TW201139523A - Process for production of element substrate and composition to be used therein - Google Patents

Abstract

A process for the production of an element substrate, characterized by including: a step (a) of applying a polyimide-based film-forming composition which comprises both a polyamic acid that contains a structural unit represented by general formula (1) and an organic solvent to a supporting body, and drying the resulting coating to form a coating film that contains the polyamic acid; a step (b) of heating the coating film to form a polyimide-based film; a step (c) of forming an element on the polyimide-based film; and a step (d) of peeling the polyimide-based film which has the element thereon from the supporting body. In general formula (1), multiple R1s are each independently a monovalent organic group having 1 to 20 carbon atoms; and n is an integer of 1 to 100.

Description

201139523 VI. [Technical Field] The present invention relates to a method for producing a substrate and a composition therefor. [Prior Art] Generally, it is obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine. The wholly aromatic polyimine has excellent heat resistance, mechanical properties, electrical properties, oxidation resistance, hydrolysis resistance, etc. due to the rigidity of the molecule or the resonance of the molecule, and strong chemical bonding. It is widely used as a film, a coating agent, a molded part, and an insulating material in the fields of batteries, automobiles, and aerospace industries. For example, a polyimine (polyimine film) obtained by polycondensing pyromellitic dianhydride and 4,4'-oxydiphenylamine is excellent in heat resistance and electrical insulation, and has high dimensional stability and can be used for flexibility. Printing substrates, etc. Specifically, the polyimine film is obtained by subjecting a polyphthalic acid solution obtained by reacting pyromellitic dianhydride with 4,4'-oxydiphenylamine by a solvent removal or thermal amination process. Usually, the polyimide film is formed on a relatively rigid support such as a stainless steel belt. The polydiimide synthesized from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and p-phenylenediamine is excellent in thermal dimensional stability (Patent Document 1 and Patent Document 2). The polyimine film of the present invention is, for example, a tetracarboxylic dianhydride having an essential component of 4,4·-oxydiphthalic dianhydride and pyromellitic dianhydride-5-201139523 and containing p-phenylenediamine. A polyimine film obtained from an aromatic diamine of 4,4-oxydiphenylamine is known (Patent Document 3). [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei No. Hei. SUMMARY OF THE INVENTION [Summary of the Invention] [Problems to be Solved by the Invention] However, the above-mentioned conventional polyimine (formation composition) is used to form a film on a support such as a ruthenium wafer or an alkali-free glass. At the time of shrinkage deformation at the time of film formation, the substrate or the film itself has a problem of warpage. Therefore, the polyimine (formation composition) is used for the production of smoothness, flexibility, flexibility, dimensional stability, and flexibility of a flexible printed circuit board or a flexible display substrate. The substrate is more difficult. Further, when a conventional polyimide film is formed on a support such as a ruthenium wafer or an alkali-free glass, it is difficult to obtain both the adhesion and the releasability of the obtained film and the support. SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate manufacturing method and a composition therefor which are more effective in preventing warpage or distortion from occurring at a low cost and in a simple manner. [Means for Solving the Problem] -6 - 201139523 In order to solve the above problems, the inventors of the present invention have carefully reviewed the results and found that a composition for forming a polyimine film containing a polyamine and a specific solvent having a specific structural unit is used. The present invention can be completed by manufacturing a substrate on a support, which can more effectively prevent the occurrence of warpage or distortion, and a composition and a production method capable of simultaneously obtaining the adhesion and releasability of the obtained film and the support. In other words, the present invention provides a method for producing a substrate comprising: (a) coating a support having a structural unit represented by the following formula (1); a step of forming a polyimide-based film-forming composition of a poly-proline and an organic solvent, forming a coating film containing poly-proline, and (b) heating the coating film containing the poly-proline a step of forming a polyimide film, (c) a step of forming an element on the polyimide film, and (d) a step of peeling the polyimine film forming the element from the support; 1] R1 - fsi - 0 -) - (1) η R1 (In the formula (1), the plural R1 groups are each independently a monovalent organic group having 1 to 20 carbon atoms, and the η is an integer of 1 to 200). The method for producing a substrate according to the above [1], wherein the polyamic acid is at least one mercapto group containing (A) selected from the group consisting of tetracarboxylic dianhydride and the reactive derivative. The component of the compound is reacted with (B) a component containing an imine group-forming compound and satisfies the following (i) and/or (ii), (i) the component (A) contains (A-1) having the above formula ( 1) A mercapto compound (Π) of the structural unit represented by the above (B) component contains (B-1) an imido group-forming compound having a structural unit represented by the above formula (1). [3] The method for producing a substrate according to the above [2], wherein the content of the imine group-forming compound having the structural unit represented by the above formula (1) in the above (B) component is relative to The total amount of the above components (B) is 1% by mass and the mass% is 5 to 70% by mass. [4] The method for producing a substrate according to the above [2] or [3], wherein the number calculated based on the amine valence of the imine group-forming compound having the structural unit represented by the above formula (1) (B-1) The method for producing a substrate according to any one of the above-mentioned items, wherein the poly (A) component and the component (B) It is obtained by reacting the molar ratio of (A) component and (B) component ((B) component / (A) component) 〇·8 to 1.2. [6] The method for producing a substrate according to any one of [1] to [5] wherein the organic solvent is selected from the group consisting of ruthenium, Ν'·dimethylimidazolidinone, γ-butyrolactone, Ν- At least one solvent group of methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile, and ethylene glycol monoethyl ether, and 50% by weight or more based on the total amount of the organic solvent . The method for producing a substrate according to any one of the above-mentioned items, wherein the polyimine which constitutes the polyimine film is subjected to differential scanning calorimetry (DSC, temperature increase rate). The glass transition temperature measured at 20 ° C / min) was above 350 ° C. [8] The method for producing a substrate according to any one of [1] to [7] wherein the heating in the step (b) is carried out in the range of 200 to 350 ° C, and in the polyimine system The glass transition temperature of the film is carried out below. [9] The method for producing a substrate according to any one of [1] to [8] wherein the support is a tantalum wafer or an alkali-free glass. [1 〇] A polyimine film for forming a substrate, which is used for the formation of a polyimide film of the method for producing a substrate according to any one of the above [1] to [9] a composition comprising a polyamic acid having a structural unit represented by the following formula (1) and an organic solvent, wherein R 1 —(—Si—〇]—(1) η R1 (in the formula (1), The plural R1 is each independently a monovalent organic group having 1 to 20 carbon atoms, and the η is an integer of 1 to 200. [Effect of the Invention] According to the method for producing a substrate of the present invention, it is easy to manufacture less -9- 201139523 The warpage or the twisted substrate is formed. The composition for forming a polyimine film of the present invention is composed of a composition containing a polyamine having a structural unit represented by the above formula (1) and an organic solvent. When the substrate is produced, warpage or distortion can be effectively prevented. By using the composition for forming a polyimide film of the present invention, it can be reduced even if it is formed on a support such as a ruthenium wafer or an alkali-free glass. The warpage generated on the substrate or the film as the shrinkage deformation at the time of film formation. Therefore, the polyfluorene of the present invention The composition for forming an amine film is suitable for applications requiring smoothness, flexibility, flexibility, and dimensional stability, and is particularly suitable for producing a flexible substrate such as a flexible printed circuit board or a flexible display substrate. In the method for producing a substrate of the present invention, even when a ruthenium wafer or an alkali-free glass as a support is used, a polyimide film which can have both adhesion and releasability to the support can be easily produced. In the present invention, the term "adhesiveness" means, for example, in the step (b) or the step (c), the polyimide film formed on the support and the substrate and the support are not easily peeled off. In the step (d), for example, the peeling property is small, and the substrate can be peeled off from the support. The present invention is a method for producing a substrate, and the characteristics thereof. (a) A composition for forming a polyimine-based film containing a polyamic acid having a structural unit represented by the following formula (1) and an organic solvent in the support, which is formed by drying - (2011) Containing polyaminic acid a step of forming a film; (b) a step of heating the coating film containing the poly-proline to obtain a polyimide film; (c) a step of forming a component on the polyimine film; (d) The step of peeling off the polyimine film forming the element from the support is carried out. [Chemical 3] R1 - fsi - 0^ - (1) η R1 In the formula (1), the plural R1 systems are each independently a carbon number of 1 The organic group of -20 is an integer of η 1 to 200. The "carbon number 1 to 2 〇" means "a carbon number of 1 or more and a carbon number of 20 or less." The same description in the present invention means the same meaning. In the above (1), R1 is a monovalent organic group having 1 to 2 carbon atoms, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms and a carbon number of at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. ~20% of the price of organic base and so on. The hydrocarbon group having 1 to 20 carbon atoms represented by R1 may, for example, be a group having a carbon number of 1 to 20, a cycloalkyl group having 3 to 2.0 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 1 carbon number, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Base, pentyl, hexyl and the like. The ring-ring base of the carbon number of 3 to 20 is preferably a ring-shaped base of a carbon number of 3 to 10, and specifically, for example, -11 - 201139523, there are, for example, a cyclopentyl group, a cyclohexyl group and the like. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and the like. The organic group having a carbon number of oxygen atoms, for example, an organic group composed of a hydrogen atom, a carbon atom, and an oxygen atom, specifically, for example, a carbon number of 1 to 2 having an ether bond, a carbonyl group, and an ester group 0 organic base and so on. The organic group having a carbon number of 1 to 20 having an ether bond is, for example, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, and a carbon number of 6 to 20 An aryloxy group and an alkoxyalkyl group having 1 to 20 carbon atoms. Specifically, it is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a phenoxy group, a propyleneoxy group, a cyclohexyloxy group, a methoxymethyl group or the like. The organic group having a carbon number of the carbonyl group is, for example, a fluorenyl group having 2 to 20 carbon atoms. Specific examples thereof include an ethyl group, a propyl group, an isopropyl group, and a benzamidine group. The organic group having a carbon number of the ester group is, for example, an anthracene group having a carbon number of 2 to 20 or the like. Specific examples thereof include an ethoxylated group, a propyloxy group, an isopropyloxy group, and a benzamidine group. The organic group having a carbon number of 1 to 20 containing a nitrogen atom, for example, an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom, specifically, for example, an imidazolyl group, a triazolyl group, a benzimidazolyl group, and a benzo group Triazolyl and the like. The organic group having 1 to 2 carbon atoms of an oxygen atom and a nitrogen atom, for example, an organic group composed of a hydrogen atom 'carbon atom, an oxygen atom and a nitrogen atom, specifically, for example, an oxazolyl group or an oxadiazole Base, benzoxazolyl and benzooxadiazolyl, etc. -12-201139523 At least one of the plural R1 in the above formula (1) is effective in preventing warpage of the obtained polyimine film or A distorted view or the like 'preferably contains an aryl group. More specifically, the plural R1 is preferably an alkyl group having 1 to 1 carbon atom and an aryl group having 6 to 12 carbon atoms. In this case, the number of moles (i) and carbon number of the alkyl group having 1 to 10 carbon atoms in all of R1 in the structural unit (hereinafter also referred to as "structural unit (1)") represented by the above formula (1). The ratio of the molar number of the aryl group of 6 to 12 (ii) (but (i) + ( Π ) = 1 〇〇) is preferably (i) : ( ii ) = 90 〜 10: 10-90, more Good for (i): (ii)=85~15: 15-85, more preferably (i): (ii) =85~6 5: 15-3 5. In R1 of all the structural units (1), when the ratio of the alkyl group (i) to the aryl group (ii) is in the above range, warpage or distortion of the obtained polyimide film can be effectively prevented. The alkyl group (i) having 1 to 10 carbon atoms is preferably a methyl group, and the aryl group (ii) having 6 to 12 carbon atoms is preferably a phenyl group. The η of the above formula (1) is an integer of from 1 to 200, preferably from 3 to 200, more preferably from 10 to 200, still more preferably from 20 to 150, still more preferably from 30 to 100, particularly preferably from 35 to 80. The integer. When η in the above formula (1) is in the above range, the polyimine obtained from the poly-proline is likely to form a microphase-separated structure, so that warpage or distortion of the obtained polyimide film can be suppressed. It inhibits the white turbidity or mechanical strength of the polyimide film. [Step (a)] First, a composition for forming a polyimine-based film containing a polyamine acid having a structural unit (1) and an organic solvent is applied onto a support, and dried to form a polyglycine-containing composition. The step of coating the film. • 13-201139523 The polyimine film-forming composition used in this step contains a polyamic acid having a structural unit (1) and an organic solvent. By using such a polyamic acid, a substrate having excellent balance between adhesion and peelability and smoothness without warpage can be obtained. In the composition for forming a polyimine-based film, an additive such as an oxidation preventive, an ultraviolet absorber, or a surfactant may be added to the extent that the object of the present invention is not impaired. The polyamic acid having the structural unit (1), preferably (A) a component containing at least one mercapto compound selected from the group consisting of four residual dianhydrides and the reactive derivative (in the present invention) It is also referred to as "(A) component") and (B) a component containing an imine group-forming compound (also referred to as "(B) component in the present invention). In this case, the component (A) is a thiol compound containing (A-1) structural unit (1) (hereinafter also referred to as "compound (A-1)"), or (B) is a component containing (B-1) structural unit. The imido group forming compound (hereinafter also referred to as "compound (B-1)") of (1) is preferred. Further, both the compound (A-1) and the compound (B-1) can also be used. According to this reaction, polylysine having a structure of a raw material compound to be used in combination can be obtained, and the amount of the starting compound used in combination can be used to obtain a polylysine having a structural unit derived from the compound. [Component (A)] The component (A) is a component containing at least one mercapto compound selected from the group consisting of tetracarboxylic dianhydride and the reactive derivative. It is preferably at least one compound containing a group of the mercapto compound (A-2) selected from the group consisting of the above compound (A-1) and the compound (A-1). -14-201139523 The specific compound (Al) is preferably a tetracarboxylic dianhydride having a structural unit (!) and at least one mercapto compound of the reactive derivative, which is preferably the following formula (2). A compound represented by the formula (2A), the formula (2B), and the formula (2C). The above reactive derivative may, for example, be a tetracarboxylic acid having a structural unit (1), an acid ester of the tetracarboxylic acid, an acid chloride of the tetracarboxylic acid or the like. 【化4】

