comparative Example 2] In place of the use of 4.88 g (24.6 mM) butane tetracarboxylic dianhydride instead of Example 4 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and the amount of 2,2·bis[4-(4-aminophenoxy)phenyl]propane, pyridine and ethylene φ anhydride The polymer was white powder (yield 13.3 g, yield 94.0%) and a film was obtained in the same manner as in Example 4 except that it was changed to 10.12 g (24.6 mmol), 8.0 ml, 7.0 ml, and was obtained in the same manner as in Example 1. In the method, the obtained polymer was subjected to structural analysis and measurement of weight average molecular weight. As a result, the characteristic absorption of the carbonyl group was ITSIcrrr1 and 1705 (refer to Fig. 13), and the weight average molecular weight was 120,000. The obtained imidization ratio of the polymer was 96%. Further, the oxime imidization ratio was 1H-NMR. The kinetic acid NH signal was calculated from the aromatic ring hydrogen signal ratio. Further, φ was evaluated for various physical properties of the obtained polymer and film as in Example 1. The results are shown in Table 1. [Comparative Example 3] except that 4.85 g (24.7 m) was used. Mole) cyclobutane tetracarboxylic acid. The acid dianhydride replaces the 2,3,5-tricarboxycyclopentyl acetic acid dianhydride used in Example 4, and 2,2-bis[4-(4-aminobenzene) The compounding amount of oxy)phenyl]propane, pyridine, and acetic anhydride was changed to 10.15 g (24.7 mmol), 8.0 ml, and 7.0 ml, respectively, and the polymer was prepared in the same manner as in Example 4, but the oxime imidization was carried out. The polymer was precipitated, so the above structural analysis was not carried out -39- 200951178 [Table 1] Solubility total light transmittance (%): Υΐ値Refractive index Tg Y YI値 after UV test γι値Tensile strength (MPa) Tensile elongation (%) Tensile modulus (GPa) Water absorption (%) Example 1 〇89.9 1.0 1.602 259 1.3 - 95 20 2.6 Example 2 〇 88.9 0.6 1.604 326 0.8 - 112 68 2.7 Example 3 〇 88.9 0.8 1.605 300 1.0 - 103 34 2.7 - Example 4 〇 89.1 0.9 1.605 280 1.2 - 127 100 2.7 - Example 5 〇89.1 1.1 1.604 275 1.4 - 107 95 2.6 - Example 6 〇89.2 0.5 1.604 325 0.6 - 108 66 2.7 - Example 7 〇89.1 0.5 1.603 325 0.7 - 105 59 2.7 - Example 8 〇89.5 0J 1.605 282 0.9 - 132 101 2.7 - Example 9 〇90 0.4 - 277 0.7*1 - - - - - Example 10 〇89 0.6 - 280 1.1*1 - - - - - Example 11 〇89 0.5 - 280 0.9*1 - - - - - Example 12 〇89 0.6 - 277 1.0*1 - - - - Reference Example 13 - 89 0.9 - 1.8*2 1.8 - - - 2.4 Example 14 - 89 0.9 - - 2.0*1 2.0 - - - 2.7 Comparative Example 1 〇87.8 3.0 1.604 >350 3.6 - 93 42 2.7 - Comparative Example 2 〇88.0 1.5 1.608 232 2.1 - 100 5 3.4 - Comparative Example 3 X - Milk heat-resistant fiber condition (i75r, 12 hours) * Heat resistance test conditions (15 〇°C, 100 hours) From Table 1, it can be understood that according to the present invention, polyimine has excellent solubility in organic solvents, and does not need to be A film (having excellent formability) can be formed by heat treatment at a temperature (for example, about 400 ° C), and the total light transmittance (transparency) of the obtained film is high, and YI 値 (yellowness) is obtained in addition to -40 to 200951178. It is also low after the heat resistance test, has a high refractive index, and has a high Tg and is excellent in heat resistance. From Examples 6 to 8 of Table 1, it can be understood that, according to the present invention, 'polyimine synthesized by a specific monomer of a specific molar ratio is a full light transmission.

