TW201139519A - 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

201139519 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polyimide precursor, a film forming method comprising the composition and a resin composition. [Prior Art] In general, aromatic tetracarboxylic dianhydride and aromatic wholly aromatic polyimine have excellent mechanical properties due to their molecular rigidity, or their chemical properties, and strong chemical bonding. It can be used as a film, a coating agent, a molded part, or an insulation under the electrical, battery, automobile, and aerospace industries. However, when the above-mentioned polyimide polyimide is used to form a film on a support such as a glass substrate, there is a problem that the substrate or the film itself is warped when it is formed. Among them, Patent Document 1 discloses that P is contained. - a flexible polyimine precursor resin composition of a polyimine precursor synthesized from benzoic acid anhydride or the like. Further, the resin composition can be formed by coating on a glass substrate or the like, and can be made heat resistant. It is excellent in properties and has a low thermal expansion coefficient, and can be peeled off beautifully when it is peeled off from the substrate glass substrate during the formation of a circuit, etc. [Previous Technical Literature] The molecule obtained from the resin group diamine of the precursor is resonance heat resistance. Exfoliation of the polyimide film on the substrate and the S-biphenyl device substrate supporting substrate, which is widely used as a material in the field of the machine and the machine industry, by the 201139519 [ [Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-2 02 729. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION However, a coating film containing a conventional polyimide precursor and a composition thereof may be used. If the residual stress is large, the film with a low glass transition temperature. SUMMARY OF THE INVENTION An object of the present invention is to provide a film forming method which can easily produce a polyimide precursor having a film having a high yield and a low warpage, a resin composition, and a resin composition. Means for Solving the Problems The inventors of the present invention have completed the present invention by performing a detailed examination of a polyimine precursor having a specific structural unit in order to solve the above problems. The present invention provides the following [1]~ [12] [1] A polyimine precursor, which has the structural unit represented by the following formula (1) having the structural unit shown in 2), and the resin of the precursor may be sometimes The result of the precursor of the glass transition temperature, found that the acid) can be solved by the following formula (Ο 0

-R1——N- H /\ /n ROOC COOR

(In the formula (1), R each independently represents a hydrogen atom or a monovalent group having a -6- group, and R1 each independently represents a group selected from the group represented by the following formula (3), and each of R2 is independently selected from the group consisting of The base of the group shown by the formula (4), η represents a positive integer.) [Chemical 2]

(In the formula (2), the plural R5 each independently represents a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200) [Chemical 3]

(R°)a3 (R°)a3

(In (3), R3 each independently represents 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, a halogen atom, or an alkane. a hydroxyl group, a hydroxy group, a nitro group, a cyano group or a sulfo group, wherein the hydrogen atom of the alkyl group and the alkyl group may be substituted by a halogen atom, and D represents an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group or a decane group. The group, the decylamino group or the decyloxy group 'al each independently represents an integer of 1 to 3, and a2 each independently represents 1 or 2' a3. The independent table 201139519 shows an integer of 1 to 4, and e represents an integer of 〇3.

201139519 A polyimine precursor described in any one of [1]~[3] of at least one type of monomeric unit of the group. [5] The monomer is a polyimine precursor described in [4] of the compound represented by the following formula (5) or (6). 【化5】

(In the formulae (5) and (6), each independently represents a group selected from the group consisting of an ether group, a sulfate group, a ketone group, an ester group 'sulfonyl group, an alkylene group, a decylamino group, and a decyloxy group. At least one group of a group, R6 each independently represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group, and a hydrogen atom of the alkyl group may be substituted by a halogen atom, and 3 each independently represents an integer of 1 to 4.) [6] Weight average The polyimine precursor described in any one of [1] to [5;] having a molecular weight of 10,000 to 1,000,000. [7] A resin composition comprising the polyimine precursor described in any one of [6] and an organic solvent. [8] The resin composition according to [7], wherein the concentration of the polyimine precursor is from 3 to 60% by mass. [9] The organic solvent is contained in 201139519 [7] or [8] containing at least one solvent selected from the group consisting of an ether solvent, a ketone solvent, a nitrile solvent, an ester solvent, and a guanamine solvent. Resin composition. [10] The resin composition according to any one of [7] to [9], wherein the viscosity is from 500 to 500,000 mPa·s, as measured by an E-type viscometer (25 ° C). [11] The resin composition according to any one of [7] to [1]. [12] A step of applying a resin composition according to any one of [7] to Π 涂布 on a substrate to form a coating film, and a film removed by evaporating the organic solvent from the coating film Film formation method. [Effects of the Invention] The resin composition containing the polyimine precursor of the present invention and the precursor can easily produce a film having a high glass transition temperature and less occurrence of back warpage. In addition, when the resin composition containing the polyimide precursor of the present invention is coated on a substrate such as a glass substrate to form a film, the resin composition can be easily formed to have excellent adhesion to the substrate and peelability. membrane. MODE FOR CARRYING OUT THE INVENTION "Polyimide precursor" The polyimine precursor (polyglycine) of the present invention has a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2) The structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1) j ) · The polyimine precursor of the present invention is easily produced with high glass -10- 201139519 A resin having a small amount of residual stress and a small amount of anti-warpage, and a resin composition containing the polyimine precursor of the present invention is formed by coating a resin composition on a substrate such as a glass substrate. In the case of a film, a film excellent in adhesion and releasability to the substrate can be easily produced. The polyimine precursor of the present invention has a structure selected from the structural unit (2) and the following formula (3) and 4) The group of the group shown has a rigid skeleton portion containing a group selected from the group represented by the following formulas (3) and (4) and a soft skeleton portion containing the structural unit (2), and the rigid skeleton portion is formed into a sea portion. The soft skeleton is the microscopic phase separation structure of the island. Since the polyimine has the microscopic phase separation structure, the residual stress of the film is reduced. Therefore, the polyimide precursor of the present invention is a film which can obtain a small residual stress and suppress the occurrence of back warpage. In the polyimine precursor of the present invention, since m in the above formula (2) is 3 or more, the flexibility of the soft skeleton portion is higher, and the micro phase separation structure is more likely to be formed, and the residual stress of the film is further reduced. Further, in the present invention, the microscopic phase separation is performed on the sea portion formed by the rigid structure portion, and the island portion formed of the soft skeleton portion is dispersed to a size of 1 nm to 1 μm. Further, in the present invention, the so-called " The adhesiveness is a property in which the coating film (film) and the substrate are not easily peeled off when the film is formed on the substrate or when a device such as a metal or the like is formed on the film, and the "peelability" is For example, when the substrate is to be peeled off (when a film is peeled off from the substrate, etc.), the peeling marks are less likely to peel off the film from the substrate. In addition, the "anti-warping" is to determine the curl of the film by visual observation. The "residual stress" is a coating of a resin composition containing the polyimide precursor of the present invention on a substrate such as a glass substrate. The stress remaining inside the film after the film is formed is an indicator of the "anti-warping" caused by the film. Specifically, the measurement can be carried out by the method described in the following examples. 【化6】 0 0.

In the above formula (1), R each independently represents a hydrogen atom or a monovalent organic group, preferably an argon atom, and R1 each independently represents a group selected from the group represented by the following formula (3), and R2 each independently represents a group selected from the group consisting of The group of the group shown in the formula (4). η represents a positive integer, preferably an integer of 1 to 2500. In the above formula (1), R is preferably a monovalent organic group, and a monovalent organic group having 1 to 2 carbon atoms is preferred. Further, "carbon number 1 to 20" means "carbon number 1 or more" and carbon number 20 or less". The same description in the present invention means the same meaning. Examples of the monovalent organic group having 1 to 20 carbon atoms in the above-mentioned R include a monovalent hydrocarbon group having 1 to 20 carbon atoms, etc., and a hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include an alkyl group having 1 to 20 carbon atoms. The alkyl group having a carbon number of 1 to 20 is preferably an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t- Butyl, .pentyl, hexyl and the like. In the above formula (1), R1 each independently represents a group selected from the group represented by the following formula (3). -12- 201139519 【化7】

In the above formula (3), R3 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; a halogen atom; An alkyl group; a hydroxyl group; a nitro group; a cyano group; or a sulfo group, wherein the hydrogen atom of the alkyl group and the alkyl group may be substituted by a halogen atom, and D represents an ether group, a thioether group, a keto group, an ester group, or a sulfonyl group. The alkylene group, the decylamino group or the decyloxy group 'al each independently represents an integer of 1 to 3, and a2 each independently represents 1 or 2, a3 each independently represents an integer of 1 to 4, and e represents an integer of 〇3. R3 is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a nitro group, a cyano group or a sulfo group, and more preferably a hydrogen atom or an alkyl group. In the above formula (3), as the alkyl group in R3, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having a carbon number is preferable, and specific examples thereof include a methyl group, an ethyl group, and a C group. Base, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl and the like. -13- 201139519 Any of these alkyl atoms may be substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the above formula (3), 'as a stretching base in R3 and D, a methyl group or an alkyl group having a carbon number of 2 to 20, etc., and a hydrogen atom of the methyl group and the alkyl group may be a halogen atom. Replace. 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 dimethyl group, a trimethyl group, a tetramethyl group, a pentamethyl group, and a hexagonal group. The methyl group, the isopropylidene group, the fluorenyl group, and any of these alkylene groups may be substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. As D, a sulfonyl group is preferred. e represents an integer of 〇~2, preferably 0 or 1, and more preferably 0. The base represented by the above formula (3) is exemplified by the following groups (3 - 1 ) to (3 - 3 ). -14- 201139519 【化8】

(3-1) -15- 201139519 【化9】 ho3s

so3H H3C-0

——ch3

[化1 0]

The group selected from the group represented by the above formula (3) is a group selected from the group represented by the following formula (3'), but the residual stress is small, and the occurrence of the anti-warpage is suppressed by the film of -16,395,395,519. Therefore, it is better. [1 1] R3 R3

In the above formula (3'), each of R3 independently represents the same as R3 in the above formula (3). In the above formula (1), R2 each independently represents a group selected from the group represented by the following formula (4). 201139519 【化1 2】

The above formula (4) +, R4 each independently represents a gas atom or a sulfhydryl group, the hydrogen atom of the yard group may be taken from the dentate atom, and d represents an acid group, a thioether ketone group, an ester group, a sulfonyl group, an alkylene group. Or a fluorinated alkyl group, b each represents I or 2, c each independently represents an integer of 1 to 3, and f represents an integer of 〇 〜 3 in the above formula (4) 'as an alkyl group in R 4 Examples of the above formula (3) include the same groups as those of the alkyl group in R3, and R4 is preferably a hydrogen atom. As D, a sulfonyl group is preferred, f is preferably an integer of 0 to 2, 0 or 1 is preferred, and 0 is more preferred. The group selected from the group represented by the above formula (4) is a group selected from the group represented by the following formula (4'), but a film having a small residual stress can be obtained, and the generation of the anti-warpage is suppressed _ 18 - 201139519, Therefore, it is preferable that the structural unit (1) contains the structural unit (2). The structural unit (2) may be contained in at least one group selected from the group R1 and R2 in the structural unit (1), or may contain the end "*" of the structural unit (1), but is contained in It is preferred that at least one base selected from the group consisting of plural R1 and R2 is preferred. In addition, when at least one group selected from the group consisting of the plural R1 and R2 contains a structural unit represented by the following formula (2), when η is 2 or more, R1 and R2 each exist in 2 or more structural units ( In 1), at least one of these plural numbers R1 and R2 contains a structural unit represented by the following formula (2). Since the polyimine precursor of the present invention contains the structural unit (2)', the resin composition containing the precursor is a film which is capable of obtaining a small residual stress, and suppresses the occurrence of back-warping. [化1 4]