(2A)

R2——R11 (2)

(2B) (2C) In the above formulae (2), (2A), (2B) and (2C), the plural R1 and η are each independently synonymous with R1 and η in the above formula (1). The scope is also the same. R2 each independently represents a divalent hydrocarbon group of carbon number. In the above formulae (2Α) and (2C), R11 each independently represents a hydrogen atom '-15-201139523 or a monovalent organic group having 1 to 20 carbon atoms, and the monovalent organic group having 1 to 20 carbon atoms is as described above. In the formula (1), the same group or the like of the monovalent organic group having a carbon number of 1 to 20 in R1. The divalent hydrocarbon group of carbon number in R2 is, for example, a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a aryl group having 6 to 20 carbon atoms. The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms, and examples thereof include a dimethylene group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentylene group, a cyclohexylene group, a cyclohexyl group, and the like. The exoaryl group having 6 to 20 carbon atoms is preferably an exoaryl group having 6 to 12 carbon atoms, for example, a phenyl group, a naphthyl group or the like. The compound (A-1) preferably has a number average molecular weight of from 200 to 10,000, more preferably from the viewpoint of obtaining polyamic acid and/or polyimide having excellent heat resistance (high glass transition temperature) and water resistance. 00~8,000. Specific examples of the compound (A-1) include DMS-Z21 (number average molecular weight: 600 to 800, n = 4 to 7) manufactured by Gelest Corporation. In the case of synthesizing polyamic acid, these compounds (A-1) may be used alone or in combination of two or more. When the component (A) contains the compound (A-1), the component (A) preferably contains the compound (A-1) in an amount of 10 to 60% by mass based on 100% by mass based on the total amount of the allyl group-based compound ((A) component). %, more preferably 20 to 50% by mass 'better than 25 to 50% by mass' is particularly good for containing 3 〇 to 50% by mass. The compound (A-1) is used in an amount of from -16 to 201139523 in the above range, from the viewpoint of obtaining heat resistance and a substrate (polyimine film) excellent in adhesion and releasability to a support. . However, a preferred blending amount of the above compound (A-1) with respect to 100% by mass of the total amount of the wholly mercapto compound (component (A)) is the case where the above compound (B-1) is not used when synthesizing polyglycine. In the case of synthesizing poly-proline, when the compound (A-1) and the compound (B-1) are used as a raw material, the total amount of the compound (A-1) and the compound (B-1) to be used is preferably the same as the above compound. The preferred blending amount of (A-1) is the same. (A-2) A mercapto compound other than the compound (A-1) The mercapto compound (A-2) other than the above compound (A-1) is selected, for example, from an aromatic tetracarboxylic dianhydride or an aliphatic group. At least one compound in which the tetracarboxylic dianhydride, the alicyclic tetracarboxylic dianhydride, and the reactive derivative are grouped. Specific examples are butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5 _Tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,5,6-tricarboxylamine-2, acetic anhydride dianhydride, 2,3,4 , 5-tetrafuran tetraresic acid dianhydride, 1,3,3&,4,5,915-hexahydro-5-(tetrahydro-2,5-monooxy-3-indolyl)-naphtho[ 1,2-<:]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3_methyl-3-cyclohexene-1,2-dicarboxylic acid An aliphatic tetrahydro acid dianhydride or an alicyclic tetraphthalic acid dianhydride such as an anhydride, a bicyclo[2,2,2]-octyl_7_server_2,3,5,6-tetraresidic acid dianhydride, and the like And other reactive derivatives; 4,4'-oxyl - Benzoic acid monohepatic, Bentotetracarboxylic dianhydride, 3,3,4,4,--benzophenone tetrahydro acid anhydride, 3,3 ',4,4'-biphenylfluorene tetraresic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3, ,4,4,. -17- 201139523 Dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 2,3,4,5 -furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyl) Phenoxy group) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl succinic anhydride, 4,4'·bis(3,4-dicarboxyl Phenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4'·biphenyltetracarboxylic acid Anhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) Aromatic tetracarboxylic acid such as anhydride, bis(triphenylphthalic acid)-4,4,-diphenyl ether dianhydride or bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride Acid dianhydride and such reactive derivatives. Among these, from the viewpoint of excellent transparency and good solubility in an organic solvent, aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferably used. Further, from the viewpoints of heat resistance, low linear expansion coefficient (size stability), and low water absorption, aromatic tetracarboxylic dianhydride is preferably used. The fluorenyl compound (A-2) is preferably a compound having a group represented by the following formula (4), and the like, from the viewpoint of effectively preventing warpage or distortion of the obtained polyimide film. A compound having a group represented by the following formula (41). [5] (R4)b

-18- 201139523

In the above formula (4), 'R4 each independently represents a hydrogen atom or a fluorenyl group, and a hydrogen atom of the alkyl group may be substituted by a halogen atom, and each of the A groups independently represents an ether group, a thioether group, a ketone group, an ester group, a sulfonate. a group of at least one group of a group consisting of a fluorenyl group, an alkylene group, a decylamino group, and a decyloxy group, wherein a hydrogen atom of an alkyl group may be substituted by a halogen atom. 'D system represents an ether group or a thioether group. a keto group, an ester group, a sulfonyl group, an alkylene group, a decylamino group or a oxalyl group. The hydrogen atom of the alkyl group may be substituted by a halogen atom. The 'b systems each independently represent 1 or 2'. An integer representing '1 to 3' is an integer representing 〇~3. In the above formula (4), the alkyl group in 'R4 is preferably a hospital group having a carbon number of 1 to 20, more preferably a carbon number of 1 to 1 Å. Specifically, for example, a methyl group or an ethyl group is used. - 201139523, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl 'hexyl, etc. Any of the hydrogen atoms in the hospital base may be a fluorine atom, a chlorine atom, a bromine atom or Substituted by iodine atoms. In the above formula (4), the alkyl group in D may, for example, be a methylene group or a C 2 to 2 alkyl group, and the hydrogen atom of the methylene group and the alkyl group may be substituted by a halogen atom. The alkylene group having 2 to 20 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, for example, a dimethylene group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropylidene group. And a thiol group and a group in which any hydrogen atom in the alkylene group is substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Each of the A lines independently represents an ether group (-0-), a thioether group (-S-), a keto group (-C ( =0 )-), and an ester group (-COO-) 'sulfonyl group (- S02-), alkylene (-R7-) 'nonylamino (-C ( =0 ) -NR8-) and oxiranyl (-Si ( R9 ) 2-0-Si ( R9 ) 2 ·) A group of at least one group of groups in which a hydrogen atom of an alkyl group may be substituted by a halogen atom. The above R8 and R9 each independently represent a hydrogen atom, an alkyl group or a halogen atom, and the hydrogen atom of the alkyl group may be substituted by a halogen atom. The alkyl group in the above R8 and R9 may, for example, be the same as the alkyl group in the above R4. The above halogen atom is preferably a chlorine atom or a fluorine atom. The alkylene group (-R7-) in the above A has, for example, the same group as the alkylene group in the above D, and among them, preferably a methylene group, an isopropylidene group or a hexafluoroisopropylidene group. And 蒹基. R4 is preferably a hydrogen atom, A is preferably an ether group, and D is preferably a sulfonyl group. -20- 201139523 f is preferably an integer of 0 to 2, more preferably 〇 or 1, more preferably 〇. 【化6】

