TWI658069B - Polyimide precursor composition, method of manufacturing polyimide, polyimide, polyimide film, and substrate - Google Patents

Abstract

The present invention relates to a polyimide precursor composition comprising a polyimide precursor and an imidazole-based compound, and the content of the imidazole-based compound relative to the repeating unit of the polyimide precursor is 1 mol to 4 mol. .

Description

Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate

The present invention relates to a solution composition (a polyimide precursor composition) containing a polyimide precursor containing a polyimide which has a small thickness direction retardation, excellent mechanical properties, and excellent transparency. ), And a method for producing polyimide. The present invention also relates to a polyimide, a polyimide film, and a substrate, which are excellent in transparency, have small thickness-phase retardation, and are also excellent in mechanical properties.

With the advent of a highly information-oriented society in recent years, the development of optical materials such as liquid crystal alignment films or protective films for color filters in display devices such as optical fibers and optical waveguides has progressed. In particular, in the field of display devices, there have been discussions of light-weight and flexible plastic substrates that replace glass substrates, or the development of bendable and roundable displays that are being actively pursued. Therefore, higher-performance optical materials that are useful in such applications are sought.

Aromatic polyfluorene imine is inherently colored yellow-brown due to the formation of intramolecular conjugates or charge transfer complexes. In order to suppress the coloring method, it has been proposed to introduce a fluorine atom into a molecule, impart flexibility to a main chain, introduce a bulky group as a side chain, and the like to hinder the formation and display of a conjugate or a charge transfer complex in the molecule. Method of transparency.

In addition, a method has also been proposed in which a semialicyclic or fully cycloaliphatic polyfluorene imine that does not form a charge transfer complex is theoretically made to exhibit transparency.

For example, Patent Documents 1 to 3 disclose semi-alicyclic polyfluorene imide having high transparency using an aromatic tetracarboxylic dianhydride as a tetracarboxylic acid component and an alicyclic diamine as a diamine component.

For example, Patent Documents 4 to 7 disclose various highly transparent semialicyclic polyfluorene imines using alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and aromatic diamine as a diamine component.

Non-Patent Document 1 discloses the use of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride Polyfluorene imide as a tetracarboxylic acid component. Further, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid used herein is described. The dianhydride includes 6 stereoisomers. Patent Document 8 also discloses the use of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acid di Polyimide having an anhydride as a tetracarboxylic acid component.

However, depending on the application, particularly in fields such as display devices, it is desirable to reduce the thickness direction retardation in addition to high transparency. Since a film having a large retardation in the thickness direction is penetrated, problems such as incorrect color display, bleeding, and narrowing of the viewing angle may occur. Therefore, particularly in the field of display devices and the like, polyimide films with small phase difference in thickness direction have been sought.

On the other hand, Patent Document 9 discloses a polyimide formed by heating a coating solution obtained by blending a polyimide precursor (polyamidic acid) with an imidazoline-based compound and / or an imidazole-based compound. More specifically, in Example 1, a polyamic acid obtained from 3,3 ', 4,4'-diphenylketone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether was obtained. A solution obtained by adding 2,4-dimethylimidazoline to the solution was coated on a substrate and heated at 200 ° C. for 1 hour to obtain an aromatic polyimide film having a film thickness of 1000 angstroms (0.1 μm). In Example 2, 2-ethylimidazoline and 1,2-dimethyl are added to a solution of polyphosphonic acid obtained from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether. A solution made of imidazole was coated on a substrate and heated at 150 ° C. for 1 hour to obtain an aromatic polyfluorene imide film having a thickness of 800 angstroms (0.08 μm). Patent Document 9 describes that by adding an imidazoline-based compound and / or an imidazole-based compound to avoid significant brown coloration, a liquid crystal display element having excellent transparency with high light transmittance can be obtained. However, the liquid crystal display element using the polyfluorene imide film (liquid crystal alignment film) of Example 1 had a light transmittance of 82% at a wavelength of 400 nm (polyimide film thickness: 0.1 μm), and the polymer of Example 2 was used. The transmissivity of the fluorene imide film (liquid crystal alignment film) of the liquid crystal display element at a wavelength of 400 nm was 83% (polyfluorene imide film thickness: 0.08 μm), and the polyfluorene imide did not have sufficient transparency.

In addition, as a method for producing a low-transparency aromatic polyimide, Patent Document 10 discloses that a polyimide precursor resin such as imidazole and N-methylimidazole is cured. A solution containing a polyimide precursor resin obtained by dissolving an accelerator in an organic polar solvent is coated on a substrate, and then a polyimide resin layer formed by drying by heat treatment and using imidization is formed on the substrate. A method for forming a polyimide resin layer that is completed in a range of 280 to 380 ° C, and describes that by using such a hardening accelerator, the coefficient of thermal linear expansion can be controlled to be low. Patent Document 10 describes that it is preferable to use a hardening accelerator whose boiling point exceeds 120 ° C, and it is preferable to select a boiling point that does not exceed the upper limit of the heat treatment. It is also described that a hardening accelerator having a boiling point of, for example, 400 ° C or higher, is used for imidization. The remaining ratio of the polyimide resin layer is high, which tends to affect the function of the polyimide resin layer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2003-192787 [Patent Document 2] JP 2004-83814 [Patent Document 3] JP 2008-308550 [Patent Document 4] JP 2003-168800 [Patent Document 5] International Publication No. 2008/146637 [Patent Document 6] Japanese Patent Publication No. 2002-69179 [Patent Document 7] Japanese Patent Publication No. 2002-146021 [Patent Document 8] International Publication No. 2011 / 099518 [Patent Document 9] Japanese Patent Laid-Open No. 61-267030 [Patent Document 10] Japanese Patent Laid-Open No. 2008-115378 [Non-Patent Document]

[Non-Patent Literature 1] Proceedings of Polymers, Vol. 68, No. 3, P. 127-131 (2011)

[Questions to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyimide which is excellent in transparency and has a small phase difference in thickness direction even with the same composition, or a small phase difference in thickness direction, and a mechanical device. Polyimide polyimide precursor composition (a polyimide precursor-containing solution composition) of polyimide, and excellent transparency, and a method for producing polyimide. [Solution to Problem]

The present invention relates to the following items. A polyimide precursor composition comprising: a polyimide precursor containing a repeating unit represented by the following chemical formula (1) or a repeating unit represented by the following chemical formula (2); and an imidazole-based compound; and an imidazole-based compound The content of the compound is less than 4 moles relative to 1 mole of the repeat unit of the polyimide precursor;

[Chemical 1] (Wherein X ₁ is a tetravalent group having an alicyclic structure, Y ₁ is a divalent group having an aromatic ring, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbons, or carbon (Number of 3 to 9 alkylsilyl groups)

[Chemical 2] (Wherein X ₂ is a tetravalent group having an aromatic ring, Y ₂ is a divalent group having an alicyclic structure, and R ₃ and R ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbons, or carbon Number 3 to 9).