In the above formula (2), the plural R5 each independently represents a monovalent organic group having 1 to 20 carbon atoms, and m represents an integer of 3 to 200. -19 - 201139519 In the above formula (2), the monovalent organic group having a carbon number of 1 to 20 in R5 may, for example, be a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent alkoxy group having 1 to 20 carbon atoms. Wait. Examples of the monovalent hydrocarbon group of the carbon number of 1 to 20 in the above R 5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The hospital base having a carbon number of 1 to 20 is preferably a hospital base having a carbon number of 1 to 10, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Amyl, hexyl and the like. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. 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, and a naphthyl group. Examples of the monovalent alkoxy group having 1 to 20 carbon atoms in the above R5 include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, and a propyleneoxy group. And cyclohexyloxy and the like. At least one of the plurality of R5 in the above formula (2) contains an aryl group, and the island portion formed of the soft skeleton portion is excellent in affinity with the sea portion formed by the rigid portion, because it is 1 nm to 1 μm. It is preferred that the size is easy (uniform) dispersion (microscopic phase separation). More specifically, it is preferred that the plural R5 is an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. At this time, in all the R5 in the structural unit (2), the molar ratio of the number of moles of the alkyl group having 1 to 10 carbon atoms (i) to the number of moles of the aryl group having a carbon number of 6 to 12 (ii) (but, i) + (ii) =1〇〇) to (〇:(丨丨)=90~10:10~90 is preferred, preferably (1):( -20- 201139519 ii ) =85 〜15: 15 ～85, more preferably (i) ·· (ii) =85~65: 15 ～35. In all R5 of the structural unit (2), if the ratio of the alkyl group (i) to the aryl group (ii) is the aforementioned range In addition, there is a concern that polyiminoimine cannot be a microscopic phase separation structure. When the ratio of alkyl group (i) to aryl group (i〇 is in the above range, it can be microscopic phase separation (framework containing structural unit (2)) The portion is a nano-dispersion), and a film having a low linear expansion coefficient and a low residual stress can be obtained. The alkyl group (i) having 1 to 10 carbon atoms is preferably a methyl group, and the aryl group having 6 to 12 carbon atoms ( Ii) is preferably a phenyl group. When the total amount of the polyimine precursor of the present invention is 1% by mass, the content of the structural unit (2) is preferably 5 to 40% by mass, and 5 to 23% by mass. % is better, preferably 8 to 22% by mass, with a quality of 9.5 to 21 % is a special super-quantity tree. If the film's rate of change is fat-coated, the ratio of the tree will be 2, and the force of the tree will be the same as that of the tree. The 布 彳 离 有 有 有 有 ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ ¥ The base is driven by glass, and the glass is coated with an amine before the time, and the film is driven by the film. Before the sub-coating, the film is condensed and the film is removed from the amine. Fan Cheng also describes the basis of the matter. The former is the same as the former. The former in the formula (2) is an integer from 3 to 200, preferably from 1 to 200. Preferably, it is 20 to 150, more preferably 30 to 100, and particularly preferably an integer of 35 to 80. When 111 is 2 or less, the polyimine obtained from the polyimide precursor is difficult to form -201139519 into a microscopic In the phase-separated structure, when m exceeds 200, the size of the island portion formed by the skeleton portion containing the structural unit (2) exceeds 1 and the coating film becomes cloudy and the mechanical strength is lowered. The polyimine of the present invention. Precursor 100% by mass of the polyimine precursor is contained in the structural unit (1), preferably 60% by mass or more, preferably 77% by mass or more, more preferably 79% by mass, still more preferably 85 to 100% by mass. %, more preferably 9 0 to 1 0 0% by mass, more preferably 9 1 to 1 0 0% by mass 'extra good for 9 2 to 1 0 0% by mass. Polyaminoimine precursor 'previous structure When the ratio of the unit (1) is in the above range, a film having a small residual stress can be obtained, which is less likely to cause a rebound. Further, when 100% by mass of the polyimine precursor is contained, when the structural unit (1) is 60% by mass or more, it means that the structural unit-NH-R^NH-, the structural unit-nh-r1-nh2, and the structural unit are contained. -co-r2(coor)2-co-, structural unit-CO-R2(COOR)2-COOH, structural unit (2), and structural unit-(Si(R5)2-0)m-Si(R5) The total of the structural units of R1, R2 and the structural unit (2) of 2-R1G-R" is 60% by mass or more. (And, R1, R2 and R are synonymous with R1, R2 and R in the above formula (1), R5 is synonymous with R5 in the above formula (2), and R1G and R11 are the following formulas (7') and (8. Further, Rle and R11 are synonymous) Further, the polyimine precursor of the present invention is a part of the structural unit (1) which can be imidized. The polyimine precursor of the present invention may be contained in a main chain of the precursor, in addition to the structural unit contained in the above formula (1), in addition to the structural unit of the above formula (1), and may be contained in a main chain selected from the group consisting of an ether group and a thioether. a monomer having at least one group of a group of a ketone group, a ketone group, an ester group, or a sulfo-22-201139519 fluorenyl group, an alkylene group, a decylamino group, and a decyloxy group (hereinafter also referred to as "monomer (I) The structural unit (hereinafter also referred to as "structural unit (56)"). Examples of the alkylene group include the same group as the alkyl group in R3 in the above formula (3). Further, the "structural unit contained in the above formula (1)" means that the structural unit -NH-W-NH-, the structural unit -NH-R^-NHz, and the structural unit -CO-R2(COOR)2-CO- are contained. , structural unit -CO-R2(COOR)2-COOH, structural unit (2), and, structural unit -(Si(R5)2-0)m-Si(Rs)2-R1Q-R", etc. R1, R2 And the structural unit of the structural unit (2) (and, R1, R2 and R are synonymous with R1, R2 and R in the above formula (1), R5 is synonymous with R5 in the above formula (2), and R1() and R11 are R1Q and R11 in the following formulas (7') and (8') are synonymous). The structural unit (5 6 ) represents a tetracarboxylic dianhydride and a structural unit (2) which are contained in the main chain of the polythenimine precursor and which do not contain the groups represented by R1 and R2 in the structural unit (1) These derivatives or imines form the structural unit of the compound. The main chain of the polyimine precursor is a chain containing R 1 or R 2 of the above structural unit (1), and for example, -CO 0R in the structural unit (1) is not a main chain and is a side chain. When the polyimine precursor of the present invention contains the structural unit (56), the linear expansion coefficient of the obtained film increases, and a film which can be blended with the desired elongation can be obtained. When the polyimine precursor of the present invention increases the content of the structural unit (5 6 ) -23- 201139519 and/or the content of the structural unit (2), the linear expansion coefficient increases, so that Cu is contained. When the resin composition is applied to a substrate or a substrate containing Si, the amount of the structural unit (56) and/or the structural unit (2) may be changed only by the substrate. Specifically, since the linear expansion coefficient of Cu is 16.8 ppm/K, when the resin composition of the present invention is applied onto a substrate made of Cu, the polyimine precursor contains a structural unit (56), which is preferable. When the wire expansion coefficient of Si is 3 ppm/K, when the resin composition of the present invention is applied onto a substrate made of Si, the polyimine precursor is preferably not contained in the structural unit (56). The chrome expansion coefficient of other chromium is 8.2 ppm/K, the linear expansion coefficient of glass is 9 ppm/K, the linear expansion coefficient of stainless steel SUS43 0 is 10.4 ppm/K, and the linear expansion coefficient of nickel is 12.8 ppm/K. When the resin composition of the present invention is applied to the substrate formed thereon, the polyimine precursor of the present invention contains 100% by mass of the polyimine precursor, and the structural unit (56) is 0 to 15% by mass. good. The monomer (I) is a compound represented by the following formula (5) (hereinafter also referred to as "compound (5)") or a compound represented by the formula (6) (hereinafter also referred to as "compound (6)"). good. [化1 5]

Ο 0 -24- 201139519 HU In the above formulas (5) and (6), each of 'A independently represents an acid group selected from the group consisting of an acid group (-〇·), a thioether group (-S-), and a keto group (_c( = 〇). ·), vinegar (-COO-), sulfonyl (-S02-), alkyl (_R7_), decyl (-C(=0)-NR8-) and decyl (-Si) R9) 2-〇_Si(R9)2) The group of at least one group of the group 'R' is unique, and the hydrogen atom of a hydrogen atom, a halogen atom, a hospital group or a nitro group is exemplified by The dentate atom is substituted, and d each independently represents an integer of 1 to 4. Further, the above R8 and R9 each independently represent a hydrogen atom, an alkyl group or a halogen atom. The hydrogen atom of the substituent may be substituted by a halogen atom. In the above-mentioned formulas (3) of R6, R8 and R9, the same formula as in the case of R3 is used. The halogen atom is preferably a chlorine atom or a fluorine atom. In the above, A is preferably an ether group, and as the above R6, a hydrogen atom is preferably used as the alkyl group (-R7-) in the above formulae (5) and (6), and the above formula (3) Among them, the same groups as the alkylene group in R3, and the like, the methyl group, the isopropylidene group, the hexafluoroisopropylidene group and the fluorenyl group are preferably used as the above compounds (5) and (6). 'For example, the compounds described in the following compound groups (5-1) to (6-9) can be mentioned. -25- 201139519 【化1 6】

NH2 (5-1) -26- 201139519

--^Π3

(5-2) 27-201139519 【化1 8】

[化1 9]

(5-4) -28- 201139519 【化2 0】

[Chem. 2 1]

H2N

(5-6) 【化2 2】 Ο Η Η Ν2Ν^^ (5-7) -29- 201139519 【化2 3】

30-201139519 【化2 4】

[化2 5]

[Chem. 2 6]

-31 - 201139519 【化2 7 Οd

〇〇:ο 【化2 8

Ο

[Chemical 2 9

Ο

ο

(6-3) (6-4) (6 - 5) 32-201139519 ο 3 匕

(6 — 6 )

-33- 201139519

-34- 201139519 【化3 3】 Ο

The polyimine precursor of the present invention contains a structural unit (56). The polyimine precursor is preferably 1% by mass in the polyimine precursor, and the unit (56) 〇 15 15% by mass is preferred. Good for containing 〇~10 quality is better for containing 〇~9% by mass 'te good for containing 〇~8 mass%. When the content of the structural unit (56) exceeds 15% by mass, the elastic modulus of the front structural portion is lowered, and it is difficult to move the residual stress to the structural portion, so that the obtained film is likely to be warped. Further, when the content of the structural unit (56) is within the above range, the film is easily inhibited, and a film which is easily stretched can be obtained. And the poly-imine precursor having the structural unit (56) when the polyimine precursor contains the structural unit (56) is a structural unit having R1 or R2 in (I) (56) The structure of the structure and (11) the structure of the polyimine precursor in which the structural unit (56) is contained outside the structural unit (1). The above (I) is the aforementioned polyimine. When the precursor is a structural unit containing the compound (5) in the above formula (1), the polyimine precursor is represented by the following formula (5Α). At this time, the term "polyimine imine precursor half mass" In %, 'containing structural unit (S6) 〇~15% by mass is preferable.) In the case of 100% by mass of the epiprene precursor, the repeating unit "in the middle, the structure % - said just soft and anti-warping, including) The situation of the Ministry of Love is shown in the example 7J 1 00, and the structure of the structure between the two - 35-201139519 NH- (containing both ends - NH-) is 0 to 15 mass%. In the case of (I), the structural unit (56) may be contained in at least one group selected from the group consisting of the plural R1 and R2 in the structural unit (1). It may also be included at the end of the aforementioned structural unit (1).

In the above formula (5A), R, R1 and R2 are each independently synonymous with R, R1 and R2 in the above formula (1), and A, R6 and d are each independently synonymous with A, R6 and d in the above formula (5). ,nl+n2 = n. The polyamidene precursor of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 10,000 to 200,000, 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 500,000, and particularly preferably from 20,000 to 20,000 00. When the weight average molecular weight or the number average molecular weight of the polyimide precursor is less than the above lower limit, the strength of the coating film may be lowered. Further, the linear expansion coefficient of the obtained film may be more than necessary. On the other hand, when the weight average molecular weight or the number average molecular weight of the polyimine precursor exceeds the above upper limit, the viscosity of the resin composition is increased. Therefore, when the resin composition is applied to a substrate such as a glass substrate to form a film, The amount of the polyimide precursor to be added to the resin composition is small, and the film thickness accuracy such as the flatness of the obtained coating film is deteriorated. -36-201139519 The molecular weight distribution of the polyimide precursor of the present invention (1 to 10 is more preferably 2 to 5, particularly preferably 2 to 4. Further, the weight average molecular weight and the number average molecular weight are measured in the same manner as in the following examples. <Polyimine The method of synthesizing the precursors is preferably a component of at least one of the group consisting of (A) carboxylic acid dianhydride and the reactive derivative (hereinafter also referred to as "(A). The component ") and (B) are compound components (hereinafter also referred to as "(B) component"). However, when the polyimine precursor is synthesized, the compound of the structural unit (2) is preferred. The reaction can be obtained in accordance with the original used. In addition, the precursor of the structural unit derived from the compound can be obtained in an amount corresponding to the amount of the raw material to be used. In this case, the formula (A) is used as the component (A). The base compound (hereinafter also referred to as "the compound (or the component (B) is an imide-forming compound represented by the above formula (2) (hereinafter also referred to as "the compound (B-2. Further, a compound (A) may also be used. · 2) and compound (B-2 [(A) component] (A) component is selected from tetracarboxylic dianhydride and their opposite