When the mercapto compound (Α-2) other than the above compound (Α-1) contains the above compound (Α-1) in the (Α) component, the total amount of the total mercapto compound ((Α) component is 100% by mass) When the (Α) component contains 40% by mass or more, it is preferable to contain 40 to 90% by mass, more preferably 50 to 80% by mass, more preferably 50 to 75% by mass, and more preferably 50 to 70% by mass. . The amount of the mercapto compound (Α-2) to be used is preferably included in the above range from the viewpoint of heat resistance and a substrate (polyimide film) excellent in adhesion to the substrate and releasability. [(Β)Component] (Β) The component is an imine group forming compound. Here, the "imine forming compound" means a compound which reacts with the component (A) to form an imine (group), and specifically, for example, a diamine compound, a diisocyanate compound, or a bis(trialkylformamidine)amine Base compound, etc. (B) Component ii is preferably at least one selected from the group consisting of the imine group-forming compound (B-2) selected from the group consisting of the above compound (B-1) and the compound (B-1). -21 - 201139523 The imine group-forming compound having a (B -1 ) structural unit (1), for example, a compound represented by the following formula (3) and formula (3A). [Chemical 7] R1 R1 H2N—R3—^~Si—〇-j—Si—R3—NH2 (3) R1 R1 if H2N— R3 Si Si—Leave Si—R3—R11 (3A) \R1 /nR1 In the formula (3), the plural R1 and n are each independently the same as R1 and η in the above formula (1), and the preferred range is also the same. In the above formula (3A), R11 is synonymous with R11 in the above formulas (2Α) and (2C). R3 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the divalent hydrocarbon group having 1 to 20 carbon atoms is, for example, in the above formulae (2), (2Α), (2Β), and (2C), in R2. The same group such as a divalent hydrocarbon group having 1 to 20 carbon atoms. The above compound (Β-1) is preferably a number average molecular weight calculated from an amine value from the viewpoint of obtaining a polylysine and/or a polyimide having excellent heat resistance (high glass transition temperature) and water resistance. 1 0,000, more preferably 1,000 to 9,000, more preferably 3,000 to 8,000. Specifically, the above compound (Β-1) has, for example, a terminal amino group-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd. 22- 1 660Β-3' (number average molecular weight 4,400, degree of polymerization 11 = 41, benzene) Base: methyl = 25:75111〇1%), Χ22-9409 (number average molecular weight 1,300)), both terminal amine-denatured dimethylpolyfluorene (Shin-Etsu Chemical Co., Ltd. Χ22-161 Α (number average molecular weight) 1,600, degree of polymerization n = 20), X22-161B (number average molecular weight 3,000 -22-201139523, degree of polymerization n = 39), KF8012 (number average molecular weight 4400, degree of polymerization n = 5 8), Toray by Dow Corning BY16- 835 U (number average molecular weight 9 〇〇, polymerization degree n = 11)) and the like. When the polyaminic acid is synthesized, the above-mentioned imine group-forming compound (B-1) may be used alone or in combination of two or more. When the component (B) contains the imine group-forming compound (B-1) having the structural unit represented by the above formula (1), the total amount of the compound ((6) component) is 100% by mass based on the total imine group-forming compound (B). The component preferably contains the compound (B-1) in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 15 to 55% by mass. The amount of the imine group-forming compound (B-1) to be used is preferably in the above range from the viewpoint of obtaining a heat-resistant and a polyimide film having excellent adhesion to a substrate and releasability. However, when the compound (B-1) is a compounding amount of the total amount of the total imine group-forming compound (the component (B)) in an amount of 1% by mass, the above compound (A - 1) The situation. (B-2) An imide group-forming compound other than the compound (B-1) The imine group-forming compound (B-2) other than the above compound (B-1) is selected, for example, from an aromatic diamine or a fat. A compound of at least one of a group consisting of a group of diamines and an alicyclic diamine. The aforementioned aromatic diamine is, for example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4,-diaminodiyl Phenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether (34,_〇DA), 33,-diaminodiphenyl ether (3,3'-ODA), 3, 3,-Dimethyl-4,4,-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino 2,2 ,_双(三-23- 201139523 fluoromethyl)biphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-, 4,4'-diaminobenzophenone , 3,3'-diaminobenzophenone bis(4-aminophenyl) sulfide, 4,4'-diaminodiphenylanthracene, aminobenzamide, l,n-double (4-Aminophenoxy)alkane, [2-(4-aminophenoxyethoxy)]ethane, 9,9-bis(4-aminopurine, 9,9-bis(4- Aminophenoxyphenyl)anthracene, 5 (6)-aminoaminomethyl)-1,3,3-trimethylindan, 1,4-bis(4-aminophenylbenzene (TPE-) Q), 1,3-bis(4-aminophenoxy)benzene (TPE 1,3-bis(3-aminophenoxy)benzene (human?8), 2,5-bis(4-amine) Biphenyl (P-TPEQ), 4,4'-bis (4-amine Phenoxy group) 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenyl)]propane, 2,2-bis(4- Aminophenoxyphenyl)hexafluoropropan[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)anthracene, 2,2-bis[4 Mono(4-aminophenoxy)phenyl]hexafluoropropanamine, 3,3-dimethoxy-4,4-diaminobiphenyl, 2,2'-dichloro-4^yl-5 , 5'-dimethoxybiphenyl, 2,2',5,5'-tetrachloro-4,4'-diamino 4,4'-methylene-bis(2-chloroaniline), 9 , 10-bis(4-aminobenzene, hydrazine-triazine maple, etc. These aromatic diamines may be used alone or in combination 2. The above aliphatic diamines have, for example, aliphatic groups having a carbon number of 2 to 30. Examples of the amines are ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentane 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane An alkanediamine such as an amine, 1,9-nonanediamine oxime diamine or 1,12-dodecanediamine; oxygen bis(2-amine), oxybis(2-aminopropane), 2-(2) -aminoethoxy)ethylene dioxygenate, 4,4'-4,4,-di1,3-diphenyl)-1-(4-oxy)-R), phenoxybiphenyl, benzene Oxyalkane, diyl)benzene Biphenyl, - biphenyl diamine above, yl) anthracene species which has diamine, siloxane diamine '1,10 ethane amine group, etc. -24-201139523 ethane. These aliphatic diamines may be used alone or in combination of two or more kinds thereof to supply a hydrazine imidization reaction. The alicyclic diamine may have at least one alicyclic group in the molecule, and the alicyclic group may be any of a monocyclic, polycyclic or condensed ring. The alicyclic diamine may be an alicyclic diamine having 4 to 30 carbon atoms, for example, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-di Methylcyclohexylmethane, 4,4'-diamino-3,3',5,5'-tetramethylcyclohexylmethane, 1,3-diaminocyclohexane, 1,4-diamine Cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,2-bis(4,4,-diaminocyclohexyl)propane, 1, 3-Diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, 2,3-diaminobicyclo[2.2.1]heptane, 2,5.diaminobicyclo[2.2 .1] heptane, 2,6-diaminobicyclo[2.2.1]heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)- Bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane , 3(4), 8(9)-bis(aminomethyl)-tricyclo[5.2.1.02'6]decane, and the like. These imine group-forming compounds may be used alone or in combination of two or more. The above-described imine group-forming compound (B-2) may be used to prevent warpage or distortion of the obtained polyimide film. A compound having a group represented by the following formula (5) is preferred, and a compound having a group represented by the following formula (51) is more preferred. -25- 201139523 【化8】

In the above formula (5), R5 each independently represents a group containing an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, a decylamino group or a decyloxy group, a hydrogen atom, or a halogen. An atom, an alkyl group, a hydroxyl group, a nitro group, a cyano group or a sulfonic acid group, wherein the hydrogen atom of the alkyl group and the alkyl group may be substituted by a halogen atom, and the a units each independently represent an integer of 1 to 3, and the a2 groups each independently represent 1 Or 2, a3 each independently represents an integer of 1 to 4, and e represents an integer of 0 to 3. A and D are each independently synonymous with A and D in the above formula (4), and preferred groups are also the same as in the above formula (5), and R5 is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group or a nitro group. The aryl group or the sulfonic acid group is preferably a hydrogen atom or an alkyl group. In the above formula (5), the alkyl group in R5 is synonymous with the alkyl group in 'R4 -26-201139523 in the above formula (4), and the above-mentioned formula (R5) in the above formula (5) In 4), the alkyl group in D is synonymous. e is preferably an integer of 0 to 2', more preferably 0 or 1 ', more preferably 0 ° [Chemical 9] R5 R5