2. The polyimide precursor composition of 1., wherein the polyimide obtained from the polyimide precursor composition has a light transmittance of a thickness of 10 μm at a wavelength of 400 nm of 75% or more. 3. The polyimide precursor composition according to 1. or 2., wherein the content of the imidazole-based compound is 0.05 mol or more and 2 mol or less relative to 1 mol of the repeating unit of the polyimide precursor. . 4. The polyimide precursor composition according to any one of 1. to 3., wherein the boiling point of the imidazole-based compound at 1 atmosphere does not reach 340 ° C. 5. The polyfluorene imide precursor composition according to any one of 1. to 4, wherein the imidazole compound is 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, Any of 2-phenylimidazole, imidazole, or benzimidazole. 6. A method for producing polyimide, characterized in that the polyimide precursor composition according to any one of 1. to 5. is subjected to a heat treatment at a maximum heating temperature exceeding 350 ° C. The amine precursor is imidized. 7. The method for manufacturing polyimide according to 6., comprising the steps of: coating the polyimide precursor composition according to any one of 1. to 5. on a substrate; and coating the substrate on the substrate; The polyimide precursor composition is subjected to a heat treatment at a maximum heating temperature exceeding 350 ° C. to thereby polyimide the precursor. 8. The method for producing polyimide according to 6. or 7., wherein the maximum heating temperature of the heat treatment exceeds 400 ° C. 9. A polyimide, which is produced by the method for producing polyimide according to any one of 6. to 8. 10. The polyfluorene imine of 9., wherein the transmittance of the film having a thickness of 10 μm at a wavelength of 400 nm is 75% or more. 11. A polyimide film, which is produced using the method for producing polyimide according to any one of 6. to 8. 12. A substrate for a display, a touch panel, or a solar cell, comprising a polyimide film such as 9. or 10. or a polyimide film such as 11. [Effect of the invention]

According to the present invention, it is possible to obtain a polyimide having excellent transparency, and even a polyimide having the same composition but a small phase difference in the thickness direction, or a small phase difference in the thickness direction, excellent mechanical properties, and transparency. Excellent polyimide precursor polyimide precursor composition (solution composition containing polyimide precursor), and method for producing polyimide.

The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention has high transparency and small phase difference in the thickness direction, and has a low linear thermal expansion coefficient, and is easy to form fine circuits. , Suitable for forming substrates for display applications and the like. In addition, the polyimide of the present invention can be ideally used for forming a substrate for a touch panel and a solar cell.

The polyimide precursor composition of the present invention includes a polyimide precursor containing at least one of the repeating unit represented by the aforementioned chemical formula (1) or the repeating unit represented by the aforementioned chemical formula (2), and imidazole The content of the imidazole compound is less than 4 moles relative to the repeating unit of the polyimide precursor.

Polyimide obtained from a polyimide precursor containing at least one of the repeating unit represented by the aforementioned chemical formula (1) or the repeating unit represented by the aforementioned chemical formula (2), that is, a semialicyclic polyimide Amine is highly transparent. In the case of such a highly transparent polyimide, it is difficult to use an additive which may cause coloring. However, the imidazole-based compound is added to the polyimide precursor at a ratio of 1 mol to 4 mol, preferably 0.05 mol to 2 mol, relative to the repeat unit of the polyfluorene imide precursor. The composition can obtain polyimide which maintains high transparency and has a small phase difference in the thickness direction. That is, according to the present invention, polyimide having a state of maintaining high transparency and a small phase difference in thickness direction can be obtained from polyimide precursors of the same composition. In addition, when an imidazole-based compound having a boiling point of less than 340 ° C at 1 atmosphere is used, the transparency of the obtained polyimide may be further improved.

Furthermore, in order to obtain polyimide with high transparency, it is generally considered that it is better to heat the polyimide precursor at a relatively low temperature to complete the imidization. However, according to the present invention, even if the maximum heating temperature exceeds 350, ℃, particularly preferably a heat treatment in excess of 400 ℃, the polyfluorene imide precursor is fluorinated, and high transparency polyfluorene can still be produced. As a result, the highest heating temperature for the heat treatment for ammonium imidization can be a high temperature exceeding 350 ° C, and particularly preferably a high temperature exceeding 400 ° C, so the mechanical properties of the obtained polyimide are improved. That is, according to the present invention, a polyimide having high transparency, a small phase difference in the thickness direction, and excellent mechanical properties can be obtained.

As described above, the polyfluorene imide precursor composition of the present invention includes a polyfluorene imide precursor containing at least one of the repeating unit represented by the aforementioned chemical formula (1) or the repeating unit represented by the aforementioned chemical formula (2).

As in the aforementioned chemical formula ₍₁₎ X 1, appropriate for the carbon number of 4 to 40. The tetravalent group the ring structure of the fat is desirable, as Y _1, appropriate for the carbon number of 6 to 40. The divalent aromatic rings Better.

The tetracarboxylic acid component which gives the repeating unit of the aforementioned chemical formula (1), for example: 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidene diphenoxybisphthalic acid, cyclohexane- 1,2,4,5-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-3,3 ', 4,4'-tetracarboxylic acid, [1,1'-bi (cyclohexane Alkanes)]-2,3,3 ', 4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4 ' -Methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4 '-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4 4,4'-oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfofluorenyl Bis (cyclohexane-1,2-dicarboxylic acid), 4,4 '-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(quad Fluoropropane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), octahydropentalene-1,3,4,6-tetracarboxylic acid, bicyclo [2.2.1] heptane Ethane-2,3,5,6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid, bicyclo [2.2.2] octane-2 , 3,5,6-tetracarboxylic acid, bicyclic [2.2.2] oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclic [4.2.2.02,5] decane-3,4 , 7,8-tetracarboxylic acid, tricyclic [4.2.2.02,5] dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxa Cyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane 5 , 5 '', 6,6 ''-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethyl bridgenaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, ( 4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethyl bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic silicon ester, tetracarboxylic acid Derivatives such as acid esters, tetracarboxylic acid chloride. The tetracarboxylic acid component may be used singly or in combination.