Mw/Mn) and a molecular weight fraction containing a structure selected from the group consisting of a tetradecyl compound containing an imine form and reacting using a structure containing a precursor compound: () structure L-2)"), structure Units) j) are good) both sides. Dependent Derivative -37- 201139519 A group of at least one mercapto compound. At least one compound containing a group of the mercapto compound (A-1) other than the compound (A-2) and the compound (A-2) is preferably contained. The mercapto compound (A-1) may be at least one compound selected from the group consisting of aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and a reactive derivative thereof. When the compound having a group selected from the group represented by the above formula (4) has a compound selected from the group represented by the above formula (4'), it can be (uniformly) dispersed in the sea portion having a high modulus of elasticity. 1 The soft skeleton portion having a size of nanometers to 1 micrometer is (microscopic phase separation structure), and the stress generated in the film formation step can be efficiently absorbed in the soft skeleton portion, and the residual stress is small, and the occurrence of back warpage is obtained. It is preferable to suppress the film point or the like. Specific examples of such a compound include pyromellitic dianhydride (PMDA), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 1,2,3,4-cyclopentanetetracarboxylic acid. Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (PMDAH), 3,3',4,4'-biphenyltetracarboxylic dianhydride (S-BPDA), 2, 2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and The compound represented by the following group (4-1) and the like are preferably aromatic tetracarboxylic dianhydride, more preferably pyromellitic dianhydride or 3,3',4,4'-biphenyl. Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, particularly preferably pyromellitic dianhydride. These compounds may be used alone or in combination of two or more. -38- 201139519 【化3 5】

Further, as the above-mentioned mercapto compound (Al)', a compound which does not have a group selected from the group represented by the above formulas (4) and (4) can be used, and examples thereof include an aromatic tetracarboxylic dianhydride and an aliphatic group. At least one compound in which a tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and a reactive derivative thereof are grouped. Specific examples thereof include butane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, and 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2, 3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxo-3-furan)-naphtho[ Ij-c] —furan-1,3-dione, 5-( 2,5·di-side oxytetrahydrofuranmethylidene)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride An aliphatic tetra-residual dianhydride or an alicyclic tetracarboxylic dianhydride such as bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like Reactive derivative; 4,4'-oxydiphthalic dianhydride (〇pda), 3,3,,4,4'-dimethyldiphenylnonanetetracarboxylic dianhydride, 3, 3,4,4,-tetraphenylnonanetetracarboxylic acid-39 201139519 dianhydride, 2,3,4,5-furan tetracarboxylic dianhydride, 4,4'·bis(3,4-dicarboxybenzene Oxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy Diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, bis(phthalic acid) benzene Phosphonium oxide dianhydride, P-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenyl-o-phenylene) An aromatic tetracarboxylic dianhydride such as formic acid)-4,4'-diphenyl ether dianhydride or bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, and the like Reactive derivative. These compounds may be used alone or in combination of two or more. Among them, an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride is preferably used from the viewpoint of excellent transparency and good solubility in an organic solvent. Further, from the viewpoint of heat resistance, low linear expansion coefficient (size stability), and low water absorbability, aromatic tetracarboxylic dianhydride is preferably used. The compounding amount of the compound (A·1) is not particularly limited, and when the total amount of the total fluorenyl compound (component (A)) is 100% by mass, it may be 100% by mass, but the component (A) contains the following compound. In the case of (A-2) and/or the compounds (6) and (6·), it may be added in an amount of from 1% by mass to the total amount of each of the compounds. Specific examples of the compound (A-2) include tetracarboxylic dianhydride having a structural unit represented by the above formula (2) and at least one mercapto compound of the reactive derivative, and the like. A compound represented by the following formula (7) (hereinafter also referred to as "compound (7)"), a compound represented by the following formula (7) (hereinafter also referred to as "compound (7))", and the following formula (8) The group of compounds represented by the -40-201139519 (hereinafter also referred to as "compound (8)") and the compound represented by the following formula (8') (hereinafter also referred to as "compound (8 ')") At least 1 compound, etc. The above-mentioned reactive derivative may, for example, be a tetracarboxylic acid having a structural unit represented by the above formula (2), an acid ester of the tetracarboxylic acid, or an acid chloride of the tetracarboxylic acid. Further, when it is desired to synthesize a structural unit (2) of at least one of the plurality of polyvalent imine precursors of the plural R2 in the structural unit (1), it is preferred to use the compound (7) and/or (8). When the polyimine precursor containing the terminal "*" of the above structural unit (1) is synthesized, the compound (7') and/or 201139519 are used.

(7)

The above formulae (7), (7'), (8) and the above are synonymous with R5 and m in the above formula (2).二 A divalent organic group having 1 to 20 carbon atoms. In the above formula (a monovalent organic group each independently having a hydrogen atom or a carbon number of 1 to 20 and having a carbon number of 1 to 20, the first three carbon atoms having a carbon number of 1 to 20, the same group, etc. may be mentioned. The dimethyl group having 1 to 20 carbon atoms, the alkylene group having 2 to 20 carbon atoms, and the extended aryl group having 3 to 6 to 20 carbon atoms.

In the alkyl group of the carbon number 2 to 20, wherein R5 and m are each independently represented by a single bond or 7') and (8'), R11 is monovalent. The organic group, as the valence organic group in the formula (2), and the R5 valence organic group, may be a cyclic alkyl group having a stretch of 20 or an alkylene group having a carbon U having a carbon number of 2 to 10 - 42-201139519. Examples include dimethyl, trimethyl, tetramethyl, pentamethyl, and hexamethylene. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 1 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. . The aryl group having 6 to 20 carbon atoms is preferably a aryl group having 6 to 12 carbon atoms, and examples thereof include a phenylene group and a naphthyl group. The compound (A-2) preferably has a number average molecular weight of from 200 to 10,000, preferably from 500 to 10,000, from the viewpoint of a film excellent in heat resistance (high glass transition temperature) and water resistance. Good for 500~ 6000. The amine value is preferably from 100 to 5,000, more preferably from 250 to 5,000, still more preferably from 1,000 to 3,000. The degree of polymerization m in the above compounds (7), (7'), (8) and (8) is the same as the above formula (2), and the preferred range is also the same. In the above formulae (7), (7'), (8) and (8), R5 is preferably a methyl group or a phenyl group, and at least one of the plural numbers R5 is preferably a phenyl group. All plural R5 is methyl or phenyl, and when at least one is phenyl, the ratio of methyl mole % of methyl group to mole % of phenyl group (% of methyl group + % of phenyl group of phenyl group = 1) 〇〇) is preferably methyl: phenyl = 5 to 95: 95 to 5, preferably methyl: phenyl = 15 to 85: 85 to 15, more preferably methyl: phenyl = 85 to 65: 15~35»The above formula

When at least one of (7'), (8), and (8') is not a phenyl group, the compatibility between the sea portion and the island portion is deteriorated, and the dispersion size of the island portion exceeds 1 μm, and heat resistance is obtained. A film with a poor film strength. Specific examples of the compound (A-2) include -43-201139519 DMS-Z2 1 (number average molecular weight 600 to 800, amine price 300 to 400, m = 4 to 7) manufactured by Gelest. Further, the compound (A 2 ) may be used singly or in combination of two or more. When the total amount of the all-raw compound ((A) component + (B) component) is 1% by mass, the compound (A-2) is blended in the case where the component (A) is contained in the above-mentioned (A) component. It is preferably from 5 to 40% by mass, preferably from 5 to 23% by mass, more preferably from 8 to 2 2% by mass, from the viewpoint of being excellent in peeling property from the substrate and obtaining a film which is less likely to cause warpage. , especially good for 9.5 ~ 21% by mass. However, the compound (A-2) is preferably blended in such a manner that when the polyimine precursor is synthesized, the compound (B-2) is not used, and when the polyimide precursor is synthesized, the raw material is used as the raw material. When the compound (A-2) and the compound (B-2) are used, the total amount of the compound (A-2) and the compound (B-2) to be used is the same as the preferred amount of the compound (A-2). The degree is better. Further, in the component (A), the compound (6) and/or the compound represented by the following formula (6') may be contained in view of the extension of the film obtained by the improvement (hereinafter also referred to as " Compound (6,)"). Further, when the main chain (removal end) of the polyimide precursor is contained in the polyimine precursor of the structural unit (56), the compound (6) is preferably used to be synthesized in the polyimide precursor. When the terminal end of the main chain contains a polyimine precursor of a structural unit (56), the compound (6') is preferably used. -44- 201139519 【化3 7】 〇

In the above formula (6'), A has the same meaning as A in the above formulas (5) and (6), and R12 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is the same as the monovalent organic group having 1 to 20 carbon atoms in the above formula (2). When the compound (6) and/or the compound (6') are contained in the component (A), the total amount of the whole raw material compound (component (A) + component (B)) is 1% by mass, and the compound ( 6) and the compound (6') is preferably 〇~15 mass%, preferably 〇10 mass%, more preferably 〇~ from the viewpoint of obtaining a film which is less likely to cause warping. 9% by mass, especially preferably 〇~8% by mass. However, the compound (6) and the compound (6, ) are preferably compounded in such a manner that the compound (5) and/or the compound (5 1 ) are not used in the synthesis of the polyimide precursor. When the compound (6) and/or the compound (6, ) and the compound (5) and/or the compound (5,) are used as the starting material, the compound (Ο, the compound (6') is used as the starting material. The amount of the compound (5) and the compound (5,) is preferably the same as the amount of the compound (6) and/or the compound (6). [(B) component] - 45-201139519 The component (B) is an imine forming compound. The term "subcompound" is a reaction with the component (A) to form an imine (group), and specifically, a diamine compound, a diisocyanate compound, and an alkyl group are mentioned. A decane) amine compound or the like. The component (B) preferably contains at least one compound selected from the group consisting of the above compound and the imine-forming compound (B-1) other than the compound (B-2). Examples of the imine-forming compound (B-1) include at least one compound selected from the group consisting of a selected diamine and an alicyclic diamine. ' From the above formulas (3) and (3-1) to (3) -3) Preferably, the group of the group shown is preferably a group having a group selected from the group represented by the above formula (3') as a compound, and specifically P-phenylenediamine (PDA) benzene Amine, 2,4-diaminotoluene, benzidine, 3,3'-dimethyl-aminobiphenyl (bi-toluidine), 2,2'-dimethyl-4,4'-di Phenyl (toluidine, mTB), 3,3'-diethyl-4,4'-diamino, 2,2'-diethyl-4,4,-diaminobiphenyl, 4,4'-Diamino-(trifluoromethyl)biphenyl (TFMB), 3,3-dimethoxy-4-ylbiphenyl, 2,2'-dichloro-4,4,- Diamino-5,5'-dimethoxy 2,2',5,5'-tetrachloro-4,4,-diaminobiphenyl, etc., and also methyl-4, A 4'-diaminobiphenyl group is preferred. These compounds may be used alone or in combination of two or more. As the thiol compound (Β-1)', a group which does not have the group represented by the formulas (3), (3-1) to (3-3) and (3') can be used, and examples thereof include a compound selected from the group consisting of The aromatic diamine, the aliphatic diamine and the aliphatic amine form a compound of bis(tris(Β-2) group self-aromatic having a compound as a compound. m-extension 4,4 '-diamine linkage Biphenyl 2,2,-bis, 4-diamine phenyl, 2,2,-difluorene, at least one compound selected from the group consisting of the above-mentioned compound cyclohexa-46 - 201139519 amine. Examples of the aromatic diamine include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether (ODA), and 3,4'-diaminodiphenyl ether. , 3,3'-diaminodiphenyl ether, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone , 3,3'-diaminobenzophenone, 4,4'-bis(4-aminophenyl) sulfide, 4,4'-diaminodiphenylanthracene, 4,4'-di Aminobenzamide, 1,n-bis(4-aminophenoxy)alkane, 1,3-bis[2-(4-aminophenoxyethoxy)]ethane, 9, 9-bis(4-aminophenyl)anthracene, 9,9-double (4-Aminophenoxyphenyl)anthracene, 5(6)-amino-1-(4-aminomethyl)-1,3,3-trimethylindan, 1,4-double ( 4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy) Benzene (APB), 2,5-bis(4-aminophenoxy)biphenyl (P-TPEQ), 4,4'-bis(4-aminophenoxy)biphenyl, 4,4 '-Bis(3-Aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxyphenyl)]propane (BAPP), 2,2-bis(4-amine Phenoxyphenyl)hexafluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]pluta, 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methyl-bis(2-chloroaniline), 9,10-bis(4-aminophenyl) And the above-mentioned aliphatic diamine may be used alone or in combination of two or more. Examples of the aliphatic diamine include aliphatic diamines having a carbon number of 2 to 30, and the like. Examples of such a specific example include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-heptanediamine, and 1,6-hexane. Amine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-decanediamine, 1,10-decanediamine, 1,12-47-201139519, dodecane Amines such as alkyldiamine; oxybis(2-aminoethane), oxybis(2-aminopropane), 2-(2-aminoethoxy)ethoxyaminoethane, etc. Oxyalkylene diamine. These aliphatic diamines may be used alone or in combination of two or more. Further, as the alicyclic diamine, at least one alicyclic group may be used in the molecule, and the alicyclic group may be any of a monocyclic ring, a polycyclic ring or a condensed ring. As the alicyclic diamine, an alicyclic diamine having 4 to 30 carbon atoms can be used, and examples thereof include 4,4,-diaminodicyclohexylmethane (MBCHA) and 4,4'-diamino group. 3,3,_Dimethylcyclohexylmethane, 4,4'-diamino-3,3',5,5'-tetramethylcyclohexylmethane, diaminocyclohexane, 1,4 - II Aminocyclohexane (CHDA), 丨-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-diamino Bicyclo[2.2.1]heptane, 2,6-diaminobicyclo[2.2.1]heptane, 2,7-diaminobicyclo[2.2.1]heptane, 2,5-bis(amino group A Bis-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2.3-bis(aminomethyl)-bicyclo[2.2.1]g Alkane, 3(4), 8(9)-bis(aminomethyl)-triterpene [5^2.1.02'6] decane, and the like. These alicyclic diamines may be used alone or in combination of two or more. The compounding amount of the compound (Β -1 ) is not particularly limited, and when the total amount of the total imine forming compound ((Β) component) is 1% by mass, it may be 100% by mass, and the (Β) component is contained. The following compound (Β_2) and/or the compounds (5) and (5') may be added in an amount of 100% by mass minus the respective compounding amounts of these compounds. -48-201139519 The compound (B2) is not particularly limited as long as it is an imine-forming compound containing a structural unit (2), and a compound represented by the following formula (9) is exemplified (hereinafter also referred to as The compound represented by the following formula (9') and the compound represented by the following formula (9') (hereinafter also referred to as "compound (9,)") are the same and the structural unit (2) to be synthesized is selected from the structural unit selected from the above. (1) In the case of at least one group of polyimine precursors in which a plurality of R1 and R2 are grouped, it is preferable to use the compound (9), and it is preferably contained in the terminal "*" of the structural unit (1). When the polyimide precursor is used, the compound (9,) is preferably used. [化3 8]