The rate (transparency) is high, the Tg is high, and the heat resistance is excellent, and the YI 値 (yellowness) after the heat resistance test is also low, and the coloring property is extremely excellent. Further, from Examples 9 to 12 of Table 1, it is understood that (A) a specific thiol compound φ substance and (B) a specific aromatic diamine compound (two kinds of aromatic two having different reactivity) according to the present invention Since the polyimide compound obtained by the reaction of the amine compound has excellent solubility in an organic solvent, it is not necessary to heat-treat at a high temperature (for example, about 400 ° C) to form a film (having excellent formability). Further, the obtained film had high total light transmittance (transparency), high Tg, and excellent heat resistance, and even after heat resistance test at a higher temperature than Examples 1 to 8, the ΥΪ値 (yellowness) was low, and the coloring property was not. Extremely excellent. In particular, a polyaryleneamine obtained by reacting the component (A) with the component (B) at a specific molar ratio (further, the molar ratio of the component (B-1) to the component (B-2) is A polyimine or the like which is formed within a specific range) is excellent in heat resistance or YI値 after heat resistance test. Further, from Examples 13 and 14 of Table 1, it can be understood that according to the present invention, since a specific catalyst is used, oxime imidization can be carried out at a lower temperature than in the prior art. Further, since the obtained polyimine has excellent solubility in an organic solvent, it is not necessary to heat-treat at a high temperature (for example, about 40 (TC or so)). Further, from Table 1, the film of the present invention can be understood. (Examples 1 to 4) The transparency (total light transmittance) was high, and the yellowing of the film immediately after formation and after the UV test was small, and the water absorption rate was low from -41 to 200951178. Further, it can be understood that even if it is implemented After the heat resistance test for a longer period of time in Examples 1 to 8, the YI 値 (yellowness) was also low rather than the coloring property. On the other hand, the (B) component was replaced with 4,4'-diaminodiphenyl ether. Comparative Example 1 was found to be not suitable for optical members immediately after the formation of the film and after the heat resistance test, and Comparative Example 3 using the cyclobutane tetracarboxylic acid as the dry component instead of the component (A) was ruthenium imine. The solubility in an organic solvent was low, and polyimine was precipitated in a solvent, and it was found that a film could not be formed. In Comparative Example 2, it was found that a film could be formed, but the obtained film had a low Tg and poor heat resistance [Simplified illustration] Fig. 1 The polymer obtained in Example 1 is shown IR spectrum chart Figure 2 shows an IR spectrum of the polymer obtained in Example 2. Figure 3 shows an IR spectrum of the polymer obtained in Example 3. Figure 4 shows the IR spectrum of the polymer obtained in Example 4. Fig. 5 shows an IR spectrum of the polymer obtained in Example 6. Fig. 6 shows an IR spectrum of the polymer obtained in Example 7. Fig. 7 shows an IR spectrum of the polymer obtained in Example 8. Figure 8 shows an IR spectrum of the polymer obtained in Example 9. Figure 9 shows an IR spectrum of the polymer obtained in Example 10. Figure 10 shows an IR spectrum of the polymer obtained in Example 11. Figure 11 The IR spectrum of the polymer obtained in Example 12 is shown. Figure 12 shows the IR spectrum of the polymer obtained in Comparative Example 1. Figure 13 shows the IR spectrum of the polymer obtained in Comparative Example 2. -42 -

Claims (1)

200951178 VII. Patent application scope: 1. A polyamidene-based material characterized by polyamic acid and/or polyimine obtained by the following reaction: (A) is selected from the following formula (1) And 2,3,5-tricarboxycyclopentyl acetic acid, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride represented by the following formula (2), and a group consisting of the reactive derivatives a group of at least one mercapto compound, and (B) an aromatic imine group represented by the following formula (3) to form a compound [Chemical Formula 1] (1) [Chemical 2] (2) [Chemical 3] (3) (In the formula (3), X is -NH2 or -N = C = 0, -NHSi(R25)(R26)(R27), Y is selected from a direct bond, -CH2-, -0-, -S- And one of -C(CH3)2-, Z is one selected from the group consisting of a direct bond, -CH2-, -〇_, -s-, -C(CH3)2-, >C = 0, -S02- The groups R1 to R1 6 are each independently selected from the group consisting of hydrogen, an alkyl group, a vinyl group, and an aryl group "R25 to R27, each independently having an alkyl group having 1 to 15 carbon atoms". -43-200951178 2. The polyimide-based material according to claim 1, wherein the (in) aromatic imine group-forming compound is in the above formula (3), and the bonding group X, hydrazine and hydrazine are all It is a compound formed by a para-bonding. 