The diamine component imparting the repeating unit of the aforementioned chemical formula (1), for example: p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis (trifluoro (Methyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, m-toluidine, 4,4'-diaminobenzidine, 3,4'-diaminobenzidine Aniline, N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-p-phenylenebis (p-aminobenzylamine), 4-aminophenoxy 4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid bis (4-aminophenyl) ester, p- Phenylene bis (p-aminobenzoate), bis (4-aminophenyl)-[1,1'-biphenyl] -4,4'-dicarboxylic acid ester, [1,1'- Biphenyl] -4,4'-diylbis (4-aminobenzoate), 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxyl Diphenylamine, p-methylenebis (phenylenediamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane Alkane, bis (4-aminophenyl) fluorene, 3,3'-bis (trifluoromethyl) benzidine, 3,3'-bis ((aminophenoxy) phenyl) propane, 2,2 '-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) diphenyl) fluorene, bis (4- (3-aminophenoxy ) Diphenyl) fluorene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diamine Benzene, 3,3'-difluoro-4,4'-diaminobiphenyl, 2 ', 4-bis (4-aminoaniline) -6-amino-1,3,5-tri 2,4-bis (4-aminoaniline) -6-methylamino-1,3,5-tri , 2,4-bis (4-aminoaniline) -6-ethylamino-1,3,5-tris , 2,4-bis (4-aminoaniline) -6-aniline-1,3,5-tris . The diamine component may be used alone or in combination.

The polyimide precursor containing at least one of the repeating units represented by the aforementioned chemical formula (1) may contain repeating units other than the repeating unit represented by the aforementioned chemical formula (1). The tetracarboxylic acid component and the diamine component imparting other repeating units are not particularly limited, and any of other known aromatic or aliphatic tetracarboxylic acids, known aromatic or aliphatic diamines can be used. The other tetracarboxylic acid components may be used alone or in combination. The other diamine components may be used alone or in combination.

The content of the repeating unit other than the repeating unit represented by the aforementioned chemical formula (1) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, and more preferably relative to all the repeating units. It is 10 mol% or less.

As X ₂ in the aforementioned chemical formula (2), a tetravalent group having an aromatic ring having 6 to 40 carbon atoms is preferable, and a divalent group having an alicyclic structure having 4 to 40 carbon atoms is preferable as Y ₂ . .

The tetracarboxylic acid component that gives the repeating unit of the aforementioned chemical formula (2), for example: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-diphenylketone tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis (3,4-dicarboxyl Phenyl) hydrazone dianhydride, m-terphenyltriphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, p-terphenyltriphenyl-3,4,3', 4'-tetracarboxylic dianhydride, bis Carboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfofluorenyl diphthalic acid, tetracarboxylic dianhydride, tetracarboxylic silicon ester, tetracarboxylic acid ester, tetracarboxylic acid Carboxyl chloride and other derivatives. The tetracarboxylic acid component may be used singly or in combination.

The diamine component imparting the repeating unit of the aforementioned chemical formula (2), for example: 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamine 2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino 2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-second butylcyclohexane, 1,4-di Amino-2-third butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, iso Furone diamine, diamino tricyclodecane, diaminomethyl tricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) isopropylidene 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy)- 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane. The diamine component may be used alone or in combination.

The polyimide precursor containing at least one of the repeating units represented by the aforementioned chemical formula (2) may contain repeating units other than the repeating unit represented by the aforementioned chemical formula (2). The tetracarboxylic acid component and the diamine component imparting other repeating units are not particularly limited, and any one of other known aromatic or aliphatic tetracarboxylic acids and known aromatic or aliphatic diamines can be used. The other tetracarboxylic acid components may be used alone or in combination. The other diamine components may be used alone or in combination.

The content of the repeating unit other than the repeating unit represented by the aforementioned chemical formula (2) is preferably 30 mol% or less, or more than 20 mol%, and more preferably relative to the total repeating unit. It is 10 mol% or less.

The polyfluorene imide precursor may include at least one of the repeating units represented by the aforementioned chemical formula (1) and at least one of the repeating units represented by the aforementioned chemical formula (2). In this case, the content of the repeating units other than the repeating units represented by the aforementioned chemical formulas (1) and (2) is preferably 30 mol% or less, or more preferably 20 mol% with respect to the total repeating units. Molar% or less, and more preferably 10 Molar% or less.

In an embodiment, the polyfluorene imide precursor is preferably, for example, a polyfluorene imide precursor including a repeating unit represented by the following chemical formula (1-1), and contains the following chemical formula (1-2) and the following chemical formula Polyimide containing at least one type of repeating unit represented by (1-3), and the total content of repeating units represented by chemical formula (1-2) and formula (1-3) is 80 mol% or more relative to all repeating units The precursor is more ideal.

[Chemical 3] (In the formula, A is a divalent group having an aromatic ring, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

[Chemical 4] (In the formula, A is a divalent group having an aromatic ring, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

[Chemical 5] (In the formula, A is a divalent group having an aromatic ring, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

However, the aforementioned chemical formula (1-1), the aforementioned chemical formula (1-2), and the aforementioned chemical formula (1-3) represent the 5- or 6-position of two norbornane rings (bicyclo [2.2.1] heptane). One of the acid groups reacts with an amine group to form an amine bond (-CON H-), and the other acid group is a group represented by -COOR ₁ or a group represented by -COOR ₂ without forming an amine bond. That is, the aforementioned chemical formula (1-1), the aforementioned chemical formula (1-2), and the aforementioned chemical formula (1-3) have four structural isomers, that is, all of the following are included: (i) -COOR _{1 at the} 5-position The base of which 6 has a base represented by -CONH-, and the base of 5 '' has a base represented by -COOR _{2 and} the base of 6 '' has a base represented by -CONH-A-; (ii) the base 6 has -COOR ₁ A base represented by 5 digits has a base represented by -CONH-, and a base of 5 '' has a base represented by -COOR ₂ and a base of 6 '' has a base represented by -CONH-A-; (iii) the base 5 has -COOR ₁ represents a base, 6 has a base represented by -CONH-, 6 '' has a base represented by -COOR ₂ and 5 '' has a base represented by -CONH-A-; (iv) 6 has a- The base represented by COOR ₁ has a base represented by -CONH- at the 5th position, and the base represented by -COOR _{2 at the} 6 "position and the base represented by -CONH-A- at the 5" position.