In the above formulae (9) and (9), R5 and m are each independently synonymous with R5 and m in the above formula (2), and R10 is independently synonymous with R10 in the above formulas (7) and (8) 'R11 Separately with the Rii synonym in the above formulas (7,) and (8), as the above compound (B-2), the soft skeleton portion can be finely dispersed in a nanometer to micron size to be formed by the rigid skeleton portion. From the viewpoint of a film having excellent heat resistance (high glass transition temperature) and excellent water resistance, the number average molecular weight is preferably 500 to 12,000, and preferably 1, 〇〇〇-49 to 201139519 to 8,000. More preferably 3,000 to 6,000. The amine valence is preferably from 250 to 6,000, preferably from 500 to 4,000, more preferably from 1,500 to 3,0 Torr, more preferably the degree of polymerization m in the above formulas (9) and (9') and the above formula ( 2) Same, the preferred range is also the same. In the above formulae (9) and (9'), R5 is preferably a methyl group or a phenyl group, and at least one of the plurality of R5 is preferably a phenyl group. All plural R5 is a methyl group or a phenyl group, and when at least one is a phenyl group, the ratio of the mole % of the methyl group to the mole % of the phenyl group (mol% of methyl group + mole % of phenyl group = 100) Methyl: phenyl = 5 to 95: 95 to 5 is preferred, preferably methyl: phenyl = 15 to 85: 85 to 15, more preferably methyl: phenyl = 85 to 65: 15 to 35 . When at least one R5 non-phenyl group in the above formulas (9) and (9) is used, the compatibility between the sea portion and the island portion is deteriorated, and the dispersion size of the island portion is more than 1 μm, and the film having heat resistance and film strength deterioration is obtained. Happening. Specific examples of the compound (B-2) include a terminal amino group-modified methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd.; Χ22·1660Β-3 (number average molecular weight 4,400 degree of polymerization m = 41, phenyl group) : methyl = 25: 75 mol%), X2 2-94 09 (number average molecular weight 1,300), and both terminal amine-modified dimethyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd.; X22-161A (number average molecular weight 1) , 600, degree of polymerization m = 2 0), X2 2-161B (number average molecular weight 3,000, degree of polymerization m = 39), KF 8012 (number average molecular weight 4400, degree of polymerization m = 58), Toray dow corning system; BY 1 6-8 3 5U (number average molecular weight 900, degree of polymerization m = U)), etc., and the above-mentioned imine-forming compound (B-2) may be used alone or in combination of two or more. 201139519 The degree of mixing m is calculated, for example, by the following formula: (when the terminal is an aminopropyl group, when all of the above formula (2) is a compound of a methyl group or a phenyl group) m = (number average molecular weight - two terminal groups) (aminopropyl) molecular weight 116.2) / (74.15 甲基 methyl 111 〇 1% >< 0.01 + 198.29) < phenyl 111 〇 1% >< 0.01 ) When the component (B) containing the compound (B-2), the total amount of the whole raw material compound ((A) component + (B) component) 100 as a mass. /. In the case where the compounding amount of the compound (B-2) is excellent in the peeling property from the substrate, a film which is less likely to cause warpage is obtained, and it is preferably 5 to 40% by mass, more preferably 5 to 23% by mass. /. More preferably, it is 8 to 22% by mass, and particularly preferably 9.5 to 2% by mass. However, a preferred compounding amount of the above compound (B-2) is a case where the above compound (A-2) is not used in the synthesis of a polyimide precursor. Further, in the component (B), the compound (5) and/or the compound represented by the following formula (5') may be contained in view of the extension of the film obtained by the improvement (hereinafter also referred to as a component). "Compound (5')"). Further, in order to synthesize a polyimine precursor containing a structural unit (56) in the main chain (except the terminal) of the polyimide precursor, it is preferred to use the compound (5) to be synthesized in the polyimide precursor. When the terminal end of the main chain contains a structural unit (56) of a polyimine precursor, the compound (5 1 ) is preferably used. [化3 9]

-51 - 201139519 In the above formula (5), a is synonymous with the above formula (5) and (( ' R12 is R12 in the above formula (6)). The above component (B) contains the aforementioned compound (5) (5) In the case of the above-mentioned compound ((a) component + (when the total amount is 100% by mass, the compounding amount of the compound (5) and the compounding amount of the compound (5) is preferably 15 mass% from the viewpoint of obtaining a film which is less likely to cause warping. Preferably, the amount is preferably from 0 to 8% by mass. However, the preferred compounding amount of the above compound (5) is not (6) and/or when the synthetic polyimide precursor is synthesized. Or the case of the compound (6') The polyimine precursor of the present invention has the component (A) as the use ratio (charge ratio) and the molar ratio of the component (A) ((A) component / (B) component) is preferably 0.8-reaction, and is carried out in a range of 0.90 to 1.0. (A) When the mercapto compound and (B) imine formation have a race equivalent or more than 1.2 equivalent, the molecular weight will be It is difficult to carry out the reaction of the component (A) and the component (B) in one step. The organic solvent is preferably dehydrated. As the organic solvent, it is used. It is preferable from the viewpoints of ease of production of the resin composition of the mixed solvent, and the properties of the obtained film, etc. The at least one (B) imine is specifically formed as the components (A) and (B). The compound is dissolved in an organic solution, and at least one (A) mercapto compound is added.