In the above formula (5'), R5 is each independently synonymous with R5 in the above formula (5). When the total amount of the imine group-forming compound (B-2) other than the compound (B-1) is 100% by mass, the component (B) preferably contains 4 0 to 90% by mass, more preferably 50 to 80% by mass, still more preferably 50 to 75% by mass, particularly preferably 50 to 70% by mass. The use amount of the imine group-forming compound (B-2) is preferably in the above range from the viewpoint of obtaining a substrate (polyimine film) excellent in heat resistance and adhesion to the substrate and releasability. . The polyimine-based film-forming composition containing a poly-proline and an organic solvent is obtained by reacting the component (A) and the component (B) in an organic solvent. In a specific method of reacting the component (A) with the component (B), for example, at least one (B) imine group-forming compound is dissolved in an organic solvent, and at least one kind of (A) is added to the obtained solution. The base compound is stirred at a temperature of 〇~it -27-201139523 for 1 to 60 hours. The above organic solvent is, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ-butyrolactone, hydrazine, An aprotic polar solvent such as Ν'-dimethylimidazolidinone, tetramethylurea, tetrahydrofuran, cyclohexanone, acetonitrile or ethylene glycol monoethyl ether; phenolic solvent such as cresol, xylenol or halogenated phenol Wait. Preferred among them are hydrazine, Ν'_dimethylimidazolidinone, γ-butyrolactone, Ν-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile and Ethylene glycol monoethyl ether. It is contained in an amount of 50% by weight or more, preferably 70% to 100% by weight, based on the total amount (100% by weight) of the organic solvent to be used, selected from the group consisting of hydrazine, Ν'-dimethylimidazolidinone, γ-butyrolactone, and hydrazine. At least one solvent of -methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile, and ethylene glycol monoethyl ether. These solvents may be used alone or in combination of two or more. The organic solvent is preferably a guanamine-based solvent and a solvent selected from the group consisting of an ether solvent, a ketone solvent, a nitrile solvent, and an ester system from the viewpoints of adhesion, peelability, and residual stress of the obtained coating film (film). A mixed solvent of at least one non-melamine-based solvent in which a solvent is a group. When the above-mentioned mixed solvent is used, it is possible to obtain a composition in which the drying speed at the time of film formation is increased, the film quality is not lowered, the productivity of the polyimide film is excellent, and the concentration of polyglycine is high. The non-amine-based solvent is preferably a solvent which is selectively evaporated in the following vacuum drying, and which can be almost completely removed from the coating film formed on the substrate, and preferably has a boiling point in the range of 40 to 200 ° C. A solvent in the range of 100 to 170 ° C. When such a solvent is used, the solvent at the time of film formation -28-201139523 is easily removed from the composition, and thus a composition excellent in productivity is obtained. In the present invention, the boiling point refers to the boiling point in the atmosphere at a lamat. The non-melamine-based solvent preferably contains at least one organic solvent selected from the group consisting of a ketone solvent, an ether solvent, and a nitrile solvent. Since these solvents have a high polarity, they tend to have a composition excellent in storage stability. The ether solvent is preferably an acid having 3 or more and 10 or less carbon atoms, more preferably an ether having 3 or more and 7 or less carbon atoms. Preferred ether solvents are, in particular, mono or dialkyl ethers such as ethylene glycol, diethylene glycol monohydrate, ethylene glycol monoethyl ether, cyclic ethers such as dioxane or tetrahydrofuran (THF), and benzoic acid. An aromatic ether such as ether. Preferred among these are tetrahydrofuran. These ether solvents may be used alone or in combination of two or more. The ketone-based solvent is preferably a ketone having a carbon number of 3 or more and 10 or less, and more preferably a ketone having 3 or more carbon atoms from the viewpoint of boiling point and cost. Preferred ketone solvents, specifically acetone (bp = 5 7 ° C) methyl ethyl ketone (bp = 80 ° C), methyl - η - propyl ketone (bp = 105 ° C), methyl - is 〇-propyl ketone (bp = 116 ° C), diethyl ketone (bp = 101 ° C), methyl - η-butyl ketone (bp = 127 ° C), methyl-iso-butyl ketone ( Bt = 118 ° C), di-alkyl ketones such as methyl-sec-butyl ketone (bp = l 18 ° C), methyl-tert-butyl ketone (bp = l 16 ° C), etc. A cyclic ketone such as pentanone (bp = 130 ° C), cyclohexanone (CHN ' bp = 156 ° C), or cycloheptanone (bp = 185 ° C). In the above-mentioned vacuum drying which is excellent in drying property and productivity, it is preferable to selectively evaporate from the viewpoint of solvent which is almost completely removed from the coating film formed on the substrate. Cyclohexanone. -29- 201139523 These ketone solvents may be used alone or in combination of two or more. The nitrile-based solvent is preferably a nitrile having a carbon number of 2 or more and 10 or less, more preferably a nitrile having a carbon number of 2 or more and 7 or less. Preferred nitrile-based solvents are, for example, acetonitrile (bp = 8 2 ° C), propionitrile (bp = 9 7 ° C), butyronitrile (bp = l), isobutyronitrile (bp = 107 ° C), valeronitrile ( Bp = 140 ° C), isovaleronitrile (bp = 129 ° C), benzonitrile (bp = 1 91 ° C) and the like. Among these, from the viewpoint of a low boiling point, etc., acetonitrile is preferred. These nitrile-based solvents may be used alone or in combination of two or more. The ester solvent is preferably an ester having 3 or more and 10 or less carbon atoms, more preferably an ester having 3 or more and 6 or less carbon atoms. Preferred ester solvents are, for example, ethyl acetate (bp = 77 ° C), propyl acetate (bp = 97 t), -i-propyl acetate (bp = 89 ° C), butyl acetate (bp = 126 ° C). a cyclic ester such as an alkyl ester or a β-propiolactone (bp = 155 ° C). These ester-based solvents may be used alone or in combination of two or more. The amide-based solvent is preferably an amide having a carbon number of 3 or more and 10 or less, more preferably an amide having a carbon number of 3 or more and 6 or less. In the above, in the step (a), the film is dried once, and then dried twice to obtain a flatness of the film obtained from a guanamine-based solvent having a boiling point equal to or higher than the primary drying temperature. The viewpoint is preferable. Specifically, a hydrazine-based solvent having a boiling point of 20 or more is preferred. Preferred examples of the guanamine-based solvent are N,N-dimethylformamide, N,N-dimethylacetamidine. a cyclic guanamine such as a alkyl guanamine such as an amine (DMAc), 1,3-dimethyl-2-imidazolidinone or N-methyl-2-pyrrolidone (NMP). N-methyl-2-pyrrolidone and N,N-dimethylacetamide are left in a vacuum drying or one drying after evaporation of a non-amine solvent, -30-201139523' at 200 ° C to 500 t In the case of drying twice, it is preferable to maintain the evaporation rate of the smoothness of the surface of the coating film, etc., and it is more preferable to use N-methyl-2-pyrrolidone in consideration of environmental pollution or the like. The solvent mixture may be used alone or in combination of two or more. The mixed solvent is preferably a mixed solvent of N-methyl-2-pyrrolidone and cyclohexanone, and N-A from the viewpoints of drying property and productivity. A mixed solvent of -2-pyrrolidone and acetonitrile, particularly preferably a mixed solvent of N-methyl-2-pyrrolidone and cyclohexanone. Further, from the viewpoint of prevention of white turbidity of the obtained film, etc., N, N-dimethyl is preferable. The mixed solvent of the acetamide and the tetrahydrofuran. The mixed solvent is preferably used in an amount of 5 to 95 parts by mass, more preferably 25 to 95 parts by mass, based on 100 parts by mass of the mixed solvent. In the case of the physical properties of the obtained film, it is more preferably 35 to 65 parts by mass. The mixed solvent is preferably contained in an amount of 40 to 60 parts by mass based on 1 part by mass of the mixed solvent, and the mixed solvent contains the mixture. When the amount of the above-mentioned amide-based solvent is obtained, it is possible to obtain a composition which is excellent in productivity and excellent in productivity, and is excellent in film properties such as white turbidity and tensile strength, storage stability, and the like, and is excellent in adhesion and peeling property to a substrate. When the amount of the guanamine-based solvent is less than 5 parts by mass, the polylysine may not be dissolved, and the composition may not be obtained. When the amount of the guanamine-based solvent exceeds 95 parts by mass, the film may sometimes be Drying speed when forming a film The amount of the component (B) and the component (A) in the reaction liquid is preferably 5 to 30% by mass based on the total amount of the reaction liquid. The polyamic acid is the component (A) and the component (B). It is preferable to carry out the reaction in a range in which the ratio (input ratio) is a molar ratio of (A) component to (B) component ((B) -31 - 201139523 component / (A) component) is 0.8 to 1.2. The reaction is preferably carried out in the range of 0.95 to 1.0. When the molar ratio of the (A) mercapto compound to the (B) imido group formation is less than 0.8 equivalents, or more than 1.2 equivalents, the molecular weight sometimes decreases to form a polyazide. The amine film is difficult. The composition of the polyamic acid and the organic solvent obtained by the above reaction can be used as the film forming composition. However, the film forming composition may also be a polylysine obtained by the above reaction. It is obtained by separating it into a solid form and then dissolving it in an organic solvent. The organic solvent to be redissolved is, for example, the same as the above organic solvent, and the mixed solvent is preferred. The method of separating the polyamic acid is, for example, a solution containing a polyamic acid, an organic solvent, or the like, which is added to a weak solvent such as methanol or isopropyl alcohol in the form of polyaminic acid to precipitate a polyamine or the like. A method in which polylysine is separated as a solid fraction by filtration, washing, drying, or the like. Polylysine refers to an acid having a structure containing -CO-NH- and -CO-OH, or a derivative thereof (for example, having -CO-NH- and -CO-OR (but R is an alkyl group, etc.) Constructor). Polylysine is dehydrated by heating, such as -CO-NH - and OH of -CO-OH (OR separation of -CO-NH - and -CO-OR) into a chemical structure having a ring shape (-CO-N-CO- (hereinafter also referred to as yttrium ring structure)) polyimine (the structure containing -CO-NH- and -CO-OH, or -C0-NH_ and _ The structure of CO_〇r (but r is an alkyl group or the like) is also called a proline structure. The polyamine acid is preferably a concentration of a polyoxonium compound of 3 to 50% calculated by the following formula. 5 to 4 0% are better, and 8 to 3 0% are better. Polyxanthene concentration [unit: %] = (polyoxyl compound weight - 32 - 201139523) / {( (A) total mercapto compound weight) + ( (B) total imine group forming compound weight) The "weight of the polyoxymethylene compound" means the total weight of the compound having the structural unit represented by the above formula (1). The weight average molecular weight (Mw) of the polyamic acid is preferably 10, 〇〇〇 ~1,000,000' is more preferably 10,000 to 200,000, still more preferably 20,000 to 150,000. The number average molecular weight (?n) is preferably from 5,000 to 10,000,000, more preferably from 5,000 to 50,000, and particularly preferably from 20,000 to 20,000. When the weight average molecular weight or the number average molecular weight of the polyamic acid does not reach the above lower limit, the strength of the coating film may be lowered. Further, the linear expansion coefficient of the obtained polyimide film is sometimes increased to more than necessary. When the weight average molecular weight or the number average molecular weight of the polyamic acid exceeds the above upper limit, the viscosity of the composition for forming a polyimine film is increased. Therefore, the composition is applied to the support, and the film is formed when the film is formed. The amount of the polyamic acid of the composition is small, and the film thickness accuracy such as the flatness of the obtained coating film may be deteriorated. The molecular weight distribution (Mw/Mn) of the polyamic acid is preferably from 1 to 1 Torr, more preferably from 2 to 5, particularly preferably from 2 to 4. The weight average molecular weight, number average molecular weight, and molecular weight distribution are the same as those measured in the examples. The viscosity of the polyimine-based film-forming composition varies depending on the molecular weight or concentration of the poly-proline, and is usually 500 to 500,000 mPa·s, preferably 1,000 to 50,000 mPa·s. When it is less than 500 mPa·s, the poor retention of the composition in the film formation may sometimes flow out from the support. When the thickness exceeds 500,000 mPa·s, the viscosity is too high, and the adjustment of the film thickness is difficult. In some cases, the shape of the polyimide film is difficult to be -33-201139523. In the viscosity of the above-mentioned composition, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., viscosity meter MODEL RE 100), which is measured at 25 ° C in the atmosphere, is used in the composition of the polyimine film forming composition. The concentration of the proline is preferably adjusted to have the viscosity of the composition in the above range, and is also preferably from 3 to 60% by mass, preferably from 5 to 40% by mass, more preferably 1 due to the molecular weight of the poly-proline. 〇~40% by mass, particularly preferably from 10 to 30% by mass. When the amount is less than 3% by mass, there is a problem that thick film formation is difficult, productivity is poor, pinholes are likely to occur, and film thickness accuracy such as flatness is poor. On the other hand, when it exceeds 60% by mass, the viscosity of the composition is too high, and a film may not easily form, and a polyimide film which lacks surface smoothness may be obtained. When the viscosity of the polyimine-based film-forming composition and the concentration of the poly-proline in the composition are within the above range, the composition can be applied to a support by using a slit coating method which is excellent in productivity and the like. In the form of a film, the polyimide film having excellent productivity and short film thickness can be formed in a short period of time. The polyimine film-forming composition may contain a partially ruminated imidized polyamine. The partially ruthenium imidized polyamine is a method of heat treatment using a dehydrating agent (chemically hydrazide) or a solution at a temperature of about 160 to 220 ° C The synthesis can be carried out by partial cyclization or the like by heating at a lower temperature. Therefore, it is preferably a chemical moiety which is imidized by chemical imidization. The dehydrating agent may, for example, be an acid anhydride such as acetic anhydride, propionic anhydride or benzoic anhydride, or an acid chloride such as these compounds, or a carbodiimide compound such as dicyclohexylcarbodiimide-34-201139523. When the chemical moiety is imidized, it is preferably heated at a temperature of from 60 to 120 °C. When the hot portion is imidized, the water produced by the dehydration reaction is excluded from the system while being preferably carried out. At this time, it is preferred to use a benzene, toluene, xylene or the like to azeotropically remove water. In the case of partial ruthenium iodide, a base catalyst such as pyridine 'isoquinoline, trimethylamine, triethylamine, hydrazine, hydrazine-dimethylaminopyridine or imidazole may be used as necessary. The dehydrating agent or the base catalyst is preferably used in the range of 0.1 to 8 mol per mol of the (Α) component. When partial oxime imidization is carried out, at least one of the functional groups involved in the cyclization reaction, such as -CO-NH- or -CO-OH, in the partial ruthenium-based polyglycolic acid, Specifically, in the total of the polyamine structure and the quinone ring structure, the ratio of the quinone ring structure (hereinafter also referred to as a ring closure ratio) is preferably 5 to 70 mol%. More preferably, it becomes 10 to 60% by mole, and is particularly good to be in a state of 20 to 50% by mole. A support for coating a composition for forming a polyimide film, for example, a germanium wafer, an alkali-free glass (plate), a polyethylene terephthalate (PET) film, or a polyethylene naphthalate Ester (ΡΕΝ) film, polybutylene terephthalate (ΡΒΤ) film, nylon 6 film, nylon 6,6 film, polypropylene film, polytetrafluoroethylene tape, glass wafer, glass (plate) (not Including alkali-free glass (plate), Cu board and SUS board. The alkali-free glass refers to a glass which does not contain an alkali component such as potassium or sodium. According to the method for producing a substrate of the present invention, a support such as a tantalum wafer or a non-inspective glass (plate) can be used for film formation. Such a support has a high dimensional stability under heating conditions of -35 to 201139523, and therefore, in step (a) or step (b), there is no dimensional change even if heated. Therefore, the polyimide film provided on the support has a small dimensional change and can easily form an element at a desired position. With such a support, it is possible to reduce the warpage or distortion of the substrate after removing the support. Therefore, it is preferable to form a film on such a support, and to form an element. A method of forming a coating film on a support by applying a composition for forming a polyimide film to a support, for example, a roll coating method, a gravure coating method, a spin coating method, a dip coating method, and a squeegee, A method of coating a mold, an applicator, a sprayer, a brush, a roll, or the like. The thickness or surface flatness of the film can be controlled by repeated coating. Among them, a slit coating method is preferred. The thickness of the obtained coating film after drying (including the thickness of the coating film of polyamic acid) is not particularly limited, and is, for example, 1 to 5 00 μm, preferably 1 to 45 0 μm, more preferably 1 to 250 μm, and even more preferably 2 to 150 μm. More preferably, it is 10~125μηι. The step of drying the coating film can be specifically carried out by heating the coating film. Heating the coating film allows the organic solvent in the coating film to be removed by evaporation. The heating conditions are not particularly limited as long as the organic solvent evaporates, for example, at 60 to 2 500 t, and heating for 1 to 5 hours. Further, the heating can be carried out in two stages. For example, after heating at 70 ° C for 30 minutes, heating at 120 ° C for 30 minutes, and the like. The heating atmosphere is not particularly limited, and it is preferably an atmosphere or an inert gas atmosphere, and particularly preferably an inert gas atmosphere. The inert gas is, for example, nitrogen, argon, helium or the like from the viewpoint of coloring property, preferably nitrogen. The above step (a) may be carried out by vacuum drying before or after the heating, to remove the organic solvent in the coating film. The true-36-201139523 air-drying system does not need to blow hot air or the like to the coating film formed on the support, and the solvent can be easily removed from the coating film, so that a polyimide film having excellent flatness can be obtained. The surface of the coating film of poly-proline is immobilized, and it is excellent in reproducibility to form a polyimide film having excellent flatness and a uniform film quality. In the vacuum drying, the pressure (decompression degree) in the apparatus in which the coating film is placed is 760 mmHg or less, preferably 100 mmHg or less, more preferably 50 mmHg or less, and particularly preferably 1 mmHg or less, and the pressure in the apparatus is preferably reduced. When the amount is more than 760 mmHg, the evaporation rate is remarkably slowed when the solvent is removed from the coating film after vacuum drying, and the productivity is sometimes poor. The vacuum drying system is carried out for 0 minutes at a pressure of 0 minutes, preferably from 0 to 60 minutes, more preferably from 〇 to 30 minutes, more preferably from 0 to 20 minutes. When it is less than 〇 minute, the drying is insufficient, and the surface of the coating film may not be fixed, and it is difficult to obtain a film having a uniform film quality. When the temperature exceeds 60 minutes, the film may be poorly produced. [Step (b)] Next, the coating film obtained in the step (a) is heated to obtain a polyimide film. In the step (b), the obtained coating film is subjected to dehydration cyclization (thermal hydrazine imidization) by, for example, heat treatment at 160 ° C to 350 ° C. The temperature at which the heat imidization is carried out is preferably 200 to 3 from the viewpoint of the peeling property of the substrate obtained by heating drying (the temperature at which the organic solvent is evaporated) in the above step (a) from the obtained substrate. 5 0 ° C, more preferably 23 0 to 270 ° C, more preferably 240 to 25 (TC. The temperature of the heat imidization is from the viewpoint of the peelability, particularly the glass transition of the polyimide film) The temperature is below. The total structure of the ruthenium amide structure and the quinone ring structure is 1 〇〇 Mo-37- 201139523 The ratio of the 'imine ring structure in the ear % is preferably 7 5 mol% or more. It is preferably 85 mol% or more, and particularly preferably 9 mol% or more. When the ratio of the quinone ring structure is less than 75 mol%, the water absorption of the polyimide film may become high. The polyimine film is composed of polyimine or the like, and the polyimide is measured by differential scanning calorimetry (DSC, temperature increase rate of 20. (: /min). The temperature ' is preferably 305 ° C or higher, more preferably 4 5 01 : or more. When the glass transition temperature of the polyimine is in the above range, the obtained The substrate exhibits excellent heat resistance. The concentration of the quinone imine of the polyimine obtained from polylysine is preferably 2.5 to 7.5 mmol/g when the ruthenium imidation ratio is assumed to be 100 mol%. Preferably, it is 3.0 to 6.0 mmol/g, more preferably 3.5 to 5.5 mmol/g. In the present invention, the thickness of the polyimine film (film) is preferably from 1 to 250 μm, more preferably from 2 to 150 μm. The glass transition temperature (Tg) of the polyimine film is preferably 350° C. or higher, more preferably 45° C. or higher, and has excellent glass transition temperature. [Step (c)] Next, an element is formed on the polyimide film obtained in the above step (b) to form a substrate. The formed element is, for example, an organic electroluminescence (EL) element or a thin film transistor ( A module such as a light-emitting element such as a TFT or a metal wiring or a semiconductor integrated circuit, etc. The organic-38-201139523 EL element, TFT element, etc. are formed on the polyimide film obtained in the above step (b). When a light-emitting element or the like is used, it can be used as a flexible display substrate or the like. When a module such as a wire or a semiconductor integrated circuit is used, it can be used as a substrate for flexible wiring, etc. A method of forming a TFT element is, for example, a sputtering method on the polyimide film obtained in the above step (b). After a film such as a metal or a metal oxide is formed, a gate electrode is provided by etching, etc., and a temperature at which a film such as a metal or a metal oxide is formed by a sputtering method or the like can be used for forming a polyimide film which can be used in combination. The composition, the support or the formed member is appropriately selected, preferably 210 ° C to 400 ° C, more preferably 220 to 3 70 ° C, still more preferably 23 0 to 3 5 0 ° C. Next, a gate insulating film such as a tantalum nitride film is formed on the polyimide film of the gate electrode by a plasma CVD method, for example. Further, an active layer made of an organic semiconductor or the like is formed on the gate insulating film by a plasma CVD method or the like. The temperature at which the film of the gate insulating film or the organic semiconductor is formed by a plasma CVD method or the like can be appropriately selected in combination with the composition for forming a polyimide film for forming a film, a support or a formed element, and is preferably 210. °C~400°C, more preferably 220~3 7 0°C, more preferably 230~3 5 0 °C. Then, a film of a metal or a metal oxide or the like is formed on the active layer by sputtering or the like, and then etching or the like is performed to provide a source electrode and a drain electrode. Finally, a tantalum nitride film or the like can be formed by a plasma CVD method or the like as a protective film to produce a thin film transistor element. The thin film transistor element of the bottom gate is described above, but the TFT element is not limited to this structure, and may be a top gate. The gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are formed of a conductive material. The conductive material is, for example, a metal or a metal oxide -39-201139523 or the like. Examples of metals are platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony,