In addition, the polyfluorene imide precursor should preferably contain a repeating unit represented by the chemical formula (1-1) in which A is a group represented by the following chemical formula (1-A), and more preferably A is represented by the following chemical formula (1-A) It is preferred that at least one of the repeating units represented by the chemical formula (1-2) and / or the chemical formula (1-3) is a base.

[Chemical 6] (In the formula, m represents an integer of 0 to 3, n represents an integer of 0 to 3, and m and n are independent of each other. V, U, and T each independently represent a member selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group One of the groups, Z and W each independently represents a direct bond, or is selected from the group consisting of a base represented by the formula: -NHCO-, -CONH-, -COO-, -OCO- 1 kind.)

In other words, in a certain aspect, the polyfluorene imide precursor system consists of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6 , 6 ''-tetracarboxylic acids, etc., more preferably trans-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc. and / or cis-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane- 5,5 '', 6,6 ''-tetracarboxylic acids and the like (tetracarboxylic acids and the like, representing tetracarboxylic acid, and tetracarboxylic dianhydride, silicon tetracarboxylic acid ester, tetracarboxylic acid ester, tetracarboxylic acid chloride, etc. The tetracarboxylic acid component of the tetracarboxylic acid derivative) and the diamine component including an aromatic ring are more preferably the chemical formula (1-1) and the chemical formula (1) which give A to the group represented by the aforementioned chemical formula (1-A) -2) or a polyimide precursor obtained from the diamine component of the diamine component of the repeating unit of the chemical formula (1-3).

As the tetracarboxylic acid component that imparts the repeating unit of the aforementioned chemical formula (1-1), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 can be used. '', 6,6 ''-tetracarboxylic acids are used alone or in combination. As the tetracarboxylic acid component that imparts the repeating unit of the aforementioned chemical formula (1-2), trans-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''- Norbornane-5,5 '', 6,6 ''-tetracarboxylic acids can be used singly or in combination. As the tetracarboxylic acid component imparting the repeating unit of the aforementioned chemical formula (1-3), cis-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''- Norbornane-5,5 '', 6,6 ''-tetracarboxylic acids are used singly or in combination.

Moreover, in the polyimide precursor in a more ideal form, only the tetracarboxylic acid component (trans-inward-inward-norbornane-2-spiro-) that imparts the repeating unit of the aforementioned chemical formula (1-2) may be used. α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc.) may be used alone or in combination with one or more of the following chemical formulas ( 1-3) tetracarboxylic acid component of the repeating unit (cis-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc.), or a tetracarboxylic acid component (trans-inward-inward-inward-norbornane) which gives a repeating unit of the aforementioned chemical formula (1-2) may be used. 2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc.) (1-3) The tetracarboxylic acid component of the repeating unit (cis-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5, 5 '', 6,6 ''-tetracarboxylic acids, etc.).

In the polyfluorene imide precursor, the total content of the repeating units represented by the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) is preferably 80 mol% or more with respect to all the repeating units, that is, it contains the foregoing At least one kind of repeating unit represented by the chemical formula (1-2) and the aforementioned chemical formula (1-3), and the total repeating unit in the total repeating unit preferably contains 80 mol% or more, and more preferably 90 mol% Above, still more preferably 95 mol% or more, even more preferably 99 mol% or more. It contains at least one kind of repeating unit represented by the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3), and the total repeating unit in all the repeating units preferably contains 80 mol% or more. The linear thermal expansion coefficient of polyimide decreases.

The diamine component imparting the repeating unit of the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2), or the aforementioned chemical formula (1-3), preferably contains one which imparts A to the base represented by the aforementioned chemical formula (1-A). Diamine is preferred.

The diamine component that gives the repeating unit of the chemical formula (1-1) or the chemical formula (1-2) or the chemical formula (1-3) to the structure A is the aforementioned chemical formula (1-A). In the case of each aromatic ring, each of the aromatic rings is directly bonded to each other independently, and is linked by a amide bond or an ester bond. The position where the aromatic rings are connected to each other is not particularly limited. The amine group or the connection to the aromatic rings forms a linear structure based on a 4-position bond. In some cases, the obtained polyimide may have a low linear thermal expansion. The aromatic ring may be substituted by a methyl group or a trifluoromethyl group. The substitution position is not particularly limited.

The diamine component that is a repeating unit of the chemical formula (1-1), or the chemical formula (1-2), or the chemical formula (1-3) that gives A the structure of the aforementioned chemical formula (1-A) is not particularly limited, for example: Phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) ) Benzidine, m-toluidine, 4,4'-diaminobenzidine aniline, 3,4'-diaminobenzidine aniline, N, N'-bis (4-aminophenyl) para Xylylenediamine, N, N'-p-phenylene bis (p-aminobenzylamine), 4-aminophenoxy-4-diaminobenzoate, bis (4-amino Phenyl) terephthalate, biphenyl-4,4'-dicarboxylic acid bis (4-aminophenyl) ester, p-phenylene bis (p-aminobenzoate), bis (4 -Aminophenyl)-[1,1'-biphenyl] -4,4'-dicarboxylic acid ester, [1,1'-biphenyl] -4,4'-diylbis (4-amino group Benzoate) and the like may be used alone or in combination. Among them, p-phenylenediamine, m-toluidine, 4,4'-diaminophenhydrazidine, 4-aminophenoxy-4-diaminobenzoate, 2,2 ' -Bis (trifluoromethyl) benzidine, benzidine, N, N'-bis (4-aminophenyl) p-xylylenediamine, biphenyl-4,4'-dicarboxylic acid bis (4- Aminophenyl) esters are more preferred, and p-phenylenediamine, 4,4'-diaminobenzidine aniline, and 2,2'-bis (trifluoromethyl) benzidine are more preferred. As the diamine component, by using p-phenylenediamine, 4,4'-diaminobenzidine aniline, and 2,2'-bis (trifluoromethyl) benzidine, the obtained polyimide will take into account both the high Heat resistance and high transmittance. These diamines may be used alone or in combination. Moreover, o-toluidine is not preferable because of its high risk.