;) in the compound (5 ') of the synonymous and / or compound B)), in the case of 〇~0~9 mass%, the compound (5 | ) is compounded with the above compound: (B) into B) Component - 1.2 range Down reaction is preferably I ear ratio less than 〇. 8 Form a film. In the case of an organic solvent, the method of the present invention (the smog and the counter method may be mentioned as a solvent, and then stirred at a temperature of 0 to 1 0 0 〇C - 52 to 201139519 for 1 to 60 hours). The total amount of the (Α) component and the (Β) component in the reaction liquid is 3 to 60% by mass based on the total amount of the reaction liquid, preferably 5 to 40% by mass, preferably 10 to 40% by mass, more preferably When the total amount of the (Α) component and the (Β) component in the reaction liquid is within the above range, the concentration of the polyimide precursor in the obtained resin composition can be preferably as follows. In the above-mentioned organic solvent, at least one solvent selected from the group consisting of an ether solvent, a ketone solvent, a nitrile solvent, an ester solvent, and a guanamine solvent is used as the ether system. The solvent is preferably an ether having a carbon number of 3 or more and 10 or less, and an ether having a carbon number of 3 or more and 7 or less is preferably a preferred ether solvent, and specific examples thereof include ethylene glycol and diethylene glycol. Monoether or dialkyl ether such as ethylene glycol monoethyl ether, cyclic ether such as dioxane or tetrahydrofuran (THF), benzene In particular, tetrahydrofuran is used as the aromatic ether such as ether. The ether solvent may be used alone or in combination of two or more. The ketone solvent may have a carbon number of 3 or more and 10 or less. The ketone is preferred, and a ketone having 3 or more carbon atoms is preferred from the viewpoint of boiling point and cost. Specific examples of the ketone solvent include acetone (bp = 57 ° C). Base (bp = 80 ° C), methyl-n-propyl hydrazine (bp = l 〇 5C), methyl-iso-propyl ketone (bp = 116 ° C), diethyl ketone (bP = 101 ° c ), methyl-η-butyl ketone (bp=127°C), methyl-iso-butyl ketone (bP=118°C) 'methyl-sec-butyl ketone (bp=118°C), A Dialkyl ketones such as thio-tert-butyl ketone (-53-201139519 bp=116°C), cyclopentanone (bp=130°C), cyclohexanone (CHN, bp=156〇C), ring A cyclic ketone such as heptanone (bp = 185 ° C), etc.. Among them, cyclohexanone is also a resin composition which is excellent in drying property and productivity, and can be selected from the following vacuum drying. Evaporating sexually, it is possible to almost completely remove the solvent of the coating film formed on the substrate. Further, the ketone-based solvent 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, and a nitrile having a carbon number of 2 or more and 7 or less. The preferred class is acetonitrile (1^ = 821), propane nitrile (bp = 97 ° C), butyronitrile (bp = 116 ° C), isobutyronitrile (bp = 107). °C), valeronitrile (bp = 140 ° C), isovaleronitrile (bp = 129 ° C), benzonitrile (bp = 191 ° C) and the like. Among them, acetonitrile is preferred from the viewpoint of low boiling point. Further, these nitrile-based solvents may be used singly or in combination of two or more. The ester solvent is preferably an ester having 3 or more and 10 or less carbon atoms, and preferably an ester having 3 or more and 6 or less carbon atoms. Preferred examples of the ester solvent include ethyl acetate (bp = 77 ° C), propyl acetate (bp = 97 ° C), acetic acid small propyl (bp = 89 * C), and butyl acetate (bp = 126 ° C), such as a cyclic ester such as an alkyl ester or a β-propiolactone (bp = 155 ° C), and the like may be used alone or in combination of two or more. The guanamine-based solvent is preferably a guanamine having a carbon number of 3 or more and 10 or less. The guanamine having a carbon number of 3 or more and 6 or less is preferable. In the same manner, the coating film formed on a glass substrate or the like is vacuum-dried, once dried, and dried twice to obtain a film, and the amide-based solvent having a boiling point of one drying temperature or higher is used as a film of -54-201139519. The flatness of the obtained film is preferable from the viewpoint of, for example, a guanamine-based solvent having a boiling point of 200 ° C or higher. Preferred examples of the amide-based solvent include alkyl decylamines such as N,N-dimethylformamide and N,N-dimethylacetamide (DMAc), and 1,3-dimethyl- A cyclic guanamine such as 2-imidazolidinone or N-methyl-2-pyrrolidone. In the same way, N-methyl-2-pyrrolidone and N,N-dimethylacetamide are left in a vacuum drying after evaporation of a non-amined solvent or after drying once, and then at 200 ° C to 500 ° C. It is preferable to carry out volatilization at the evaporation rate at the smoothness of the surface of the coating film at the time of the second drying, and it is preferable to use N-methyl-2-pyrrolidone in consideration of environmental pollution or the like. Further, the amide-based solvents may be used alone or in combination of two or more. As the organic solvent, a mixed solvent of a guanamine-based solvent and at least one non-amine-based solvent selected from the group consisting of an ether solvent, a ketone solvent, a nitrile solvent, and an ester solvent is used, and the obtained coating film is used. The adhesion (peelability), the peeling property, and the residual stress of the film are preferable. Further, when the above-mentioned mixed solvent is used, a resin composition having a high drying rate when the film is formed, a film quality is not lowered, and a film having high productivity, and having a high concentration of a polyimide precursor is obtained. The non-melamine-based solvent is preferably a solvent which is selectively evaporated in the following vacuum drying, and is preferably a solvent which is almost completely removed from the coating film formed on the substrate, and a solvent having a boiling point of 40 to 200 ° C is preferable. A solvent in the range of 1 Torr to 170 ° C is preferred. When such a solvent is used, the solvent can be easily removed from the resin composition at the time of film formation, and a resin composition excellent in productivity can be obtained. -55- 201139519 In the present invention, the boiling point is the boiling point in the atmosphere at 1 atm. In addition, it is preferred that the non-melamine-based solvent contains at least one organic solvent selected from the group consisting of a ketone solvent and a solvent. Since these solvents are relatively high in reactivity, it is possible to obtain a resin composition having excellent storage stability. The mixed solvent is a mixed solvent of N-yl-2-pyrrolidone and cyclohexanone, a mixed solvent of N,N-dimethylacetamidine and cyclohexanone, and N-A from the viewpoints of drying property and productivity. A mixed solvent of keto-2-pyrrolidone and acetonitrile is preferred, and a mixture of N-methyl-2-pyrrolidone and cyclohexanone is particularly preferred. Further, from the viewpoint of prevention of white turbidity of the obtained film, etc., a mixed solvent of N,N-diethylacetamide and tetrahydrofuran is preferred. The mixed solvent is preferably from 5 to 95 parts by mass of the guanamine-based solvent, and preferably from 25 to 95 parts by mass, based on 100 parts by mass of the mixed solvent, and preferably contains 3 to 5 parts by weight in consideration of the physical properties of the obtained film. 6 5 parts by mass is preferred. Further, the mixed solvent is particularly preferably used in an amount of 40 to 60 parts by mass of the above-described guanamine solvent in the case of the mixed solvent of 100 parts by mass, and the drying rate is fast when the above-mentioned guanamine solvent is contained in the mixed solvent. Further, a resin composition having excellent productivity can be obtained, which is excellent in film properties such as white turbidity and tensile strength, storage stability, and the like, and is excellent in adhesion to the substrate, and is excellent in peeling and peeling. When the amount of the guanamine-based solvent is less than 5 parts by mass, the polyamide precursor is not dissolved, and when the resin composition is not obtained, when the amount of the guanamine-based solvent exceeds a part by mass, the drying rate at the time of film formation becomes slow, and production is performed. There will be a deterioration of the nitrile carbamide compound A, and - 刖 is the case of -56-201139519 which is more moderately sub-95. <<Resin Composition>> The resin composition of the present invention contains the above-mentioned polyimine precursor of the present invention and an organic solvent. As the organic solvent, the above mixed solvent is preferred. The resin composition containing the polyimine precursor of the present invention can easily produce a film having a high glass transition temperature and a small residual stress in a short time and with good productivity. In the resin composition, when a resin composition is formed on a substrate such as a glass substrate, a film excellent in adhesion and releasability to the substrate can be easily formed. The composition containing the polyimine precursor obtained by the above reaction and the organic solvent may be used as the resin composition as it is, and the resin composition is a solid polyimide precursor obtained by the above reaction. After the components are separated, they are dissolved in an organic solvent to obtain. As a method of separating a polyimide precursor, a solution containing a polyimide precursor, an organic solvent, or the like is added to a poor solvent such as methanol or isopropyl alcohol for a polyimide precursor to form a polymer. A method in which a ruthenium imine precursor is precipitated, and the polyimide precursor is separated as a solid by filtration, washing, drying, or the like. Further, an additive such as an antioxidant, an ultraviolet absorber, or a surfactant may be added to the resin composition insofar as the object of the present invention is not impaired. The viscosity of the foregoing resin composition is generally 500 to 500,000 mPa.s, preferably 1, 〇〇〇-57-201139519 to 50,000 111?&amp;.8», depending on the molecular weight or concentration of the polyimide precursor. When it is less than 500 111?&amp;.3, the retention of the resin composition in the film formation will deteriorate, and it will flow from a board|substrate. On the other hand, when it exceeds 500,000 mPa «s, the viscosity is too high, and the film thickness adjustment becomes difficult, and formation of a film becomes difficult. Further, the viscosity of the resin composition was measured using an E-type viscometer (manufactured by Toki Industries, Ltd., viscosity meter MODEL RE100) at 25 ° C in the air. The concentration of the polyimide precursor in the resin composition is preferably adjusted to the above range of the viscosity of the resin composition, and is also preferably from 3 to 60% by mass, preferably from 3 to 60% by mass, based on the molecular weight of the polyimide precursor. 5 to 40% by mass, more preferably 10 to 40% by mass, particularly preferably 10 to 30% by mass. When the amount is less than 3% by mass, there is a concern that it is difficult to form a thick film, the productivity is deteriorated, pinholes are easily formed, and film thickness accuracy such as flatness is deteriorated. On the other hand, when the amount is more than 60% by mass, the viscosity of the resin composition is too high, and it is difficult to form a film, and a film having a lack of surface smoothness is obtained. When the viscosity of the resin composition and the concentration of the polyimide intermediate in the composition are within the above range, the resin composition can be applied onto a substrate by using a fine slit coating method which is excellent in productivity, etc., and can be produced. The film is excellent in the film thickness accuracy and the like in a short time. "Method for forming a film" The method for forming a film (polyimine film) according to the present invention includes a step of applying the resin composition onto a substrate to form a coating film, and evaporating the film from the film. Method of removing the organic solvent and the like - 58-201139519 The method of applying the resin composition on a substrate to form a coating film includes a roll coating method, a gravure coating method, a spin coating method, and a fine coating method. A slit coating method, a dipping method, and a method of coating using a doctor blade, an extrusion die, an applicator, a spray, a bristles, a roller, or the like. And the film thickness or surface smoothness and the like can be controlled by repeated coating. They are also preferred to use the slit coating method. The thickness of the coating film can be appropriately selected in accordance with the intended use, and is not particularly limited, and is, for example, preferably 1 to 500 μm, preferably 1 to 450 μm, more preferably 2 to 250 μm, still more preferably 2 to 150 μm. Preferably, the substrate is 5 to 125 μηι 〇, and examples of the substrate include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polybutylene terephthalate ( PBT) film, nylon 6 film, nylon 6,6 film, polypropylene film, polytetrafluoroethylene belt, enamel wafer, glass wafer, glass substrate (containing alkali-free glass substrate), Cu substrate, SUS plate, and the like. In particular, since the resin composition of the present invention is excellent in adhesion and releasability to the substrates, it is possible to form a film for a tantalum wafer, a glass wafer, a glass substrate, a Cu substrate, and a SUS plate. Further, the step of removing the organic solvent by evaporating the organic solvent from the coating film, specifically, the coating film can be carried out by vacuum drying or heating. The heating condition can only evaporate the organic solvent, and the polyimine precursor of the present invention can be imidized, and is preferably determined only by blending the substrate or the polyimide precursor, but for example, at a heating temperature of 60 ° C. 3 50 ° C is better. Further, as the heating time, it is preferably from 10 minutes to 5 hours. -59- 201139519 and 'heating can be carried out above the second stage. Specifically, for example, after drying at a temperature of 60 to 25 ° C for 10 minutes to 2 hours, at i60 ° C to 3 50 ° C, preferably at 200 to 3 50 ° C, more preferably Perform heating for 10 minutes to 2 hours at 23 0 to 270 Torr. Further, it may be dried under reduced pressure as necessary. 加热 The heating environment is not particularly limited, and it is preferably in an atmosphere or an inert gas atmosphere. It is particularly preferable in an inert gas atmosphere. As the inert gas, nitrogen, argon, helium or the like is mentioned from the viewpoint of coloring properties, but nitrogen is preferred. Further, the drying is performed by drying the coating film formed on the substrate, but the substrate may be dried to some extent without affecting the properties of the substrate (for example, when heating in the second step or more) After the heating step is performed, the coating film formed on the substrate is peeled off from the substrate, and then dried. Further, in the step of removing the mixed solvent from the coating film, it is preferred to carry out vacuum drying before the heating. In the vacuum drying, the coating film formed on the substrate does not need to be blown by hot air or the like, and the solvent can be easily removed by the coating film, so that a film having excellent flatness can be obtained, and since the surface of the coating film is fixed, It is excellent in reproducibility to form a film having a uniform film quality excellent in flatness. In the above vacuum drying, the pressure in the apparatus is reduced to a pressure (decompression degree) in the apparatus in which the coating film is placed to below 760 mmHg, preferably less than 100 mmHg, more preferably less than 50 mmHg, and particularly preferably 1 mmHg. the following. When it exceeds 760 mmHg, the evaporation rate at the time of further removing the solvent from the coating film after vacuum drying is remarkably slow, and the productivity is deteriorated. Further, vacuum drying is carried out for -60 to 201139519 for 0 minutes, preferably 0 to 60 minutes, preferably 〇~30 minutes, more preferably 0 to 20 minutes until the pressure is lowered. Drying for less than 0 minutes is not sufficient, and the surface of the self-coating film may not be fixed, and it is difficult to obtain a film of uniform film quality. On the other hand, if it exceeds 60 minutes, the productivity of the film may deteriorate. The resulting film can be used after being peeled off from the substrate or used directly without peeling off. The thickness of the film may be appropriately selected in accordance with the intended use, preferably from 1 to 200 μm, preferably from 5 to ΙΟΟμηη, more preferably from 10 to 50 μηη, particularly preferably from 2 0 to 4 0 μηη, obtained from the resin composition of the present invention. The modulus of the film is 5 to 2 0 GP a , and particularly preferably 5 to 10 GPa. When the modulus of elasticity of the film is less than 5 GPa, the film tends to be easily extended, but the residual stress becomes high, causing back-warping, becoming brittle when it exceeds 20 GPa, and causing cracks in the film during handling. The extension of the film may be appropriately selected in accordance with the intended use, and is preferably 2% or more, more preferably 4% or more, and particularly preferably 10% or more. When the film is stretched by less than 2%, the film is cracked during the treatment. The glass transition temperature of the film is 250 ° C or higher, preferably 35 (TC or more, particularly preferably 450 ° C or higher. When the glass transition temperature is less than 25 ° C, the reflow soldering step or the device is heated to 250 ° when the device is formed. When the coating film is used for such a use, the film is deformed. The preferred use of the film includes a flexible substrate such as a flexible printed circuit board or a flexible display substrate, and a semiconductor device. An insulating film for electronic components such as a thin film transistor type liquid crystal display element or a magnetic head element, an integrated circuit element, a solid photographic element, a mounting substrate, and the like, and a film for various capacitors - 61 - 201139519, that is, in these electronic parts It is possible to use an insulating film (a super-coated film, a protective layer, or the like) to provide an interlayer insulating film or a planarizing insulating film or a surface protective insulating film (such as an ultra-coated film or a protective layer) in a wiring layer which is disposed in a general layer. It is used as a film such as a light guide plate, a polarizing plate, a display film, a film for a disk, a transparent conductive film, or a waveguide plate. In particular, the film is adhered to a glass substrate and The peeling property is excellent, and it is not necessary to provide an adhesive layer or the like between the film and the substrate, and the number of steps in forming the flexible substrate can be reduced. [Embodiment] [Embodiment] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited by the examples. (1) Glass transition temperature (Tg) Using the films obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2, the glass transition temperature of the polyimide was used in Rigaku. The company's 8 2 3 0 DSC measuring device was measured by setting the temperature increase rate to 20 ° C / min. (2 ) The concentration of the polyoxyxide compound was obtained by using the following Examples 1 to 13 or Comparative Examples 1 and 2. The polyphosphonium polyoxynitride (compound containing structural unit (2)) concentration is obtained by the following formula: -62- 201139519 Polyxanthene concentration [unit: %] = (weight of polyoxyxide) ) / {( (A) the weight of the total sulfhydryl compound) + ( (B) the weight of the total imine forming compound)} χ 1 〇〇 the weight of the polyoxy compound = the weight of the compound (Α-2) + compound (Β -2) The weight (3) of the imine concentration assumes that the imidization ratio is 1 〇〇 mol% when 'under The molecular weight of the repeating unit in the polyimine obtained in Examples 1 to 13 or Comparative Examples 1 and 2 was determined by (molecular weight of mercapto compound) + (molecular weight of diamine) _2 χ (molecular weight of water). The repeating unit contains two imine groups. Therefore, the imine groups of the polymers obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 have an assumed imidization ratio of 1 〇〇 mol %. Theoretical 値) is obtained by the following formula: [Imino group concentration] (unit: mmol / g) = 2 / { (molecular weight of mercapto compound) + (molecular weight of diamine) - 2 x (molecular weight of water)} xl 〇〇〇(4) Adhesion is carried out in the following examples 1 to 13 or the imidization step (drying at 25 ° C) in Comparative Examples 1 and 2, and then cooled to room temperature with polyfluorene The support of the imide film was heated to 30 (TC after 30 minutes, and then the process of cooling to room temperature over 30 minutes was used as one cycle, and after repeating 10 cycles, it was evaluated as [◎] by the support peeler. After 5 cycles of this cycle, it was evaluated as [〇] by the support peeler, and it was observed that the peeler was evaluated as [X]. -63- 201139519 (5) Peelability After the imidization step (drying at 250 ° C) in Examples 1 to 13 or Comparative Examples 1 and 2 below, the support can be completely peeled off from the support. The amine film was evaluated as [◎], and the part of the peeling residue that could be fully peeled off was evaluated as [〇]', and the part that could not be peeled off was evaluated as [△], and the one who could not be fully peeled off was evaluated as [X]. (6) Film anti-warping The polyimide film peeled off from the support obtained in the following Examples 1 to 13 or Comparative Examples 1 and 2 was cut out to 40×40 mm, and the anti-warping was carried out (the obtained polyphthalate was placed on a horizontal substrate). For the amine film, the distance between the film and the substrate in the four corners of the film is measured, and the average 値) is less than 1.0 mm, and the evaluation is [◎], and the anti-warping is 1_〇1^11 or more, which is less than 2.〇111111. The evaluation was [〇], the anti-warping was 2.0〇1111 or more, the evaluation was [△] if it was less than 3.0 mm, and the weight average molecular weight was evaluated as (7) the weight average molecular weight of the following Examples 1 to 1 3 or The weight average molecular weight of the polylysine obtained in Comparative Examples 1 and 2 was measured using a HPC-8020 type GPC apparatus manufactured by TOSOH. Lithium bromide and citric acid were added to the solvent, and a molecular weight in terms of polystyrene was determined using N-methyl-2-pyrrolidone (NMP) at a measurement temperature of 40 °C. [Example 1]