3_ A polyimide-based material according to claim 1 or 2, wherein the polyamine and/or the polyimine are converted to polystyrene having a weight average molecular weight of 50,000 to 500,000. 4. The polyimide-based material according to any one of claims 1 to 3, wherein the poly-proline and/or the polyimine are (使) mercapto compounds and (Β) aromatic sub- The molar ratio of the amine group formation ((Α) mercapto compound: (Β) aromatic imine group former) is obtained by reacting in a manner of 1.000:0.960 to 1.000:0.995. 5. A polyimide-based material according to any one of claims 1 to 4, wherein the polyaminic acid and/or polyimine is further substituted with a substituent constant obtained by Hammett's law. The total σ (wherein the total σ is an amine group as a reference, and the substituent constant of the amine-free body is not included) is an aromatic diamine compound in an amount exceeding -0.11 and 2.0 or less as an aromatic imine group. The compound is obtained by reaction. 6. A polyimine-based resin composition, characterized by comprising the polyimide-based material of any one of claims 1 to 5 and an organic solvent 〇. It is characterized by containing the polyimide-based material of any one of claims 1 to 5. 8. A film of a polyimide film according to item 7 of the patent application, which is used for an optical member. -44- 200951178 9. The polyimine film according to item 7 of the patent application is used for a substrate for a printed circuit. 10. A method for producing a polythene sublimine material, characterized by comprising the step of: (Α) selected from 2,3,5-tris-carboxycyclopentylacetic acid represented by the following formula (;!), The at least one mercapto compound of the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride represented by the following formula (2) and the reactive derivative thereof, and 0 (Β) are represented by the following formula (3) a step of reacting the aromatic imine group forming compound 9 in an organic solvent to obtain a polyproline, and a step of imidating at least a portion of the polyamic acid, [Chemical Formula 1] H〇〇C^/\^COOH ΛΤ (l) HOOC^一\^-co〇H [Chemical 2] ❿ 1 (2) β [Chemical 3] (In equation (3), X 舄·Νη2 or _N = C = 〇, _NHSi(R2 5)(R26)(R2 7) , Y is selected from direct bonds, _CH2_, -〇-, -s-, - C(CH3)2- is a group selected from the group consisting of a direct bond, ch2_, _〇_, -S-, -C(CH3)2-, >c = 0, -S〇2- -45- 200951178 One of the groups, rLr1 6 is independently selected from the group consisting of hydrogen, alkyl, vinyl, aryl, and halogen, and R25 to R27 are each independently an alkyl group having 1 to 15 carbon atoms. 11. The method of producing a polyimide-based material according to claim 10, wherein at least a portion of the poly-proline is ruthenium imidized in the presence of an alicyclic tertiary monoamine. 12. The method for producing a polyimide-based material according to claim 11, wherein the alicyclic tertiary monoamine is a compound represented by the following formula (6): [Chemical 4] (In the formula (6), R is a hospital group having a carbon number of 1 to 4, X is an oxygen atom or a sulfur atom, 1 is 0 or 1, and m and η are each independently an integer of 0 to 2). 13. The method for producing a polyimide-based material according to claim 11 or 12, which further comprises using an acid anhydride selected from the group consisting of acetic anhydride, propionic anhydride, and phthalic anhydride, and hydrazine chloride corresponding to the acid anhydride At least one dehydrating agent of the group consisting of: and a carbodiimide compound. A method for producing a polyimide film, comprising: coating a solution of a poly' fluorene-based material obtained by the method of any one of claims 10 to 13 and an organic solvent; A coating film & step is formed on the substrate, and the organic solvent is removed from the coating film by evaporation to obtain a polyimide film. -46 -