Molybdenum, indium, aluminum, zinc, magnesium, and the like, and examples of metal oxides include ITO, IZO, ZnO, and 203η203. Further, in addition to the above, a conductive polymer can be used as the conductive material in consideration of adhesion to a polyimide film, and if a metal oxide is used, a transparent electrode can be formed, which is preferable. . Further, a method of forming an organic EL device is, for example, a method of forming an insulating layer, a first electrode, an organic semiconductor layer, a second electrode, and a protective layer from the film surface side on the polyimide film. Further, a method of forming a metal wiring, for example, a copper layer is formed on a polyimide film by lamination or metallization, and a metal wiring can be provided by treating the copper layer by a conventional method. In the case of lamination, for example, a metal foil such as a copper foil is heat-pressed on the film, and a copper layer can be provided. In the metallization method, for example, a sheet layer composed of a Ni-based metal bonded to the polyfluorene-based film is formed by a vapor deposition method or a sputtering method. Further, a copper layer having a predetermined film thickness can be provided by wet plating. Further, when the metallization method is used, the surface of the polyimide film may be modified in advance to exhibit affinity with metal. The polyimide film (thin film) is excellent in heat resistance and excellent in adhesion to a support. Therefore, when a device is formed on a film (film), a temperature range can be widened, and a substrate excellent in performance can be obtained. [Step (d)] -40 - 201139523 Next, the substrate obtained in the above step (c) is peeled off from the above support. Since the substrate obtained from the above polyimide film is excellent in peelability, the substrate can be easily peeled off from the support. For the peeling method, for example, the protective tape is adhered to the end portion of the substrate in advance. After performing the above steps (a) to (c), the protective tape is peeled off as a starting point to peel the substrate, or the end of the support is cut. As a starting point, a method of peeling off, or a method of immersing in a solvent such as water or alcohol, and the like are carried out. The temperature at the time of peeling is usually from 0 to 100 t, preferably from 10 to 70 ° C, more preferably from 20 to 50 ° C. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples. (1) Glass transition temperature (Tg) Using the films obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2, the film was measured at a temperature increase rate of 20 ° C/min using a Model 823 0 DSC measuring apparatus manufactured by Rigaku Co., Ltd. The glass transition temperature of polyimine. (2) Concentration of polyoxymethylene compound The concentration of the polyoxymethylene compound of the polyamic acid obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2 was determined by the following formula. Polyxanthene concentration [unit: %] = (weight of polyoxyl compound) / {((A) weight of total mercapto compound) + ((B) weight of total imine forming compound)}χ1〇〇 -41 - 201139523 Weight of polyoxyxide = weight of compound (Α·1) + weight of compound (B-1) (3) concentration of quinone imine, assuming that the imidization ratio is 190% by mole The molecular weight of the repeating unit in the polyimine obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2 is (molecular weight of the mercapto compound) + (molecular weight of the diamine) - 2 χ (molecular weight of water) get. This repeating unit has 2 quinone imine groups, so the yttrium imine group concentration of the polymers obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2 (assuming the oxime imidization ratio is 100 mol%) The theoretical 値) is obtained by the following formula: 醯 [醯 imine concentration] (unit: mmol / g) = 2 / { (molecular weight of mercapto compound) + (molecular weight of diamine) - 2x (water Molecular weight) Bu 1000 (4) Adhesion Agglomeration of the following Examples 1 to 16 or Comparative Examples 1 and 2 after the imidization step (250 ° C drying) was completed, and the mixture was cooled to room temperature. The support of the imide film was heated to 300 ° C for 30 minutes, and then cooled to room temperature for 30 minutes as one cycle. After repeating this cycle for 1 time, no peeling from the support was evaluated as [ ◎], after repeating this cycle 5 times, the peeler without the support was evaluated as [〇], and the peeler was found to be [called. (5) Peelability The following examples 1 to 16 or the imidization steps of Comparative Examples 1 and 2 (-42-201139523 2 50 ° C drying) were completed, and the polyimide film was completely peeled off from the support. The person's evaluation was [◎], which could be completely peeled off and a part of the residual peeling marks was evaluated as [〇], and some of them could not be peeled off, and the evaluation was [△], and it could not be fully peeled off, and the evaluation was [X]. (6) Film warpage The polyimine film obtained by the following Examples 1 to 16 or Comparative Examples 1 and 2, which was peeled off from the support, was cut into 40 × 40 mm, and warped (the obtained polyimine film was obtained). The film was placed on a horizontal substrate, and the separation distance between the film at the four corners of the film and the substrate was measured. When the average 値) of the film was less than 1.0 mm, the evaluation was [◎], and the warpage was 1.0 mm or more, which was less than 2.0. When it was mm, it was evaluated as [〇], the fin shape was 2.0 mm or more, and when it was less than 3.0 mm, it was evaluated as [Δ], and when the warpage was 3.0 mm or more, it was evaluated as [X]. (7) Weight average molecular weight The weight average molecular weight of the polyamines obtained in the following Examples 1 to 16 or Comparative Examples 1 and 2 was measured using a GPC apparatus manufactured by TOSOH Model HLC-8020. In the solvent, N-methyl-2-pyrrolidone (NMP) containing lithium bromide and citric acid was used to measure the temperature at 4 (polystyrene-converted molecular weight at TC) [Example 1] A thermometer, a stirrer, and a nitrogen introduction were installed. In a 300-mL four-necked flask of a tube and a cooling tube, a component (B-2): 2,2'-dimethyl-4,4'-diaminobiphenyl (hereinafter also referred to as "m-TB") is added. 6.07g (-43-201139523 28.6mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., 乂22-16608-3, number average molecular weight 4,400) 2.57g (0.6mmol Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") and 20 ml of tetrahydrofuran (hereinafter also referred to as "THF") were added, and the mixture was stirred until uniform. In the obtained solution, 6.36 g (29.2 mmol) of a component (A·2 ): pyromellitic acid dioxide (hereinafter also referred to as "PMDA") was added at room temperature, and stirring was continued for 24 hours at this temperature. Composition (poly-proline solution). Using one of the obtained compositions, the composition was isolated from poly-proline. The weight average molecular weight of the proline, the concentration of the polyoxygen oxide, and the concentration of the quinone imine (the theoretical enthalpy when the oxime imidization rate is 100 mol%). Next, the obtained polyaminic acid solution is spin coated. The cloth (rotated at 300 rpm for 5 seconds, and then rotated at ll rpm for 1 sec.) was applied to an alkali-free glass support, dried at 7 ° C for 30 minutes, and then dried at 120 ° C for 30 minutes. The film obtained by the ruthenium imidization step was further dried at 25 ° C for 2 hours, and then peeled off from the alkali-free glass support to obtain a polyimide film (film) having a film thickness of 30 μm (0_03 mm). Further, the polyimide-based film was evaluated for adhesion to the support, peelability, and warpage of the polyimide film. The results are shown in Table 1. [Example 2] Thermometer, mixer, nitrogen inlet tube, cooling tube -44 - 201139523 300mL four-necked flask, add (B-2) component: 2,2'-dimethyl-4,4 5 - one Η Co-benction 6.07g (28.6mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (Xin Yue Chemical, X22-1660B-3, number average Molecular weight 4,400) 2.57 g (〇.6 mmol). Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide was added and stirred until uniform. The obtained solution was added at room temperature (A). -2) Component: 6.36 g ( 29.2 mmol) of pyromellitic dianhydride, and stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at a random number of times and for a film having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 3] A (B-2) component: 2,2,-dimethyl-4,4'-di was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Aminobiphenyl 6.68 g (31.4 mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B-3, number average molecular weight 4,400) 1.40 g (0.3 Mmmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide and 20 ml of tetrahydrofuran were added and stirred until uniform. In the obtained solution, 6.13 g (31.8 mmol) of a component (A-2): pyromellitic dianhydride was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). The polyimine film was obtained by applying f to the film (film) having a film thickness of 〇_〇3 mm, except that the obtained polyamic acid solution was applied at an arbitrary number of revolutions and time -45-201139523. The physical properties of the obtained polyimine and polyimine film are shown in Table 1. [Example 4] In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube of 300 mL, a component (B-2): p-benzene (also referred to as "PDA") was added, and 1.42 g (13_1 mmol) and 2, 2' were added. -Phenylphenoxy)phenyl]propane (hereinafter also referred to as "BAPP 13.1mmol" and (B-1) component: two terminal amine-denatured sand oxygen (Xinhwa Chemical, X22-1660B-3, number average). 2.36 g (0.5 mmol). Next, 58 ml of N,N-dimethylacetamide and 20 ml of tetrahydrofuran were added to the flask, and the mixture was stirred. In the obtained solution, (A-2) component dianhydride was added at room temperature. 5.84 g (26.8 mmol), at this temperature, stirring was continued to obtain a composition (polyglycine solution). The obtained polyamic acid solution was obtained at an arbitrary number of revolutions to obtain a film having a film thickness of 〇3 mm (film). In addition, with the implementation of {, a polyimide film was obtained. The physical properties of the obtained polyimide and polyimine film were as shown in Table 1. [Example 5] A thermometer, a stirrer, and nitrogen were installed. Into a four-necked flask of 300 mL, a component (B-2) was added: J 1 was similarly operated with a diamine of an amine acid, a polyfluorene, and a cooling tube (hereinafter bis [4-(4-amine)) 5.39 g ( The amount of methylphenyl polycondensate is 4,400). After the generation, it is added until it is uniform: the mixture is mixed with pyromellitic acid for 24 hours, and the time is applied. The river 1 is also operated with the amine acid, polyfluorene, and cooling tube -46-201139523 4,4 '-Diaminodiphenyl ether (hereinafter also referred to as "ODA") 6.46 g (32.3 mmol) and (Β·1) component: both terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., Χ2) 2-1660Β-3, number average molecular weight 4,4〇〇) 1.43g (0.3mmol). Next, after replacing the inside of the flask with nitrogen, add 58 ml of N,N-dimethylacetamide and 20 ml of tetrahydrofuran, and stir until In the obtained solution, (A-2) component: pyromellitic dianhydride 7.1 lg (32.6 mmol) was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyproline). The solution was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at any number of revolutions and time to obtain a film (film) having a film thickness of mm3 mm. The physical properties of the obtained polyimine, polylysine, and polyimide membranes are shown in Table 1. [Example 6] A thermometer was installed and stirred. In a 300 mL four-necked flask of a mixer, a nitrogen introduction tube, and a cooling tube, a component (B-2): 6.04 g (28.4 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was added. And (B-1) component: a two-terminal amine-denatured methylphenyl polyfluorene (X22-9409, number average molecular weight 1,300) 2.36 g (1.8 mmol). Next, after nitrogen substitution in the flask, 5 ml of N,N-dimethylacetamide was added, and the mixture was stirred until uniform. In the obtained solution, (A-2) component: 6.60 g (30.3 mmol) of pyromellitic dianhydride was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). . A polyimide film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at a random number and time, -47-201139523 to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine and polyimine film are shown in Table 1. [Example 7] A (B-2) component: 2.1 g of 2,2' 4,4'-diaminobiphenyl was added to a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a 300 mL ( 30.2 mmol) and (B-1) terminal amino group-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-average molecular weight 3,000) 1.85 g (0.6 mmol). Next, after replacing nitrogen with nitrogen, 58 ml of hydrazine, hydrazine-dimethylacetamide was added, and the solution obtained by stirring was added, and 6.73 g (30.9 mmol) of the acid dianhydride of (A-2) component was added at room temperature. At this temperature, stirring was continued to obtain a composition (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was obtained in an arbitrary number of revolutions to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine and polyimine film are shown in Table 1. [Example 8] A (B-2) component: 2,2' 4,4'-diaminobiphenyl 6.29 g was placed in a three-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a 300 mL. (29.6mmol) and (B-1) terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X2 2- is the same as the acid, and the poly- oxime is the tube - dimethyl-minute: two ends 161B > The number of flasks into the sentence is: benzene is tetrazed with 2 4 hours of coating, the same operation of acid, poly- sputum but tube - dimethyl-minute: two 161A, number -48- 201139523 average molecular weight 1,600) 1.98 g (1.2 mmol). Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide was added, and the mixture was stirred until uniform. In the obtained solution, (A-2) component: 6.73 g (30.9 mm 〇l) of pyromellitic dianhydride was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyproline). Solution). The polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at an arbitrary number of revolutions and time to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 9] A (B-2) component: 2,2,-dimethyl-4,4'-di was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Aminobiphenyl 6.65 g (31.3 mmol). Next, after nitrogen substitution in the flask, 58 ml of hydrazine, hydrazine-dimethylacetamide was added, and the mixture was stirred until the same sentence. In the obtained solution, (A-2) component: 6.15 g (28.2 mmol) of pyromellitic dianhydride and (A-1) component: two-terminal anhydride denatured methyl polyfluorene (made by GELEST) was added at room temperature. DMS-Z21, number average molecular weight 7 〇〇) 2.1 9 g (3.1 mmol), stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at a random number of times and time to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and poly M imine films are shown in Table 1. -49-201139523 [Example 〇] In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, a component (B-2) was added: 2,2'-dimethyl-4 , 4'-diaminobiphenyl 6.59g (31.0mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1 660B-3, number average molecular weight 4,400 ) 1 · 3 8 g (0.3 mm ο 1 ). Next, after nitrogen substitution in the flask, 58 ml of hydrazine, hydrazine dimethylacetamide was added, and the mixture was stirred until uniform. In the obtained solution, a component (A-2): 7.03 g (31.4 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter also referred to as "PMDAH") was added at room temperature. Stirring was continued for 24 hours at the temperature to obtain a composition (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at a random number of times and time to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 1 1] In a 300-neck four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, a component (B-2) was added: 4,4,-diaminodicyclohexyl group. (hereinafter also referred to as "MBCHA") 6.64 g (31.6 mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1 660B-3, number average molecular weight) 4,400 ) 1.40g (〇-3mmol). Next, after nitrogen substitution in the flask, 58 ml of N,N-di-50-201139523 methyl acetamide was added, and the mixture was stirred until uniform. In the obtained solution, (6-2 g (3 1.9 mmol) of pyromellitic dianhydride was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). . A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary number of revolutions and time to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 12] A (B-2) component: 1,4-diaminocyclohexane (hereinafter also referred to as a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube) "CHDA") 2.87g (25.1mmol) and (B-1) component: a two-terminal amine-denatured methylphenyl polyfluorene (X22- 1 660B-3, number average molecular weight 4,400) 3.42g ( 〇.8mmol). Next, after nitrogen substitution in the flask, N,N-dimethylacetamide 58 ml' was added and stirred until uniform. In the obtained solution, (A-2) component: diphenyl-3,3\4,4'-tetracarboxylic dianhydride (hereinafter also referred to as "s-BPDA") 8.71 g (25.9) was added at room temperature. Methyl) 'At this temperature, stirring was continued for 24 hours to obtain a composition (polyglycine solution). A polyimide film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at an arbitrary number of revolutions and time to obtain a film (film) having a film thickness of 0·0 3 m. The physical properties of the obtained polyimine, poly-araminic acid, and polyiamine film are shown in Table 1. -51 - 201139523 [Example 13] In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a 300 mL, a component (B-2) was added: 2.94 g (26.2 mmol) of 1,4-second house and ( B-1) Component: a two-terminal aminophenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number 1,300) 2.5 6 g (2.0 mmol). Next, the flask was placed, and 58 ml of N,N-dimethylacetamide was added thereto, and the mixture was stirred until homogeneous. The component (A-2) was added at room temperature: diphenyl-3::carboxylic acid dianhydride 9.46 g (28.1 mmol), at this temperature, continued, the composition (polyglycine solution) was obtained. A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied in an arbitrary number of revolutions to obtain a film (film) having a film thickness of mm3 mm. The physical properties of the obtained polyimine and polyimine film are shown in Table 1. [Example 14] In a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a 300 mL, a component (B-2) was added: 4,4' 2,2'-bis(trifluoromethyl) Benzene (hereinafter also referred to as "TFMB (24.5mmol) and (B-1) components: two-terminal amine-denatured polyfluorene (Xinith Chemical's X22-9409, number average molecule: 2.03g (1.6mmol). Secondly' The flask was subjected to nitrogen substitution of 58 ml of N,N-dimethylacetamide, and the mixture was stirred until uniform. The resulting amine tube was substituted with an aminocyclohexyl modified methyl-average molecular weight nitrogen. The resulting 3', 4, 4'-four Stir the mixture for 24 hours, and operate the acid, polyfluorene cooling tube -diamine-") 7.85g methylphenyl 1,1,00 00), then add the solution -52-201139523 at room temperature Addition of (Ad) component: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "CBDA") 5.12 g (26.1 mmol), and stirring was continued at this temperature for 24 hours to obtain a composition. (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at a random number of times and time to obtain a film (film) having a film thickness of 〇3 nm nm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 15] A (B-2) component: 2,2'-dimethyl-4,4'-di was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Aminobiphenyl 6.34g (29.9mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (X22- 1 660B-3, number average molecular weight 4,400) 2.68g ( 0.6mmol). Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide was added, and the mixture was stirred until it became homogeneous. In the obtained solution, (A-2) component: 1,2,3,4-cyclobutanic acid dianhydride 5.98 g (30.5 mmol) was added at room temperature, and stirring was continued for 24 hours at this temperature. Composition (polyglycine solution). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyaminic acid solution was applied at a random number of times and time to obtain a film (film) having a film thickness of 〇3 mm. The physical properties of the obtained polyimine, polylysine, and polyamidimide films are shown in Table 1. [Example 1 6 ] -53- 201139523 A (B-2) component: 2,2'-dimethyl-4 was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. 4'-diaminobiphenyl 4.78g (22.3mmol) and (B-1) component: two-terminal amine-denatured methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1 660B-3, number average molecular weight 4,400) 5.16g (1.2mmol). Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide was added, and the mixture was stirred until it became homogeneous. In the obtained solution, (A-2) component: pyromellitic dianhydride 5·1 lg (23.4 mmol) was added at room temperature, and stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution). ). A polyimine film was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at a random number of revolutions and time to obtain a film (film) having a film thickness of 0.03 mm. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 17] The polylysine solution (composition) prepared in the above Example 1 was cast-coated on a non-alkali glass support by a spin coater to obtain a coating film thickness of 25 μm. The film was dried at 70 ° C for 30 minutes, and then dried at 12 (TC for 30 minutes) to obtain a coating film. Thereafter, the film obtained by the cyclization (hydrazylation) step was further dried at 250 ° C for 2 hours. A transparent conductive film (element) was formed on the surface of the obtained coating film by a sputtering apparatus under the argon atmosphere at a film formation condition of 23 ° C for 5 minutes. The target material was ITO. The specific resistance of the substrate obtained was 値2χ10·4 (Ω·cm). The polyimide film provided with a transparent conductive film is peeled off from the alkali-free glass branch-54-201139523 to obtain a flexible substrate. The substrate can be completely peeled off from the support. [Comparative Example 1] A (B-2) component: 2,2'-dimethyl 4 was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. 4,-diaminobiphenyl 7.40g (34.9mm〇l). Secondly, after the nitrogen substitution in the flask, Ν,Ν-dimethyl Acetylamine 58 ml 'stirred until homogeneous. In the obtained solution, (A·2 ) component: pyromellitic dianhydride 7.60 g (34.9 mmoI) was added at room temperature, and stirring was continued for 24 hours at this temperature. The composition (polyamine acid solution) was obtained. The same procedure as in Example 1 was carried out except that the obtained polyaminic acid solution was applied at an arbitrary number of revolutions and time to obtain a film (film) having a film thickness of 〇3 mm. The polyimine film was obtained, and the physical properties of the obtained polyimine, polylysine, and polyimine film were as shown in Table 1. [Comparative Example 2] A thermometer, a stirrer, and a nitrogen introduction were installed. A 300 mL four-necked flask of a tube and a cooling tube was added with a component (b-2): 2.25 g (22.5 mmol) of 2,2,-bis[4-(4-aminophenoxy)phenyl]propane. After replacing the inside of the flask with nitrogen, 58 ml of hydrazine, hydrazine-dimethylacetamide was added, and the mixture was stirred until homogeneous. In the obtained solution, (A_2) component was added at room temperature: pyromellitic dianhydride 2.95 g ( 13.5 mmol) and 4,4,- oxydiphthalic dianhydride (hereinafter also referred to as "ODPA") 2.80 g (0.9 mmol), and the temperature is -55-201139523, stirring is continued 24 When the film (thickness) having a film thickness of mm3 mm was obtained by coating the obtained polyamic acid solution at an arbitrary number of revolutions and time to obtain a film (film) having a film thickness of 〇3 mm, and Example 1 In the same manner, a polyimide film was obtained, and the physical properties of the obtained polyimine, polylysine, and polyimine film were as shown in Table 1. ° -56 - 201139523 s rent-sensitive 骟 ◎ ◎ 〇〇 ◎ ◎ 〇〇〇〇〇 ◎ ◎ ◎ ◎ <X 1 peelability ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 O ◎ ◎ ◎ ◎ < 〇X Adhesiveness ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Ο o ◎ ◎ ◎ ◎ 〇 ◎ ◎ Film appearance m • mi transparent uniform 1 welcoming m welcoming mm Item S mmmm JjT m ϋΓ ST m ϋΓ ST Helmet m m JIT 驭s OUT m ϋΓ ίΓ Helmet mm ^ Μ :4.18 | 1 4.18 J (SB I » CO t- r-» Γ 4.35 1 ? | 4.45 | l«2 J 1 4.52 J | 4.60 | I 3.99 IL«? j δ I 4-38 I ο u> I 3.18 I Polyoxane concentration [%] Bu _ 5 C9 〇> ! 15.8 | CO 〇» 1 15.7 I rp csi CNJ ci CO 〇> 5 | 22.8 | 1 13.6 j a> 丨34.3 1 o ο Tg of polyimine (°C) ! >350 | 1 >350 1 ! >350 | [>350 Ί I >350 | I >350 II &gt ;350 | Γ >350 1 Γ >35(ΓΊ 1 >350 1 I >350 | | >350 | | >350 | I >350 | | >350 | Γ >350 1 I >350 | s CM Polymethane Mw Γ 95,000 | ο ο σ» Γ 84,000 | o 〇 _ O o 〇o CO I 83,000 | O o OO CO | 94,000 I 1 72,000 Π I 65,000 | O os | 82,000 · | | 76,000 | I 69.000 I ο 1 〇> 1 101,000 I 〇§ ci c〇1 iDMAc/THFl 1 DMAc 1 |DMAc/THF| iDMAcAHF l |DMAc/THF| I DMAc | I DMAc II DMAc | | DMAc 1 1 DMAc 1 | DMAc | I DMAc | 丨DMAc I | DMAc | | DMAc I 1 DMAc 1 | DMAc | | DMAc | (B-1) 1X22 -1660B-3 1 1 Χ22-1660Β-3 | 1 X22-1660B-3 | 1 Χ22-1Θ60Β-3 | I X22-1660B-3 | I X22-9409 | | X22-161B | | X22-161A | 1 X22 -1660B-3 | I X22-1660B-3 | IX22-1660B-3 | | X22-9 Overview 1 | X22-9409 | I X22-1660B-3 | 1 Χ22-1660Β-3 I 1 (B-2) 1_ | BAPP | | ODA | IMBCHAl I BAPP ] | m-TB 1 I m-TB | I m-TB II PDA II m-TB | | m-TB | I m-TB I | m-TB | I m-TB I | CHDA 1 "CHDA j I TFMB | i m-TB | 1 m-TB | I m-TB | (A-1) 1 DMS-Z21 | 1 (A-2) 1 1_ I ODPA | | PMDA | I PMDA | | PMDA | | PMDA I PMDA | | PMDA II PMDA ] I PMDA I | PMDA | IPMDAHj I PMDA I |s-BPDA| |s-BPDA| I CBDA I 1 CBDA 1 1 PMDA | I PMDA | | mm Μ 1Example 2] mm inch m grip K vr> 匡m peo omm K grip K 00 1 撢Os grip tilt 0 1 m grip i grip 飘 c〇| grip im lion VO im 御 v〇im I comparison Example 1 1 m ±3 -57- 201139523 (1 Weight average molecular weight (Mw), number average molecular weight (?n), and molecular weight distribution (Mw/Mn) The weight average molecular weight (Mw) and number average molecular weight of the polylysine obtained in the following Examples 18 to 27 and Comparative Example 3. (Μη) and molecular weight distribution (Mw/Mn) were measured using a HPC-8220 GPC apparatus (protective column: TSK guard colomn ALPHA column: TSKgelALPHA - Μ, developing solvent: ΝΜΡ) manufactured by TOSOH. (2) Storage stability at -15 °C The varnish (polyimine film-forming composition) obtained in the following Examples 18 to 27 and Comparative Example 3 was stored at -15 ° C for 48 hours. By visual inspection, those who were transparent and free of sediment were evaluated as 〇, and those who were opaque and precipitated were evaluated as X. (3) Varnish viscosity Using the following varnishes of Examples 18 to 27 and Comparative Example 3, 1.5 g of varnish was used to measure the varnish viscosity at 25 t. Specifically, it was measured using a Toki Shoji viscometer MODEL RE 100. (4) The coating film after vacuum drying was fixed in the central portion of the coating film of the glass-attached support after vacuum drying, which was obtained in the following Examples 18 to 27 and Comparative Example 3, and the center portion of the glass support. Place the support with the coated film upright for 1 〇. When there is no change in the height of the marking line on the coating film and the marking line on the glass support, it is judged that the fixing is -55-201139523. (5) Polymer (poly-proline) concentration after vacuum drying The concentration of the polymer (poly-proline) in the vacuum-dried coating film obtained in the following Examples 18 to 27 and Comparative Example 3 was The formula is calculated. Varnish weight after coating = weight of glass support after varnish coating - polymer concentration before varnish coating, polymer concentration (%) = total amount of input monomer / (input monomer amount + total amount of input solvent) xl 00 polymer weight after coating = varnish weight after coating X polymer concentration at input (%) film weight after vacuum drying = glass support weight of coated film after vacuum drying - glass support before varnish coating Polymer concentration after vacuum drying (%) = (weight of polymer after coating / weight of film after vacuum drying) χ1 00 (6) Solvent composition ratio after vacuum drying The following Examples 18 to 27 and Comparative Examples 3 The solvent composition ratio in the obtained coating film after vacuum drying is calculated according to the above formula and the following formula. Solvent weight after coating = weight of varnish after coating - weight of polymer after coating, weight of non-amined solvent after coating = weight of solvent after coating X input of non-amined solvent (non-amine in mixed solvent) Solvent ratio) (%) Solvent weight after vacuum drying = film weight after vacuum drying - after coating poly-59-201139523 Compound weight by vacuum drying After evaporation solvent weight = solvent weight after coating _ vacuum drying solvent Weight of non-melamine solvent after vacuum drying = weight of non-amined solvent after coating - composition ratio of solvent-weight non-amined solvent after evaporation by vacuum drying (%) = (non-guanamine after vacuum drying) Solvent weight / solvent weight after vacuum drying X 1 00 ) Composition ratio of guanamine solvent (%) = 1 〇〇-non-amine amine solvent composition ratio (solvent in vacuum solvent evaporation is defined as a mixed solvent) The solvent having the lowest boiling point (non-melamine-based solvent)) (7) Adhesiveness after one-time drying (Tack) The coating film obtained by drying each of the following Examples 18 to 27 and Comparative Example 3 was made of a metal scraper. Friction by force, the film does not move. No significant viscosity, the coating film were evaluated as mobile adhesion. (8) Optical characteristics The coating film formed on the glass support after one drying and the second drying obtained in the following Examples 18 to 27 and Comparative Example 3 was measured for Haze according to the viscous test method of JIS K7 105, respectively. Haze). Specifically, it was measured using a SC-3H type Haze meter manufactured by SUGA Testing Machine Co., Ltd. (9) Glass transition temperature (Tg) -60-201139523 The polyimine film obtained in the following Examples 18 to 27 and Comparative Example 3 was peeled off from the glass support, and the polyimide film after peeling was used. The Thermo Plus DSC 823 0 (differential scanning calorimetry) manufactured by Rigaku was measured at a temperature rise rate of 20 ° C / min and a range of 40 to 450 ° C under nitrogen. (1 〇) Line Expansion Coefficient The polyimine film obtained in the following Examples 18 to 27 and Comparative Example 3 was peeled off from the glass support, and the sequined imide film after peeling was Seiko Instrument SSC/5200. The measurement was carried out at a temperature rising rate of 6 ° C / min and 25 to 3 50 ° C. The linear expansion coefficient of 100 to 200 ° C was calculated from the measurement results. (1 1 ) Residual stress of the coating film The varnish obtained in the following Examples 18 to 27 and the comparative example 3 was used in a ruthenium wafer sheet (manufactured by KLA Co., Ltd.) for use in the measurement of residual stress, and was made by Chichibu Electronics Co., Ltd. A film of 30 μm after drying was formed twice on the thickness = 300 μm, diameter = 4 Å, and warpage was measured by laser, and the stress of the coating film was calculated by the following formula. From the viewpoint of suppressing the warpage of the obtained polyimide film, the residual stress of the coating film is preferably 10 MPa or less, more preferably 5 MPa or less. [Equation 1] Eh2 6 (lv) Rt σ: residual stress of the film t: thickness of the film R: radius of curvature measured h: thickness of the substrate E: Young's modulus of the substrate v: poisson of the substrate -61 - 201139523 (1 2 ) oxime imidization ratio The ruthenium imidization ratio of the polyimine in the polyimine film obtained after drying twice in the following Examples 18 to 27 and Comparative Example 3 Quantification was carried out according to the following method using FT-IR (manufactured by Thermo F i sher Sci ific ific, Thermο NIC OLET6 7 00). The peak of the peak of the NH variable angle vibration (1520CHT1) from the poly-proline acid and the peak of the aromatic asymmetric three-received 'CH-external angle-angle vibration (990(:11^1) area with the Gaussian distribution, the peak Separation 'quantitative. Determine the peak area ratio of the poly-proline before the drying (the peak area of 990 CHT1 / the peak area of 1 5 20 (: 1 ^ 1) and the peak area ratio after 2 drying, use The oxime imidization ratio was calculated by the following formula: 醯 imidization ratio (%) = (peak area ratio after 1 - 2 drying / peak area ratio before 1 drying) x 1 〇〇 (13) poly 醯For the strength of the imide film, the polyimine film having a film thickness of 30 μm was obtained by peeling off the dried glass support obtained in the following Examples 18 to 27 and Comparative Example 3 using the dumbbell No. 7 of JIS K6 25 1 The film was subjected to a tensile test at 23 ° C and a speed of 50 mm/min, and the tensile strength, tensile strength, and elastic modulus were measured. (1 4 ) Peeling property with the glass support The following Examples 18 to 27 and comparison were carried out. The 3 〇μπι coating film of the glass support after the second drying obtained in Example 3 was cut into a width l〇mmx length 50 mm by a cutter, -62-201139523 After peeling to a length of 20 mm, the peel strength was measured at an angle of 180 degrees and at a speed of 50 mm / mi η. (15) Warpage of the polyimide film was carried out in the following Examples 1 to 2 7 and Comparative Examples (3) The 30 μηι coating film of the glass-supported body obtained after the second drying was cut into a width of 60 mm×60 mm by a dicing blade, and then the four ends were floated upward to calculate an average enthalpy. [Example 18] A thermometer and a nitrogen introduction tube were attached. And stirring the leaf three-necked flask, adding m-triazine (m-TB) 45.23099g (0.2 1 3 06 mol), and dimerizing the side chain phenyl group. X-22- 1 660B-3 [9.4694g ( 0.002 1 5 2 1 mο 1 )], the concentration of poly-proline in the varnish is 14%, and dehydrated N-methyl-2-pyrrolidone (NMP) is added. 307g and 307g of dehydrated cyclohexanone (CHN), stirred for 10 minutes until m-TB and X-22-1 660B-3 are completely dissolved. Add pyromellitic dianhydride (PMDA) 22_6498g (0.10384mol) and stir for 30 minutes. After that, add PMDA22.6498g (0.103 84mol) to the end of the reaction for 60 minutes to complete the reaction, followed by a filter made of polytetrafluoroethylene (aperture ΐμη Precision filter for making a varnish (PMDA / (mTB + X-22- 1 660B-3) = 0.96 5 eq). The varnish properties are shown in Table 2. X-22-1 660B-3 : Shin-Etsu Chemical Co., Ltd., two-terminal amine-denatured side chain phenyl-methyl polyoxyl (composed of H-NMR methyl group and phenyl molybdenum) The ratio is 75: 25, the number average molecular weight is 4,400, and the catalogue is: Shin-Etsu-63-201139523 Chemical Industry Co., Ltd., Polyoxane Business Unit Headquarters Reference Poly Oxygen News No. 122, July, 2002) Glass support (width: 300mmx Length: 3 50 claws 111> <Thickness: 〇.7 mm) Fixed to a control coating machine set vertically to the gravity. After drying twice, the film thickness was 30 μm, the gap interval was set to 405 μm, and the varnish was 12 g to the glass. The center of the support body is formed into a coating film having a width of 200 mm x length: 220 mm. Thereafter, the pressure was reduced to 0.1 mmHg after vacuum drying for 10 minutes at 25 t using a vacuum dryer, and then returned to normal pressure (760 mmHg) to complete vacuum drying. The physical properties of the coating film after vacuum drying are shown in Table 2. The film after vacuum drying is transparent, the coating film is fixed, and there is no dripping of liquid droplets. After vacuum drying, the peak regions of 1520 CHT1 and 990 (:1^1) of the polyglycolic acid were vacuum dried at 5.09 and 6.89, respectively, and then dried in a hot air dryer at 130 ° C for 1 〇 minute. The results of the physical property evaluation of the coating film sample after the secondary drying are shown in Table 2. Next, the drying was performed twice at 300 ° C for 1 hour. The evaluation results are shown in Table 2. The polyimide film was obtained without warping. The Tg is also a tough polyimine film having a heat resistance of 45 (TC or more, excellent heat resistance, transparency, smoothness, and low linear expansion coefficient. Further, the obtained coating film has a high drying speed, and is 1 In the secondary drying and the secondary drying, the adhesion to the Boma support is excellent, and the polyimide film obtained after the second drying is excellent in peelability from the glass support. [Example 19] • 64 - 201139523 In Example 18, except that the amount of use of "ΤΒ, X-22-1660B-3, and PMDA was changed as shown in Table 2, the same operation as in Example 8 was carried out. The results are shown in Table 2. Heat resistance, It is excellent in transparency and smoothness, and has no warpage or tough polyimide film. In addition, the obtained coating film is dried at a high speed. It is excellent in the adhesion to the glass support in the i-time drying and the second-time drying, and the polyi-imide film obtained after the second drying is excellent in the releasability from the glass support. [Example 20] In Example 18, except that the amounts of use of m-TB, X-22-1 660B-3 and PMDA were changed as shown in Table 2, the same operation as in Example 8 was carried out. The results are shown in Table 2. Heat resistance was obtained. It is excellent in transparency and smoothness, and has no warpage or tough polyimide film. In addition, the obtained coating film has a high drying speed, and is adhered to the glass support in i-time drying and secondary drying. It is excellent in the properties, and the polyimide film obtained after the second drying is excellent in peelability from the glass support. [Example 21] In Example 18, except that 111-butyl 832.56478 § and 4,4'-diamine were used. The use amount of 7.8760 g of the substituted diphenyl ether (ODA) instead of m-TB45.23099g - X-22- 1660B-3 and PMDA was changed as shown in Table 2, and the results were as shown in Table 2. A polyimide film having improved heat resistance, transparency, and smoothness and having no warpage can be obtained, and the obtained coating film system can be obtained. Dry-65-201139523 Fast speed 'In the first drying and the second drying, the polyimine film obtained after two times of drying with excellent glass support is excellent in glass peeling property. [Example 22] Example 18 In addition to hydrazine-based solvent, hydrazine-di(DMAc) was used in place of hydrazine, and the same operation as in Example 18 was carried out. It was excellent in heat resistance, transparency, smoothness, and low tensile modulus. Further, the obtained polyimine film has a high drying rate, and is excellent in glass branching property in primary drying and secondary drying, and the polyimide film obtained by drying twice is excellent in peelability. [Example 23] In Example 18, except that the non-amine-based solvent was used, CHN307g was used, and the amount of NMP used was changed to the same as shown in Table 2 except that the same procedure was carried out. The results are shown in Table 2. A tough polyimide film which is excellent in heat resistance, transparency, smoothness, and lowness of onset can be obtained. Further, the obtained drying speed is fast, and it is excellent in glass branching in one drying and two drying, and the polyimide film obtained by drying twice is excellent in peeling property. Methyl acetamide of the close-contact glass support of the body. The results are shown in Table 2. The warp and the swell of the coating film are replaced by the dense glass support nitrile 430g, and the examples are warped and inflated. Coating film dry support dense glass support -66-201139523 [Example 2 4] In Example 18, except for the use of Shin-Etsu Chemical, the two-terminal amine-denatured side chain methyl type polyoxyl KF8010 (Number average molecular weight (44 Å, m = 58)) 2.8408 g and X22-1660B-3 (6.6286 g) were substituted in the same manner as in Example 18 except that χ_22-1660Β-3 (9.4694 g) was used. The results are shown in Table 2. A tough polyimide film which is excellent in heat resistance, transparency, and smoothness, and has no warpage and a low linear expansion coefficient can be obtained. Further, the obtained coating film has a high drying rate, and is excellent in adhesion to the glass support in one drying and two dryings. The polyimine film obtained after drying twice is peeled off from the glass support. Excellent sex. [Example 2 5] The same procedure as in Example 18 was carried out in the same manner as in Example 18 except that the amounts of NMP and CHN used were as shown in Table 2. The results are shown in Table 2. A polyimide film which is excellent in heat resistance and smoothness and which is free from warpage and toughness can be obtained. Further, the obtained coating film has a high drying speed, and is excellent in adhesion to a glass support in one drying and two drying, and the polyimine film obtained after drying twice is peeled off from the glass support. Excellent sex. [Example 2 6] In Example 18, the same operation as in Example 18 was carried out except that ethylene glycol monomethyl ether was used instead of chn. The results are shown in Table 2. A polyimide film having excellent heat resistance, transparency, and smoothness, and having no warpage or a strong weft edge can be obtained. Further, the obtained coating film has a high drying speed, and is excellent in adhesion to the glass support in the -67-201139523 drying and secondary drying, and the polyimide film obtained after the second drying is made of glass. The support is excellent in peelability. [Example 27] In Example 18, except that NMP614 was used instead of NMP3 07g and CHN3〇7g, the same operation as in Example 18 was carried out. The results are shown in Table 2. A polyimide film which is excellent in heat resistance and smoothness and has no warpage can be obtained. In addition, the obtained coating film is excellent in adhesion to the glass support in one drying and two dryings. The polyimide film obtained by drying twice is excellent in peelability from the glass support. [Comparative Example 3] In Example 27, the same operation as in Example 27 was carried out except that χ·22_166〇Β-3 was not used, and the amounts of use of m_TB and PMD A were changed as shown in Table 2. The results are shown in Table 2. The varnish obtained in Comparative Example 3 had a slow drying rate. Further, after the secondary drying, the residual stress increased, and the polyimide film which was peeled off by the glass support exhibited a large warpage. -68- 201139523 r> CO rj r> CM s' I 4400 2200 ! I ! 49.7β66 l_ 614 1 丨110000 1 37900 1 3 0 I 250000 | 胆 ηη g 〇1—1—30 I e CN G Γ; - S: m CN 1 100 I -3.5 eo ο cc up to 4501C, not detected by m CM O 45.23099 I X-22- 1660B-3 4400 I 2200 1 ,9.4694 | I to σ> Cl in 1__ 814 _ I <β· 1 73500 1 I 24500 1 L 3.00 I 0 1 4300 I seedling rj〇〇 〇 g o CD a rj - m m, CS α <〇rg iO e (ΟCO to 45〇r, no CM is observed o 45.23099 I i 7 11 4400 \ 2200 I 5 9.4694 II '45.2896 1 307 1 r» n 46000 1 1 14400 IO ri X 3300 J g 晅aa C0 ο a **! Ο rs - W n P3 〇〇r· - s Ξ to 4501: not observed - do 45.23099Π X-22- 1660B-3 4400 | 2200 1 9.4694 1 I 45.2990 1 o 5 to 62000 1 ο w 2.44 IX 12000 1 ms S I__130___I om » ο cn - m -n 〇I 100 1 CJ - o α> Up to 450X: Not observed - ϋ o 5 45.23099 i X-22- 1660B-3 4400 1 2200 1 6,6286 1 KF8012 1 4400 1 1 2200 1 g Γ2·β4〇8 1 1 45.2996 1 5 CO Γ 307 | 713001 I 23200 I 3.07 I 0 1 4000 1 with ϋ m OJ CM & Γ5 ο om 3 ο r> - Miao 5 〇〇1 210 ' OB to 4501C, no CO do 45.23099 1 X-2Z-1660B-3 4400 | 2200 | 9.4694 1 1 (O σ>〇> CSJ JO _m_ § in ί 73000 1 I 24300 I f 3.00 Ί o I 6500 Ί Sleep o O 〇§ o 璀η 1 300 1 - m η η e C|J <» β> eo up to 450*C, Γ5 5 o 翠脑〇> g rs IA X-22- 1660B-3 4400 1 2200 1 9.4694 1 1 CD Oi in CM JO 307 1 g rj a 1 70000I I 21200 I o 1 5200 1 1 晅ss - 1_130_! m rj 1 300 - 粕Γ> ο ο ο ο ο 1 42.2528 1 % 96700 Ί I 35200 I "2) 5 I o I in 1 s eo L_132_I o 薜§ 1 5 ο CD s <〇η to 450T; so far, no σ»r> doa 38.91890 Π X-22· 1660B-3 4400 \ 2200 1 20.6Θ33 I 1 40.3978 1 1 -307 Ί 1 307 1 1 102000 1 I 32900 I o 12000 i ί s s βο LZ.130-H o to C«J 1 - grain Ν different α CO CO to 450 TC, not observed ο 5 o α> 42.67864 I X-22- 1660B-3 4400 I 2200 1 13.4707 I 1 43.8507 1 307 io' i OI 33770 I to P3 o 1 16000 IK s rs i__m_I a 雔eg 1 - m CSl ο oo ir> oi to 450X; until, no observation (Ο 5 o CO 45.23099 I X- 22- 1660Β·3 4400 1 2200 | 9.4694 I 1 45.2996 Ί 307 1 g 72400 1 22300__ 3.25 1 o 4200 I ίSi CD I__m_] o Grip f〇1 300 1 - Then Γ > CjJ σ> e to 450* 0, until the Γ 観 Γ Γ Γ MM MM MM MM MM MM MM MM MM MM MM MM MM MM a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a & im embed m 铤em ε &<〇 Θ Θ i m. Θ m 联 ® u ! £Γ β- 截 β I 65 m Θ ε <π Θ Θ m 0 联 PMDA 1 i CN i 揉 DMAci Boiling «=1660 1 1 i <*·> ά % m NJ 汽1 Q寒u 轾 I I Mw/Mn 1 by 琳趄 P 2 1 结妇海笔 1 a 珀辰味埋Η § im 味β 雔I 1 Miao Li Yue • MS | s Λ N 邮 n • M 徂 徂 1 1 1 1 I Μ 教 CS a class © hanging 1 culvert PI g £ 1 1 1 fiei want to cut m glass transition temperature § S3 i SI by Ban Ban Supports the irritating film, the warp monomer solvent, the poly-amic acid varnish, the vacuum drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying, the drying