Add 2,2'-dimethyl-4,4'-diamine linkage as component (B) to a 4-neck flask containing a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube of 300 mL -64 - 201139519 Phenyl (hereinafter also referred to as "mTB") 6.07 g (28.6 mmol) and 2.57 g (0-6 mmol) of the amine-modified methylphenyl polyfluorene (X22-1 660B-3) at both ends. Next, after replacing the inside of the flask with nitrogen, 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 the same sentence. 6.36 g ( 29.2 mmol) of pyromellitic dianhydride (hereinafter also referred to as "PMDA") as a component (A) was added to the obtained solution at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition. (polyglycine solution). The polyamine acid is separated from the composition using a portion of the resulting composition. The weight average molecular weight, polyoxyxide concentration, and imine group concentration of the isolated polylysine were evaluated (the theoretical enthalpy when the imidization ratio was 1 〇〇 mol%). Next, the obtained polyaminic acid solution was applied onto an alkali-free glass support by spin coating (rotation at 100 rpm for 5 seconds, and rotation at 1 OO rpm for 10 seconds), and dried at 70 ° C for 30 minutes. After continuing to dry at 120 ° C for 30 minutes, a coating film was obtained. The obtained coating film was further dried at 250 ° C for 2 hours as an imidization step, and then peeled off from the alkali-free glass support to obtain a polyimide film having a film thickness of 30 μm (〇.〇3 mm). With respect to the above polyimide film, adhesion to the support, peelability, and back-up of the polyimide film were evaluated. The results are shown in Table 1. X-22-166 0B-3; two-terminal amine-modified side chain phenyl-methyl-type polyfluorene oxygen manufactured by Shin-Etsu Chemical Co., Ltd. (Molecular composition of methyl and phenyl groups obtained by 1H-NMR) The ratio is 75: 25 (in all the R5 in the above formula (9), -65 - 201139519, the molar composition ratio of the methyl group to the phenyl group is 75:25), the number average molecular weight 4400, the degree of polymerization m = 4l, catalogue: reference Shin-Etsu Chemical Industry Co., Ltd., General Assembly Department of Poly-Oxygen Division, Poly-Oxygen News No. 122, July, 2002) [Example 2] 4 ports of 300 ml with thermometer, mixer, nitrogen inlet tube, and cooling tube In the flask, as a component (B), 6.07 g (28.6 mmol) of 2,2'-dimethyl-4,4,-diaminobiphenyl group and a terminal amino group-modified methylphenyl polyoxyl ( X22-1660B-3) 2.57 g (0.6 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring to homogeneity. To the resulting solution, 6.36 g ( 29.2 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that a film (film) having a film thickness of 0.03 mm was applied at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 3] 2,2'-dimethyl-4,4'-diamino group as a component (B) was added to a 300 mL 4-neck flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Biphenyl 6.68 g (31.4 mmol) and a two-terminal amine-modified methylphenyl polyfluorene (X22-1660B-3) 1.40 g (0'3 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide and 20 ml of tetrahydrofuran-66 - 201139519 were added and stirred until homogeneous. To the obtained solution, 6.93 g (31.8 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that the film (film) having a film thickness of 〇3 mm was applied at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 4] 2,2'-dimethyl-4,4'-diamino group as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Biphenyl 6.04 g (28.4 mmol) and a two-terminal amine-modified methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X22-9409, number average molecular weight 1,300) 2.36 g (1.8 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of hydrazine, hydrazine-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 6.60 g (3 0.3 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied to a film having a film thickness of 0.3 mm to obtain a film having a film thickness of 0.3 mm, and the same procedure as in Example 1 was carried out to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. -67-201139519 [Example 5] 2,2'-dimethyl-4,4 as a component (B) was added to a 300-neck flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. '-Diaminobiphenyl 6.41g (30.2 mmol) and two-terminal amine-modified methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., 乂22-1618, number average molecular weight 3,000) 1.85g (0.6 mmol) . Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 6.73 g (30.9 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that the film (film) having a film thickness of 〇. 3 mm was applied at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 6] 2,2'-dimethyl-4,4'-diamine as a component (B) was added to a 300-neck flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. The base phenyl group 6.29 g (29.6 mmol) and the two-terminal amine-modified methylphenyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., X2 2-161A, number average molecular weight 1,600) 1.98 g (1.2 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of hydrazine, hydrazine-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 6.73 g (30.9 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (-68-201139519 polylysine). Solution). The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that a film (film) having a film thickness of 0.03 mm was applied at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 7] 2,2'-dimethyl-4,4,- as a component (B) was added to a 3-neck flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Diaminobiphenyl 6.65 g (31.3 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 6.15 g (28.2 mmol) of pyromellitic dianhydride as the component (A) and methyl oxonium (£) 1^-Z2 1 ) at the two terminal anhydrides were added at room temperature. 2.19 g ( 3_1 mmol), stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied at a desired number of revolutions and time to obtain a film thickness 〇. The film of the 〇 3 mm (film) was subjected to the same procedure as in Example ’ to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. DMS-Z2 1 ; two-terminal anhydride-modified methyl polyfluorene manufactured by Gelest (number average molecular weight 600~800, amine price 300~400, degree of polymerization m = 4 [Example 8] -69- 201139519 2,2,-dimethyl-4,4'-diaminobiphenyl 6.59 g (31.0) as a component (B) was added to a 300 m L four-necked flask of a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. Methyl) with a two-terminal amine-modified methylphenyl polyoxalate (X22-1660B-3) 1.38 g (0.3 mmol). Secondly, after the flask was replaced with nitrogen, N,N-dimethylacetamidine was added. 58 ml of the amine was stirred until homogeneous. In the obtained solution, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter also referred to as "PMDAH") as the component (A) was added at room temperature. 7.03 g (31.4 mmol), stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied at any number of revolutions and time to obtain a film thickness. A film of a 3 mm film (film) was produced in the same manner as in Example 1 to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimide film were as follows. (Example 9) 1,4-diaminocyclohexane as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube (hereinafter also It is called "CHDA") 2.87g (25.1 mmol) and the terminal amino group modified methylphenyl polyoxyl (X22-1 660B-3) 3.42g (0.8 mmol). Secondly, after the flask is replaced by nitrogen After adding 5 ml of N,N-dimethylacetamide, it was stirred until homogeneous. In the obtained solution, diphenyl-3,3',4,4'_4 as (A) component was added at room temperature. 8.71 g (25.9 mmol) of carboxylic acid dianhydride (hereinafter also referred to as "8_BPDA"), and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). -70-201139519 The proline solution was applied at a desired number of revolutions and time to obtain a film (film) having a film thickness of 〇3 mm, and the same procedure as in Example 1 was carried out to obtain a polyimine film. The physical properties of the polylysine and the polyimide film are shown in Table 1. [Example 1 〇] 30 〇mI^ with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. In a 4-necked flask, 2.99 g (26.2 mmol) of 1,4-diaminocyclohexan as a component (B) and 2.56 g of methylaminopolyoxyl (X22-9409) modified at both ends were added ( 2.0 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added and stirred until homogeneous. To the obtained solution, 9.46 g ( 28.1 mmol) of diphenyl-3,3',4,4,-tetracarboxylic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature. After hours, the composition (polyglycine solution) was obtained. The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that a film (film) having a film thickness of 0.03 mm was applied at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 11] 4,4'-diamino-2,2'-double as a component (B) was added to a 30-mL flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. (Trifluoromethyl)biphenyl (hereinafter also referred to as "TFMB") 7.85 g (24.5 mmol) and both terminal amine-modified methylphenyl polyoxyl (X22-71 - 201139519 9409) 2.03 g ( 1.6 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "CBDA") as a component (A), 5 to 12 g (26.1 mmol), at this temperature, at this temperature Stirring was continued for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied at any number of revolutions and time to obtain a film thickness 〇. 〇3 mm film (film) Example 1 was carried out in the same manner to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 12] 2,2'-dimethyl-4,4'-diamino group as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Biphenyl 6.34 g (29.9 mmol) and two terminal amine-modified methylphenyl polyfluorene (X22-1 660B-3) 2.68 g (0.6 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring until uniform. To the obtained solution, 5.98 g (30.5 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours. Composition (polyglycine solution). The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that a film (film) having a film thickness of 〇3 mm was obtained at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine and polylysine' polyimine film are shown in Table 1. -72-201139519 [Example 13] 2,2,-dimethyl-4,4 as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. -diaminobiphenyl 4.78 g (22.3 mmol) and a two-terminal amine-modified methylphenyl polyoxalate (X22-1660B-3) 5.16 g (i_2 mmol). Next, after replacing the inside of the flask with nitrogen, N,N-dimethylacetamide 58 m was added, and the mixture was stirred until homogeneous. To the resulting solution, 5.11 g (23.4 mmol) of benzenetetracarboxylic dianhydride as the component (A) was added at room temperature, and stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution). The obtained polyaminic acid solution was applied at a desired number of revolutions and time to obtain a film having a film thickness of 〇 3 mm, except for the film (film) of 3 mm, in the same manner as in Example 1 to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Example 14] The poly-proline solution (composition) prepared in the above Example 1 was applied to the alkali-free glass support by a spin coating flow to a thickness of 25 μm of the obtained coating film. Drying was carried out for 30 minutes at 7 ° C, and drying was continued at 120 ° C for 30 minutes to obtain a coating film. Thereafter, the coating film obtained in the cyclization (imidization) step was further dried at 250 ° C for 2 hours.