As the diamine component that imparts the repeating unit of the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2), or the aforementioned chemical formula (1-3), those that impart A to the structure of the aforementioned chemical formula (1-A) may be used in combination. Diamine other than the diamine component. As other diamine components, other aromatic or aliphatic diamines can be used. As other diamine components, for example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, bis (4-aminophenyl) sulfide, P-methylenebis (phenylenediamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4 -Aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenyl) fluorene, 3,3-bis ((aminophenoxy) phenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, Bis (4- (4-aminophenoxy) diphenyl) fluorene, bis (4- (3-aminophenoxy) diphenyl) fluorene, octafluorobenzidine, 3,3'-dimethyl Oxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl Benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) Biphenyl, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4- Diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-second butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane , 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1 , 3-bis (aminomethyl) cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, isophor Ketone diamine, diamino tricyclodecane, diaminomethyl tricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) isopropylidene 6,6'-bis ( 3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3 The derivatives of 3,3 ', 3'-tetramethyl-1,1'-spiroindane, and the like may be used alone or in combination.

The polyfluorene imide precursor of the present invention preferably contains at least one repeating unit of the aforementioned chemical formula (1-1) represented by the A-based aforementioned chemical formula (1-A), and more preferably contains the A-based aforementioned chemical formula (1-A) The at least one repeating unit of the aforementioned chemical formula (1-2) and / or A represents at least one repeating unit of the aforementioned chemical formula (1-3) represented by the aforementioned chemical formula (1-A). In other words, the repeating unit imparted to the aforementioned chemical formula (1-1) is more preferably a diamine component of the repeating unit of the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3), and it is preferable to contain a diamine component imparting A to the aforementioned chemical formula (1- The diamine component of the structure A) is preferred. By providing the repeating unit of the aforementioned chemical formula (1-1), it is more preferable that the diamine component of the aforementioned chemical formula (1-2) and the A in the aforementioned chemical formula (1-3) is the same as that of the aforementioned chemical formula (1-A) The diamine component of the structure improves the heat resistance of the obtained polyimide.

In the polyfluorene imide precursor of the present invention, 100 mol% of the diamine component imparted to the aforementioned chemical formula (1-1), or A in the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3), is provided. The total ratio of the diamine component of the structure of the aforementioned chemical formula (1-A) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more preferably 90 Molar% or more, particularly preferably 100 Molar%. In other words, A is the total proportion of one or more of the aforementioned chemical formula (1-1) of the structure of the aforementioned chemical formula (1-A), or the repeating unit of the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3). Among all the repeating units represented by the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3), it is preferably 50 mol% or more, more preferably 70 mol% or more, and It is more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 100 mol%. When the ratio of the diamine component which gives the structure of said chemical formula (1-A) is less than 50 mol%, the linear thermal expansion coefficient of the obtained polyimide may increase. In a certain aspect, considering the viewpoint of the mechanical properties of the obtained polyimide, the diamine of A in the aforementioned chemical formula (1-1) or the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) is given. Of the 100 mol% of the component, the total ratio of the diamine component imparting the structure of the aforementioned chemical formula (1-A) is preferably 80 mol% or less, more preferably 90 mol% or less, or less than 90 mol%. For example, other aromatic or aliphatic diamines such as 4,4'-oxydiphenylamine can be added to the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1- 3) The diamine component of the repeating unit of 100 mole% is preferably less than 20 mole%, more preferably less than 10 mole%, and still more preferably less than 10 mole%.

In an embodiment, the polyimide precursor of the present invention containing the repeating unit represented by the aforementioned chemical formula (1-1) may sometimes contain the chemical formula (1-1) of the A represented by the aforementioned chemical formula (1-A) At least two repeating units are preferred. In an embodiment, the polyimide precursor of the present invention containing the repeating unit represented by the aforementioned chemical formula (1-2) and / or the repeating unit represented by the aforementioned chemical formula (1-3) may sometimes contain an A-based It is preferable that at least two kinds of the repeating unit of the chemical formula (1-2) or the chemical formula (1-2) are represented by the chemical formula (1-A). In other words, the diamine component imparted to the repeating unit of the aforementioned chemical formula (1-1) or the diamine component imparted to the repeating unit of the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) may contain an A-based system. At least two types of diamine components of the structure of the aforementioned chemical formula (1-A) are preferred. Those who give A in the aforementioned chemical formula (1-1), or give a diamine component in the aforementioned chemical formula (1-2) and A in the aforementioned chemical formula (1-3) by containing the structure given the aforementioned chemical formula (1-A) At least two kinds of diamine components can achieve the balance between high transparency and low linear thermal expansion of the obtained polyimide (that is, polyimide with high transparency and low linear thermal expansion coefficient) .

In addition, the polyfluorene imide precursor of the present invention may contain at least two types of repeating units of the aforementioned chemical formula (1-2) having the structure of the A-based chemical formula (1-A), and may also contain the A-based chemical formula ( 1-A) has at least two repeating units of the aforementioned chemical formula (1-3) in the structure, and may contain at least 1 repeating units of the aforementioned chemical formula (1-2) in the structure of the A-based chemical formula (1-A) At least one kind of the repeating unit of the aforementioned chemical formula (1-3) which has a structure of A and the aforementioned chemical formula (1-A).

In a certain aspect, the polyfluorene imide precursor of the present invention may sometimes: (i) contain A-based m and / or n is 1 to 3, Z and / or W are each independently -NHCO-,- The chemical formula (1-1) of the structure of the chemical formula (1-A) of any one of CONH-, -COO-, or -OCO- is preferably the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1) -3) at least one repeating unit (I), and (ii) a structure containing the aforementioned chemical formula (1-A) in which A is m and n is 0, or m and / or n is 1 to 3, Z and W The aforementioned chemical formula (1-1), which is a structure of the aforementioned chemical formula (1-A) directly bonded, is preferably at least one of the aforementioned chemical formula (1-2) and the repeating unit (II) of the aforementioned chemical formula (1-3). Better.