Claims (1)

201139523 VII. Patent application scope: 1. A method for producing a substrate, comprising: (a) coating a support comprising a polyamine acid having a structural unit represented by the following formula (1) and an organic solvent; a step of forming a coating film containing a polyaminic acid by drying a composition for forming a quinone imine film, and (b) heating the coating film containing polyamic acid to obtain a polyimide film; c) a step of forming an element on the polyimide film, and (d) a step of peeling off the polyimide film forming the element from the support, [1] R1 - fsi - 0 - ( 1) I η R1 (In the formula (1), the plural R1 groups are each independently a monovalent organic group having 1 to 20 carbon atoms, and the η is an integer of 1 to 200). 2. The method for producing a substrate according to claim 1, wherein the polyamic acid is at least one mercapto compound containing (A) selected from the group consisting of tetracarboxylic dianhydride and the reactive derivative. The component (B) reacts with the component containing the imine group-forming compound and satisfies the following (i) and/or (Π), (i) the component (A) contains (A-1) having the above formula (1) ) A mercapto compound represented by the structural unit of the present invention. 70-201139523 (ii) The component (B) contains (II) an imine group-forming compound having a structural unit represented by the above formula (1). 3. The method for producing a substrate according to the second aspect of the invention, wherein the content of the imine group-forming compound having the structural unit represented by the above formula (1) in the above (B) component is relative to 100% by mass of the total amount of the component (B) is 5 to 70% by mass. 4. The method for producing a substrate according to claim 2, wherein the number average molecular weight calculated based on the amine valence of the imine group-forming compound having the structural unit represented by the above formula (1) (B-1) For 500~10,000. The method for producing a substrate according to any one of claims 2 to 4, wherein the polyamic acid is such that the component (A) and the component (B) are in the components (A) and (B). The molar ratio ((B) component / (A) component) is obtained by reacting in the range of 0.8 to 1.2. The method for producing a substrate according to any one of claims 1 to 5, wherein the organic solvent is selected from the group consisting of ruthenium, Ν'-dimethylimidazolidinone, γ-butyrolactone, Ν-methyl At least one solvent of the group consisting of -2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, tetrahydrofuran, cyclohexanone, acetonitrile, and ethylene glycol monoethyl ether contains 50% by weight or more based on the total amount of the organic solvent. 7. The method for producing a substrate according to any one of claims 1 to 6, wherein the polyimine of the polyimine film is measured by differential scanning calorimetry (DSC, temperature increase rate: 20 ° C) /min) The measured glass transition temperature was 350 ° C or higher. 8. The method of manufacturing a substrate according to any one of claims 1 to 7, wherein the heating in the step (b) is carried out in the range of 20 0 to 350 ° C, and It is carried out below the glass transition temperature of the polyimide film. 9. The method of producing a substrate according to any one of claims 1 to 8, wherein the support is a tantalum wafer or an alkali-free glass. A composition for forming a polyimine-based film, which is characterized in that the composition for forming a substrate of the method for producing a substrate according to any one of claims 1 to 9 is Further, the polyglycine and the organic solvent having the structural unit represented by the following formula (1) are contained, and R1 — fsi — (1) η Ri (in the formula (1), the plural R1 systems are each independently The number of carbon atoms is 1 to 20, and the η is an integer of 1 to 200. • 72- 201139523 Four designated representatives: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No 201139523 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no