Further, a transparent conductive film (element) was formed under the film forming conditions of 230 ° C in an argon atmosphere on the surface of the obtained coating film by a sputter ring apparatus under a film forming condition of 5 minutes. And ITO is used as the target material. The specific resistance of the obtained substrate was 2 X -73 - 201139519 1 Ο '4 ( Ω · cm ). A polyimide substrate provided with a transparent conductive film was peeled off from the glassless support to obtain a flexible substrate. And the substrate was completely peeled off from the support, and no warping was observed. [Comparative Example 1] 2,2'-dimethyl-4,4'-diamino group as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Biphenyl 7.40 g (34.9 mmol). Next, after replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added, followed by stirring until uniform. To the resulting solution, 7.60 g (34.9 mmol) of pyromellitic dianhydride as the component (A) was added at room temperature, and the mixture was directly stirred at this temperature for 24 hours to obtain a polyaminic acid solution. The obtained polyaminic acid solution was applied in the same manner as in Example 1 except that a film (film) having a film thickness of 〇3 mm was obtained at a desired number of revolutions and time to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are shown in Table 1. [Comparative Example 2] 2,2'-bis[4-(4-amine) as a component (B) was placed in a 30-mL flask equipped with a thermometer, a mixer, and a nitrogen introduction tube 'cooling tube. Phenyloxy)phenyl]propane (hereinafter also referred to as "BAPP") 9.25 g (22.5 mmol). Next, after replacing the inside of the flask with gas, Ν, Ν-dimethylacetamide 5 8 m 1 was added and stirred until homogeneous. To the obtained solution, 2.95 g (13.5 mmol) and 4,4,--74-201139519 oxydiphthalic dianhydride (hereinafter also referred to as pyromellitic dianhydride) as component (A) were added at room temperature. For r ODPA") 2.80 g (0.99 mmol) 'Stirring was continued at this temperature for 24 hours to obtain a polyaminic acid solution. The obtained polyaminic acid solution was applied to a film having a film thickness of 〇3 mm in the same manner as in Example 1 except that a film having a film thickness of 〇3 mm was obtained, to obtain a polyimide film. The physical properties of the obtained polyimine, polylysine, and polyimine film are as shown in Table 1. ° -75 - 201139519 [I* film ◎ ◎ Ο ○ o 〇 oo ◎ ◎ ◎ ◎ &lt; X ( Peelability @ 0 ® ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ &lt; 〇X i ◎ ◎ ◎ ® ◎ ◎ o ◎ ◎ ◎ ◎ 〇 ◎ ◎ mirn^s. Bright even 1 陲•m 丨 Transparent uniform 1 ST sms? sr m 丨transparent uniform 1 m 丨transparent uniform 1 丨transparent uniform I ϋΓ m I transparent uniform j 1 transparent uniform 1 耵if s 粕丨transparent uniform I 丨transparent uniform collision base (mmol/g) - .Λ5Β,, 135 J丨4.44 | 1 4.45 1 mj m I 3.99 | I 4.39 I 1 4.38 1 丨3.31 II 5.07 j I 3.18 I Polyfluorene oxidation [%] Bu· *? σ&gt; 丨 Old 1 1 12-3 1 丨13.2 1 I 6 | CM σ&gt; I 22.8 | ί 17.1 I 丨13.6 l 1 17.9 ] II oo Tg (°C) of polyimine 1 &gt;350 I 1 &gt;350 1 1 &gt;350 1 1 &gt;350 . 1 &gt;350 1 1 &gt;350 1 I &gt;350 1 1 &gt;350 | I &gt;350 II &gt;350 | I &gt;350 | I &gt;350 I 丨&gt;350 II &gt;350 | I 252 I Polyacid Mw I 95,000 | 1 97,000 1 1 84,000 1 | 76.000 | sos 1 68.000 I | 94.000 | | 72.000 | | 103.000 I | 82.000 | 〇o CO | 69.000 | | 95.000 | so EI 83.000 | Solvents | DMAc/THF| 1 DMAc 1 |DMAc/THF| | DMAc | I DMAc | 1 DMAc DMAc | | DMAc | | DMAc. | I DMAc | | DMAc | I DMAc | | DMAc | I DMAc | (8) Component 1 X22-1660B-3 | 1 X22-1660B-3 | 1 X22-1660B- 3 | 1X22-9409 | | X22-161B | 1 X22-161A | | X22-1660B-3 | I X22-1680B-3 | | X22-9409 | I X22-9409 | I X22-1660B-3 | | X22- 1660B-3 | iBAPPl | mTB 1 1 mTB 1 I mTB I | mTB | | mTB | I mTB II mTB | | mTB | | CHDA | I CHDA | I TFMB | | mTB | I mTB | I mTB | (VIII) Ingredients | -Z21| I ODPA | 1 PMDA 1 1 PMDA 1 I PMDA II PMDA II PMDA I PMDA I PMDA II PMDAH] I s-BPDAl Is^BPOAi [CBDA II CBDA II PMDA | 丨PMDA II PMDA | Example 1 CM CO bank m 匡mmmm me &lt;〇垣i according to m Example B σ&gt; 揖m 0 1 m Foot Example 11 CM i 垣ni According to the foot! 1 嵩a -76- 201139519 (1) Weight average molecular weight (Mw) , number average molecular weight (Μη) and points Amount distribution (Mw/Mn) The weight average molecular weight (Mw), number average molecular weight (?n), and molecular weight distribution (Mw/Mn) of the polyimine precursors obtained in the following Examples 15 to 20 and Comparative Example 3 were determined using TOSOH. The HLC-8220 type GPC apparatus (protective column: TSK guard colomn ALPHA column: TSKgelALPHA-M, development solvent: NMP) was measured. (2) Storage stability at -15 ° C

After the varnish (resin composition) obtained in the following Examples 15 to 20 and Comparative Example 3 was stored at -1 5 ° C for 48 hours, 'the transparent and precipitate-free one was visually evaluated as 〇, opaque and The sediment precipitated was visually evaluated as X (3 ) varnish viscosity. 1.5 g of the varnish obtained in the following Examples 15 to 20 and Comparative Example 3 was used, and the varnish viscosity at 25 ° C was measured. Specifically, it is determined by using the Dongji Industrial Viscometer MODEL RE100. (4) Fixation of the coating film after vacuum drying The center line of the vacuum-dried glass substrate coating film obtained in the following Examples 15 to 20 and Comparative Example 3 and the center portion of the glass substrate were pulled out, and the coating was applied. The film substrate was placed vertically for 10 minutes. The mark drawn on the film and the mark drawn on the glass substrate were judged to be immobilized if there was no change, and it was judged to be fluidized if -77-201139519 was changed. (5) Polymer (polyimine precursor) in the coating film after vacuum drying The concentration of the polymer in the vacuum-dried coating film obtained in the following Examples 15 to 20 and Comparative Example 3 (polymerization) The concentration of the quinone imine precursor was calculated according to the following formula. Coated varnish weight = weight of glass substrate after varnish coating - weight of glass substrate before varnish coating

Polymer concentration (%) at the time of loading = total amount of charged monomer / (mount of monomer charged + total amount of charged solvent) xlOO Weight of coated polymer = weight of coated varnish X polymer concentration when charged (%) Coating weight after vacuum drying = weight of coating film after vacuum drying - weight of glass substrate before varnish coating

Polymer concentration (%) after vacuum drying = (weight of coated polymer / weight of coating film after vacuum drying) xlOO (6) Solvent composition ratio in a coating film after vacuum drying will be in the following Examples 15 to 20 The solvent composition ratio in the vacuum-dried coating film obtained in Comparative Example 3 was calculated based on the above formula and the following formula. Coated solvent weight = coated varnish weight - coated polymer weight coated non-amine weight solvent weight = coated solvent weight X non-78-201139519 Amine-based solvent Loading amount (ratio of non-melamine solvent in mixed solvent) (%) Solvent weight after vacuum drying = weight of coating film after vacuum drying - weight of coated polymer in vacuum drying Evaporated solvent weight = coated Solvent weight of cloth - solvent weight after vacuum drying Non-ammonamide solvent weight after vacuum drying = weight of coated non-amined solvent - vacuum drying solvent weight of evaporated solvent composition ratio of non-amined solvent ) = (non-amine weight solvent weight after vacuum drying / solvent weight X 1 00 after vacuum drying) Composition ratio of guanamine solvent (%) = 1 0 0 - composition ratio of non-amine solvent (and vacuum) The solvent which is evaporated and evaporated is defined as the solvent having the lowest boiling point in the mixed solvent (non-melamine solvent). (7) The folding property after drying once will be obtained once in the following Examples 15 to 20 and Comparative Example 3. The dried coating film is strongly scraped with a metal spatula, and the coating film is not removed. Were evaluated as non-foldability, the coating film were assessed as mobile foldability. (8) Optical characteristics For each of the coating films formed on the glass substrate after drying once and twice after drying obtained in the following Examples 15 to 20 and Comparative Example 3, Haze (haze) was used: HS K7 105 The transparency test method was used for the measurement. Specifically used -79- 201139519

The SC-3H type smog tester manufactured by Suga Test Machine Co., Ltd. was measured. (9) Glass transition temperature (Tg)

The film obtained in the following Examples 15 to 20 and Comparative Example 3 was peeled off from the glass substrate, and the film after peeling was a Thermo Plus DSC8230 manufactured by Rigaku, and the temperature was raised at 20 ° C/min under a nitrogen gas, 40 to 450. The range of °C was measured. (1 〇) Line Expansion Coefficient The films obtained in the following Examples 15 to 20 and Comparative Example 3 were peeled off from the glass substrate, and the peeled film was used in Seiko Instrument SSC/5200 » at a temperature rising rate of 61 / min, 25~ Measured at a temperature of 350 °C. From the measurement results, a linear expansion coefficient of 100 to 200 ° C was calculated. (1 1 ) The residual stress of the coating film was obtained by using FLX-2 3 20 (manufactured by KLA Co., Ltd.) in the varnish obtained in the following Examples 16 to 21 and Comparative Example 3 on the wafer substrate (for residual stress measurement, Chichibu) The thickness of the company made by Electronic Co., Ltd. = 300 μm, diameter = 4 inches). The film thickness after film formation to 2 times of drying is 30 μm, and the pressure of the film is measured by laser 'measurement' Calculated by the formula. The back warpage of the obtained film is suppressed, and the residual stress of the coating film is preferably 10 MPa or less, and preferably 5 MPa or less. -80- 201139519 [Number 1]

Eh2 σ~ 6(lu)Rt σ: residual stress of the film t: thickness of the film R: measured radius of curvature h: thickness of the substrate E: pressure ratio of the substrate v: Poisson's ratio of the substrate (1 2 ) Amination rate The imidization ratio of the polyimine in the two dried films obtained in the following Examples 15 to 20 and Comparative Example 3 was carried out by the following method using FT-IR Thermo Fisher Scientific ( Thermo NICOLET 6700 ). Quantitative. The peak of the peak (1 520 cm·1 ) of the NH variable angle vibration from the polyimide precursor and the peak of the CH_sexon angle vibration (PQOcnr1) of the aromatic asymmetric trisubstituted body are separated by a Gaussian distribution. And quantitative. The peak area ratio of the polyimine precursor before drying (the peak area of 990 CHT1 / the peak area of 1 520 (: 1 ^ 1) and the ratio of the peak areas after the second drying were measured, and the following calculation formula was used. The imidization ratio was calculated. The imidization ratio (%) = (the peak area ratio after 1-2 drying/the peak area ratio before the first drying) XI 〇〇 (1 3 ) The film strength was measured using No. 7 of JIS K625 1 The dumbbells were subjected to a tensile test at 23 ° C and a speed of 50 mm/min from the 30 μπι film-81 - 201139519 which was peeled off from the dried glass substrate obtained in the following Examples 15 to 20 and Comparative Example 3. 'Measurement of tensile elongation, tensile strength, and elastic modulus. (1 4 ) Peelability with glass substrate The glass substrate 30 μm was coated twice after drying in the following Examples 15 to 20 and Comparative Example 3. The film was cut into a width of 10 mm by a cutter, and the length was 50 mm. After peeling to a length of 20 mm, the peeling strength was measured at an angle of 180 degrees at a speed of 50 mm/mi η. (15) The film was reversed in the following examples. The 20μηι coating film with glass substrate obtained after drying twice from 15 to 20 and Comparative Example 3 was cut into 60 mm X 60 by a cutter. After the size of mm, the floating of the four ends was measured, and the average enthalpy was calculated. [Example I5] A three-necked flask equipped with a thermometer, a nitrogen introduction tube, and a stirring blade was placed under a nitrogen flow at 25 ° C. o-Toluidine (mTB) 45.23 099g (〇.2 1 306mol ), two-terminal amine-modified side chain phenyl-methyl type polyoxo X-22-1 660B-3 [9.4694g ( 0.002 1 521mol)] Then add 307g of dehydrated N-methyl-2-pyrrolidone (NMP) and 307g of dehydrated cyclohexanone (CHN) to the concentration of 14% of the polyimide precursor in the varnish, and stir for 10 minutes to mTB and X. -22-1660B-3 completely dissolved. Add 22.6498g (0.1 03 84mol) of pyromellitic dianhydride (PMDA) and stir for 30 minutes, then add PMDA22.6498g (0.103 84mol) for 60 minutes to stir -82- 201139519