In this embodiment, the aforementioned repeating unit (I), for example: A is a repeating unit of the aforementioned chemical formula (1-1) represented by any one of the following chemical formulas (D-1) to (D-3) Ideally, A is a repeating unit of the aforementioned chemical formula (1-1) represented by any one of the following chemical formulas (D-1) to (D-2). In addition, the diamine component imparting the repeating unit of the aforementioned chemical formula (1-1) represented by the following chemical formula (D-1) or the following chemical formula (D-2) to A is 4,4'-diaminobenzidine. The diamine component that imparts the repeating unit of the aforementioned chemical formula (1-1) represented by A to the following chemical formula (D-3) is bis (4-aminophenyl) terephthalate, and these diamines may be They can be used alone or in combination.

[Chemical 7]

In this embodiment, the aforementioned repeating unit (II), for example: A is a repeating unit of the aforementioned chemical formula (1-1) represented by any one of the following chemical formulas (D-4) to (D-6) Preferably, A is a repeating unit of the aforementioned chemical formula (1-1) represented by any one of the following chemical formulas (D-4) to (D-5). Furthermore, the diamine component of the repeating unit of the aforementioned chemical formula (1-1) given to A is represented by the following chemical formula (D-4) is p-phenylenediamine, and the aforementioned chemical formula of A represented by the following chemical formula (D-5) is given The diamine component of the repeating unit of (1-1) is 2,2'-bis (trifluoromethyl) benzidine, and A is given as a repeat of the aforementioned chemical formula (1-1) represented by the following chemical formula (D-6) The diamine component of the unit is m-toluidine, and these diamines may be used alone or in combination.

[Chemical 8]

In the polyfluorene imide precursor according to this embodiment, the total ratio of one or more types of the repeating unit (I) is 30 mol% or more and 70 mol or more in all the repeating units represented by the chemical formula (1-1). % Or less, the total proportion of one or more of the repeating unit (II) is preferably 30 mol% or more and 70 mol% or less in all the repeating units represented by the aforementioned chemical formula (1-1), and the repeating unit (I) The total proportion of one or more kinds is 40 mol% or more and 60 mol% or less in all the repeating units represented by the aforementioned chemical formula (1-1), and the total proportion of one or more kinds of the repeating unit (II) is in the aforementioned chemical formula (1). -1) is more preferably 40 mol% or more and 60 mol% or less in all the repeating units. In an embodiment, the total proportion of the repeating unit (I) is preferably less than 60 mol%, and more preferably less than 50 mol% in all the repeating units represented by the aforementioned chemical formula (1-1). Below 40 mol% is particularly preferred. Moreover, in an embodiment, the repeating unit represented by the aforementioned chemical formula (1-1) other than the repeating unit (I) and the repeating unit (II) (for example, A has a large number of aromatic rings and the aromatic rings are ethers with each other). The bond (-O-) linker) may be less than 20 mol%, more preferably 10 mol% or less, and even more preferably less than 10 mol in all the repeating units represented by the aforementioned chemical formula (1-1). The usage of% is better. Furthermore, in an embodiment, the total proportion of one or more repeating units (I) is 20 mol% or more and 80 mol% or less in all the repeating units represented by the chemical formula (1-1). The total proportion of one or more repeating units (II) is preferably 20 mol% or more and 80 mol% or less in all the repeating units represented by the aforementioned chemical formula (1-1).

In an embodiment, the polyimide precursor of the present invention containing the aforementioned chemical formula (1-1), or the repeating unit of the aforementioned chemical formula (1-2) and / or the aforementioned chemical formula (1-3), imparts the aforementioned Chemical formula (1-1), or the diamine component of A in the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) (the repeating unit given to the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2) ) And the diamine component of the repeating unit of the aforementioned chemical formula (1-3)) contains at least two types of diamine components imparting the structure of the aforementioned chemical formula (1-A), and one of them is free of 4,4'-diaminobenzene Pantefenil is preferred. The diamine component imparting the chemical formula (1-1), or the A in the chemical formula (1-2) and the chemical formula (1-3) contains at least two types of diamine components imparting the structure of the chemical formula (1-A). In addition, if one of them is 4,4'-diaminobenzidine aniline, polyimide having high transparency and low thermal expansion and high heat resistance can be obtained.

In an embodiment, the polyimide precursor of the present invention containing the aforementioned chemical formula (1-1), or the repeating unit of the aforementioned chemical formula (1-2) and / or the aforementioned chemical formula (1-3), imparts the aforementioned Chemical formula (1-1), or the diamine component of A in the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) (repeating unit of the aforementioned chemical formula (1-1), or imparting the aforementioned chemical formula (1-2) ) And the diamine component of the repeating unit of the aforementioned chemical formula (1-3)) is particularly preferred to contain at least one and 4 selected from 2,2'-bis (trifluoromethyl) benzidine and p-phenylenediamine. , 4'-Diaminobenzidine aniline. By combining these diamine components, polyimide having high transparency, low linear thermal expansion, and heat resistance can be obtained.

In this embodiment, as the diamine component imparted to the aforementioned chemical formula (1-1), or A in the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) (given in the aforementioned chemical formula (1-1) The repeating unit or the diamine component of the aforementioned chemical formula (1-2) and the repeating unit of the aforementioned chemical formula (1-3)) preferably contains 20 mol% or more of 4,4'-diaminobenzidine aniline, 80 mol% or less, and containing either or both of p-phenylenediamine and 2,2'-bis (trifluoromethyl) benzidine 20 mol% or more and 80 mol% or less Contains 4,4'-diaminobenzidine aniline 30 mol% or more and 70 mol% or less, and contains any of p-phenylenediamine and 2,2'-bis (trifluoromethyl) benzidine It is more preferable that it is 30 mol% or more and 70 mol% or less. It is particularly preferable that it contains 4,4'-diaminobenzidine aniline 40 mol% or more and 60 mol% or less and contains p-benzene. Either or both of the diamine and 2,2'-bis (trifluoromethyl) benzidine is more than 40 mol% and more preferably 60 mol% or less. As the diamine component that imparts A in the aforementioned chemical formula (1-1), or the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3), a 4,4′-diaminobenzidine aniline 30 is contained. Molar% or more and 70 Molar% or less, and either or both of p-phenylenediamine and 2,2'-bis (trifluoromethyl) benzidine is 30 Molar% or more and 70 Molar% or less Polyimide having high transparency, low linear thermal expansion, and heat resistance can be obtained. In an embodiment, as the diamine component imparting the aforementioned chemical formula (1-1), or A in the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) (the one imparting the aforementioned chemical formula (1-1) The repeating unit, or the diamine component of the aforementioned chemical formula (1-2) and the repeating unit of the aforementioned chemical formula (1-3)), preferably contains 4,4'-diaminobenzidine aniline up to 60 mole% It is more preferably 50 mol% or less, and more preferably 40 mol% or less.