After the completion of the reaction, a filter made of polytetrafluoroethylene (pore size Ιμηι) was used, and fine filtration was carried out to prepare a varnish (PMDA/(mTB + X-22-1660B-3) = 0.965 equivalent). The varnish properties are shown in Table 2. As a result of measurement by NMR, the polyimine precursor having the above structural unit (1) was confirmed in the obtained varnish. Fix the glass substrate (horizontal: 300 mm x vertical: 350 mm x thickness: 0.7 mm) on a control coating table set to be perpendicular to gravity, and set the gap interval to 405 μm after two dryings to make the film thickness 30 μm, varnish 12 g was cast in the center of the glass substrate, and a coating film of 200 mm x vertical: 220 mm was cast. Thereafter, the pressure was reduced to 0.1 mmHg after 10 minutes at 25 t in a vacuum dryer, and then returned to normal pressure (760 mmHg), and vacuum drying was completed. The physical properties of the coating film after vacuum drying are shown in Table 2. After the vacuum drying, the coating film is transparent, the coating film is fixed, and no liquid leakage occurs. The peak areas of 1520 cm·1 and 990 cm·1 of the polyimide precursor after vacuum drying were 5.09 and 6.89, respectively. After vacuum drying, it was dried at 130 ° C for 10 minutes in a hot air dryer. The coating film after one drying was subjected to physical property evaluation after sampling, and the results 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. It can obtain a film-free anti-warping, Tg is also 45 (TC or more, excellent heat resistance, excellent transparency, smoothness, low linear expansion coefficient and strong film. Moreover, the obtained coating film has a fast drying speed, and It is excellent in the adhesion to the glass substrate in the drying and the second drying, and the film obtained after the second drying is excellent in the peeling property from the glass substrate. -83 - 201139519 [Example 16] In Example 15, 'mTB, The same procedure as in Example 15 was carried out except that the amount of use of X-22-1660B-3 and PMDA was changed as shown in Table 2. The results are shown in Table 2. The results of the measurement were confirmed by NMR, and the obtained varnish was confirmed to have the aforementioned structure. The polyimine precursor of the unit (1) can obtain a tough film which is excellent in heat resistance, transparency, smoothness and anti-warping. Moreover, the obtained coating film has a fast drying speed, and is dried once every 2 times. The adhesion to the glass substrate during drying is excellent, and the film obtained after the second drying is excellent in peelability from the glass substrate. [Example 17] In Example 15, the amounts of mTB, X-22-1660B-3, and PMDA were used. Changed to be as shown in Table 2, and synchronized with Example 15. The results are shown in Table 2. The results of the measurement were carried out by NMR, and the obtained varnish was confirmed to have a polyimine precursor having the above structural unit (1). Excellent heat resistance, transparency, smoothness, and no warping resistance were obtained. Further, the obtained coating film has a fast drying speed, and is excellent in adhesion to a glass substrate in one drying and two drying, and the film obtained after two drying is excellent in peeling property from a glass substrate. ^ [Example 18] -84- 201139519 In Example 15, substituting mTB45.23 099g using mTB3 2.56478g and 4,4'-diaminodiphenyl ether (ODA) 7.87 60g, X-22-1 660B The same procedure as in Example 15 was carried out except that the amount of use of -3 and PMDA was changed. The results are shown in Table 2. The results of the measurement were measured by NMR, and the obtained varnish was confirmed to have the above structural unit (1). Polyimine precursor can improve the elongation of the film, and has excellent heat resistance, transparency and smoothness, and has no opposite film. Moreover, the obtained coating film has a fast drying speed in one drying and two drying times. Excellent adhesion to glass substrate, 2 times dry The film obtained after the film was excellent in peelability from the glass substrate. [Example 19] Example 1 5 Substituted X - 2 2 - 1 6 6 Ο Β - 3 ( 9.4 6 9 4 g ) using a two-terminal amine manufactured by Shin-Etsu Chemical Co., Ltd. Base-modified side chain methyl type polyfluorene KF8010 (in all R5 in the above formula (9), the molar composition ratio of methyl group to phenyl group is 1〇〇: 〇, number average molecular weight (4400, m=58) The same procedure as in Example 15 was carried out except that 2.8408 g and X22-1660B-3 (6.22 8 6g) were used. The results are shown in Table 2. The polyimide obtained by the NMR measurement results was confirmed to have the polyimine precursor having the above structural unit (1). A tough film having excellent heat resistance, transparency, and smoothness, and having no back 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 a glass substrate in one drying, and a film obtained after secondary drying is excellent in peelability from a glass substrate. -85-201139519 [Embodiment 20]

In Example 18, the amount of use of mTB and X-22-1660B was changed to as shown in Table 2, and the steps were carried out. The results are shown in Table 2. The results of the measurement were carried out by NMR, and the obtained polyimine precursor of the structural unit (1) was obtained. After two dryings, the residual stress increases, and after the glass is selected, a certain amount of anti-warping is produced, but a heat-resistant and transparent film can be obtained. Further, the obtained coating film was excellent in the drying speed and the adhesion to the glass substrate in the secondary drying, and the film was excellent in peeling property from the glass substrate. [Comparative Example 3] In Example 15, the amount of use of X-22-1 660B PMD A was not changed as shown in Table 2, and the same procedure was carried out. The results are shown in Table 2. The residual stress of the varnish obtained in Comparative Example 3 was slow after the drying speed was slow, and the film was warped by the glass substrate. -3, ODA and PMD A [Identification of the same I in Example 1 8 has the above-mentioned ί substrate, the film is peeled off, the smoothness is excellent, and the speed is 3, and after drying twice, the mTB and f is in phase with Example 15. Also, after 2 times of drying, IJ has a large anti-86-201139519

WT m ΓΛ 50.21338 1 1 49.7866 TT | 110000 I 37931 1 | 2.90 〇I 250000 I zone m ίΝ O § O rs o O — l &lt;Ν ο 〇w-ΐ r*S 1 〇〇〇〇oo Bu·· M mm 枨U^i fN Sign mw 宕1 31.47400 1 | 9.4542 I X-22-1660B-3 I 4400 I 1 2200 I 5 1 I_ 46.1642 II 77600 | 1 30600 I L_2.54 . I 〇1 4500 I Solid &lt;Ν Si 00 § o &lt;N oo — Transparent 1 Ο 〇〇O' 'ό m m P *Λ m Ο ο O' 1 45.23099 1 X-22-1660B-3 1 _4400 I 2200 I 6.6286 I KF8012 | 4400 I 2200 , oo ! 2.8408 1 I 45.2996 | 1 307 I 1 307 I 兮71300 | 1 23200 I 1_1〇1_J 〇4000 | η画 fS (Ν SS § o deer m O o fo - 1 Ο 〇 〇210 | 〇\ •sr&lt; w\ 跶伥Ρ 跶伥Ρ η 1⁄4 ΓΟ Ο ο oo 1 32.56478 II 7.8760 | | X-22-1660B-3 | | 4400 | | 2200 | | 17.3064 | 1 | 42.2528 | 1______ 307 I ΓΟ | 96700 | I 35200 | 1_2,75_I 〇| 5200 | 1 画&lt;N OO 00 § o 戡〇om — Transparent 1 ο 〇〇〇&lt;^ί fN 267 | s〇wS mm 骚4Κ Ρ jn Μ O' cn Ο ο 卜 I 38.9189 0 1 1 X-22-1660B-3 | | 4400 | | 2200 | | 20.6833 : 1 | 40.3978 | L_ 307,__I inch | 102000 | I 32903 Π 1_3J0_I 〇| 12000 | S Painting &lt;N 00 § omr* O o ΓΛ — m (Ν Ο 〇 00 守 OO = η 赖Ρ inchο Ο ο s〇I 42.67864 1 | X-22-1660B-3 i 1 4400 1 1 2200 | 1 13.4707 1 1 43.8507 ! _307_ 1_307_I 103000 | 33770 | _3^5_I 〇丨16000 1 § Painting &lt;N fS £ ΓΛ go 蕻CM o 1 300 ] — (Ν Ο 〇Ο 〇fN V» 〇sm 媲m 伥Ό Ο Ο ο VI [ 45.23099 1 1 X- 22-I660B-3 | I 4400 | | 2200 1 1 9.4694 | 1 | 45.2996 | 1_307_I | 72400 1 | 22300 | 1_3,25_I 〇I 4200| Λ3 η draw m &lt;N Si 00 § o Ml ΓΛ o 1__300_I — transparent 1 Ο 〇&lt;N 214 | 〇s OO m spider ρ ΓΟ ο ο u Ul cm SJ] CU3 U] SJQ mPa · s | System PP ε * α MPa 1 GPa | P MPa 1 N/cm 1 Β Β ImTB I lODA i 一 ¢: Θ m Θ g ε Θ Θ S g Θ © 闺It m !+· Φ 5Γ &amp; m © Θ m ϊϋ US? m ε &lt;π 广1 Θ Μ © © 联 [ PMDA 1 g fN 1 2 P «Λ TI m 1 联 Mw | C 2 Mw/Mn | η 瀵P ώ i S 匣-Ν 1 Zhao mm 联jj U mem 铤§ m ΛΖ s 妄m smu 颏m 1 ii _! g iK I ~N mi LU 3: g iZ&lt; css m mm &lt;N ϋ i &lt;NIN m η UJ 3: -Ν m fN Eij 坚 iSJ mold (N Λ: fun Ρ 〇&lt;Ν gii Chu stretch extension 1 m 1 mm i 迨m Residual stress. 1 am 韹1: δ m 绡mmmm £·Χ I •S Monomer solvent Polyimine precursor Precursor 万 万 万 万 万 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干 干-

Claims (1)

201139519 VII. Patent application scope: 1. A polyimine precursor characterized by having a structural unit represented by the following formula (1) containing a structural unit represented by the following formula (2), [Chemical Formula 1] Ο 0 (In the formula (1), R each independently represents a hydrogen atom or a monovalent organic group, and R1 each independently represents a group selected from the group represented by the following formula (3), and R2 each independently represents a group selected from the following formula (4); The base of the group, η represents a positive integer) (In the formula (2), the plural R5 each independently represents a monovalent organic group having a carbon number of 1 to 2 Å, and m represents an integer of 3 to 200.) -88 - 201139519 (3) Sister ((3) 'R3 each iL table is not acid group, sulfur-brinding group, mercapto group, vinegar group, sulfonyl group, alkylene group, base containing decylamino group or decyloxy group, hydrogen An atom, a halogen atom, an alkyl group, a hydroxyl group, a nitro group, a cyano group or a sulfo group, the hydrogen atom of the alkyl group and the alkylene group may be substituted by a halogen atom, and D represents an ether group, a thioether group, a ketone group, an ester group, Sulfhydryl, alkylene, decyl or decylalkyl, al each independently represents an integer from 1 to 3, a2 each independently represents 1 or 2, a3 each independently represents an integer from 1 to 4, and e represents 0 to 3 The integer) 201139519 【化4】 (4) (In (4), R4 each independently represents a hydrogen atom or an alkyl group, the hydrogen atom of the alkyl group may be substituted by a halogen atom, and D represents an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, or an extension group. Alkyl, decylamino or decyloxy, b each independently represents 1 or 2, c each independently represents an integer of 1 to 3, and f represents an integer of 0 to 3). 2. The polyimine precursor according to claim 1, wherein the polyimine precursor contains 5 to 40% by mass of the structural unit represented by the above formula (2). -90- 201139519 3 - Polyimine precursor as claimed in claim 1 or 2, wherein in the above formula (2), at least one of the plural R1 contains an aryl group. The polyamidiamine precursor according to any one of item 1, wherein the poly-imine precursor is contained in the polyimine precursor, in addition to the structural unit contained in the above formula (1). The main chain containing from 0 to 15% by mass of the precursor contains an ether group, a thioether group, a ketone group, an ester group, a sulfonyl group, an alkylene group, a decylamino group and a decyloxy group. A structural unit of at least one group of monomers of the group. 5. The polyimine precursor according to claim 4, wherein the monomer is a compound represented by the following formula (5) or (6); Ο 0 (In the formulas (5) and (6), 'A each independently means a group selected from the group consisting of an ether group, a sulfate group, a ketone group, an ester group, a sulfonyl group, an alkylene group, an anthranyl group, and an anthracene group. At least one group of groups, R6 each independently represents a hydrogen atom, a garden atom, a nominee or a nitro group, and a gas atom of the courtyard group may be substituted by a halogen atom, and 4 each independently represents an integer of 1 to 4. 6. The polyimine-91 - 1 201139519 precursor of any one of claims 1 to 5, wherein the weight average molecular weight is 10,000 to 1,000,000. A resin composition characterized by containing the polyimine precursor of any one of items 1 to 6 of the patent application and an organic solvent. 8. The resin composition of claim 7, wherein the concentration of the polyimine precursor is from 3 to 60% by mass in the resin composition. 9. The resin composition according to claim 7 or 8, wherein the organic solvent contains a group selected from the group consisting of an ether solvent, a ketone solvent, a nitrile solvent, an ester solvent, and a guanamine solvent. At least one solvent. 10. The resin composition of any one of claims 7 to 9 wherein the viscosity measured by an E-type viscosity meter (25 ° C) is in the range of 500 to 500000 mPa · s 〇 1 1. The resin composition according to any one of claims 7 to 10, which is used for film formation. 12. A method of forming a seed film, comprising the step of applying a resin composition according to any one of claims 7 to 11 to a substrate to form a coating film, and by using the coating film The step of obtaining a film by evaporating to remove the aforementioned organic solvent. • 92 - 201139519 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No-3-201139519 If there is a chemical formula in the case, please reveal the best invention Chemical formula of the feature: none