The polyfluorene imide precursor of the present invention may contain a repeating unit other than the repeating units represented by the aforementioned chemical formula (1-1) or the aforementioned chemical formula (1-2).

As the tetracarboxylic acid component imparting other repeating units, other aromatic or aliphatic tetracarboxylic acids can be used. For example: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene -1,2-dicarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-diphenylketone tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2, 3,3 ', 4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) pyrene dihydrate, m-triphenyl-3, 4,3 ', 4'-tetracarboxylic dianhydride, terphenyltriphenyl-3,4,3', 4'-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxyphenoxydiamine Phenyl sulfide, sulfofluorenyl diphthalic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane-1,2 , 4,5-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-3,3 ', 4,4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)] -2,3,3 ', 4'-tetracarboxylic acid, [1,1'-bi (cyclohexane)]-2,2', 3,3'-tetracarboxylic acid, 4,4'-methylene Bis (cyclohexane-1,2-dicarboxylic acid), 4,4 '-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4' -Oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfofluorenylbis (cyclo Hexane-1,2-dicarboxylic acid), 4,4 '-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl) bis (cyclohexane -1,2-dicarboxylic acid), octahydropentadiene-1,3,4,6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, 6 -(Carboxymethyl) bicyclic [2.2.1] heptane-2,3,5-tricarboxylic acid, bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic acid, bicyclic [2.2. 2] oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclic [4.2.2.02,5] decane-3,4,7,8-tetracarboxylic acid, tricyclic [4.2.2.02 , 5] dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid, ( 4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethyl bridgenaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c- Derivatives such as dimethyl bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, and such acid dianhydrides may be used alone or in combination. Among these, bicyclic [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclic [2.2.2] octane-2,3,5,6-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethyl bridgenaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethylform Derivatives such as bridgenaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, etc., and these acid dianhydrides are easy to produce polyimide, and the obtained polyimide is excellent in heat resistance, so it is preferable. These acid dianhydrides may be used alone or in combination.

In addition, in the case of a polyfluorene imide precursor containing a repeating unit of the aforementioned chemical formula (1-2) and / or the aforementioned chemical formula (1-3), as a tetracarboxylic acid component imparting another repeating unit, cis- Inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc., and Formula-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids etc. Other norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc. (eg, norbornane 4 stereoisomers of alkane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride) .

The diamine component imparting another repeating unit may be a diamine component imparting a structure of the aforementioned chemical formula (1-A). In other words, as the diamine component that imparts another repeating unit, a repeating unit of the aforementioned chemical formula (1-1) that imparts a structure of A to the aforementioned chemical formula (1-A), or an A The diamine exemplified by the diamine component of the repeating unit of the aforementioned chemical formula (1-2) and the aforementioned chemical formula (1-3) in the structure. These diamines may be used alone or in combination.

As a diamine component imparting another repeating unit, other aromatic or aliphatic diamines can be used. For example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, bis (4-aminophenyl) sulfide, p-methylenebis ( Phenylenediamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-amino Phenyl) fluorene, 3,3-bis ((aminophenoxy) phenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4 -Aminophenoxy) diphenyl) fluorene, bis (4- (3-aminophenoxy) diphenyl) fluorene, octafluorobenzidine, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 9,9- Bis (4-aminophenyl) fluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 1,4 -Diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2- N-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2 -Isobutyl ring Alkane, 1,4-diamino-2-second butylcyclohexane, 1,4-diamino-2-third butylcyclohexane, 1,2-diaminocyclohexane, 1 1,4-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane , Diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, isophoronediamine, diaminotricyclodecane, Diaminomethyltricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) isopropylidene 6,6'-bis (3-aminophenoxy) -3,3, 3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl- The derivatives of 1,1'-spiro-indane and the like may be used alone or in combination.

Also, the synthesis method of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids and the like is not special It is limited, and it can synthesize | combine by the method etc. which are described in patent document 8. As described in Non-Patent Document 1, depending on the synthesis method, several stereoisomers may be included. By adding norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids, etc., or intermediate The body is purified by a column or the like, and the stereoisomers can be separately classified or a mixture of several kinds.

For trans-intro-intro-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic acids Etc., and cis-inward-inward-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetra Individuals such as carboxylic acids, or mixtures of these can also be obtained by adding norbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '' , 6,6 ''-tetracarboxylic acids and the like, or intermediates thereof are purified by column or the like.

When the tetracarboxylic acid component and the diamine component contain an isomer, the isomer may be isolated and used for polymerization or the like, or the isomer may be directly used for polymerization or the like as a mixture.

In the polyfluorene imide precursor of the present invention, R ₁ and R ₂ of the aforementioned chemical formula (1), and R ₃ and R _{4 of the} aforementioned chemical formula (2) are each independently hydrogen and a carbon number of 1 to 6, preferably carbon. Either an alkyl group having 1 to 3 or an alkylsilyl group having 3 to 9 carbons. R ₁ and R ₂ , R ₃ and R ₄ can be changed in the type of the functional group and the introduction rate of the functional group by a production method described later.

When R ₁ and R ₂ , R ₃ and R ₄ are hydrogen, the production of polyimide tends to be easy.

When R ₁ and R ₂ , R ₃ and R ₄ are alkyl groups having 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms, the storage stability of the polyfluorene imide precursor tends to be excellent. In this case, it is more preferable that R ₁ and R ₂ , R ₃ and R ₄ are methyl or ethyl.

When R ₁ and R ₂ , R ₃ and R ₄ are alkylsilyl groups having 3 to 9 carbon atoms, the solubility of the polyfluorene imide precursor tends to be excellent. In this case, it is more preferable that R ₁ and R ₂ , R ₃ and R ₄ are a trimethylsilyl group or a third butyldimethylsilyl group.

The introduction rate of the functional group is not particularly limited. When an alkyl group or an alkylsilyl group is introduced, each of R ₁ and R ₂ , R ₃ and R ₄ can have 25% or more, preferably 50% or more, more preferably 75% or more. Alkyl or alkylsilyl.

The polyimide precursors of the present invention, depending on the chemical structure adopted by R ₁ and R ₂ , R ₃ and R ₄ , can be classified as: 1) polyamidic acid (R ₁ and R ₂ , R ₃ and R ₄ is hydrogen), 2) polyamide acid ester (R ₁ and R _2, R ₃ and R ₄ is an alkyl group of at least a part), 3) 4) silicon polyamide acid ester (R ₁ and R _2, R ₃ And at least a part of R ₄ is an alkylsilyl group). In addition, the polyimide precursor of the present invention can be easily produced by the following production method according to its classification. However, the manufacturing method of the polyimide precursor of this invention is not limited to the following manufacturing methods.

1) Polyfluorinated acid The polyfluorinated imide precursor of the present invention can be obtained by using a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in the solvent, so that it is slightly moir, preferably a diamine. The molar ratio of the component to the tetracarboxylic acid component [mole number of the diamine component / mole number of the tetracarboxylic acid component] is 0.90 to 1.10, and more preferably 0.95 to 1.05. The reaction is carried out at a low temperature in a state where the fluorene imidization is suppressed, and it is ideally obtained in the form of a polyfluorene imine precursor solution composition.

It is not limited, and more specifically, the diamine can be dissolved by the organic solvent, and tetracarboxylic dianhydride is slowly added to the solution in a stirred state, and the mixture is stirred at 0 to 120 ° C, preferably 5 to 80 ° C. From 1 to 72 hours, a polyimide precursor is obtained. When the reaction is carried out at a temperature of 80 ° C or higher, the molecular weight changes depending on the temperature history during polymerization and the fluorene imidization is performed by heat. Therefore, the polyfluorene imide precursor may not be stably produced. The order of addition of the diamine and tetracarboxylic dianhydride in the above manufacturing method is easy to increase the molecular weight of the polyfluorene imide precursor, so it is preferable. In addition, the order of addition of diamine and tetracarboxylic dianhydride in the above-mentioned production method may be reversed, and it is preferable from the viewpoint of reducing the amount of precipitates.

When the molar ratio of the tetracarboxylic acid component to the diamine component is an excessive amount of the diamine component, if necessary, a carboxylic acid derivative may be added in an amount corresponding to an excessive molar number of the diamine component, and the tetracarboxylic acid may be added. The molar ratio of the component to the diamine component is approximately equivalent. As a carboxylic acid derivative herein, it is preferable that the viscosity of the polyimide precursor solution is not substantially increased, that is, the tetracarboxylic acid that does not substantially involve the extension of the molecular chain, or the tricarboxylic acid and its anhydride as a terminal stopper. Dicarboxylic acids and their anhydrides are preferred.

2) Polyphosphonate reacts a tetracarboxylic dianhydride with any alcohol to obtain a diester dicarboxylic acid, and then reacts with a chlorinated reagent (such as thionyl chloride, chloracetin, etc.) to obtain a diester dicarboxylic acid醯 Chlorine. The diester dicarboxylic acid chloride and diamine are stirred at a temperature of −20 to 120 ° C., preferably −5 to 80 ° C. for 1 to 72 hours to obtain a polyfluorene imide precursor. When the reaction is carried out at a temperature of 80 ° C or higher, the molecular weight changes depending on the temperature history during the polymerization and the fluorene imidization is performed due to heat, so that the polyfluorene imide precursor may not be stably produced. In addition, a polyamidine precursor can also be obtained simply by dehydrating condensation of a diester dicarboxylic acid and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.

The polyimide precursor obtained by this method is stable, so it can also be purified by reprecipitation such as adding water or alcohol.

3) Polysiloxane (indirect method) The diamine is reacted with a silylating agent in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Dissolve the silylated diamine in a dehydrated solvent, and add tetracarboxylic dianhydride while stirring. Stir for 1 to 72 hours at 0 to 120 ° C, preferably 5 to 80 ° C. , Can obtain polyimide precursors. When the reaction is carried out at a temperature of 80 ° C or higher, the molecular weight changes depending on the temperature history during the polymerization and the fluorene imidization is performed due to heat, so that the polyfluorene imide precursor may not be stably produced.

For the silylating agent used here, the use of a silylating agent that does not contain chlorine does not require refining the silylated diamine, which is ideal. Silicides without chlorine atoms, such as N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, hexamethyldisilazide Nitrogen. Containing no fluorine atom, from the viewpoint of low cost, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred.

In the silylation reaction of diamines, in order to promote the reaction, amine catalysts such as pyridine, piperidine, and triethylamine can be used. This catalyst can be directly used as a polymerization catalyst for polyimide precursors.

4) Polysiloxane (direct method) Mix the polyamino acid solution obtained in the method 1) with the silylating agent, and stir it at 0 ~ 120 ° C, preferably 5 ~ 80 ° C, for 1 ~ 72. In hours, a polyimide precursor can be obtained. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history during the polymerization and the fluorene imidization is performed by heat, so that the polyfluorene imide precursor may not be stably produced.

The silylating agent used here, using a silylating agent that does not contain chlorine, is not necessary to refine the silylated polyamic acid or the obtained polyimide, which is ideal. Examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamidamine, and hexamethyl Disilazane. Containing no fluorine atom, from the viewpoint of low cost, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred.

The aforementioned manufacturing methods can all be performed ideally in an organic solvent, and as a result, a solution or a solution composition containing a polyfluorene imide precursor can be easily obtained.

Solvents used in the preparation of polyimide precursors, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl Aprotic solvents such as 2-methylimidazolidone, dimethylimide, etc. are preferred, especially N, N-dimethylacetamide, but as long as the raw material monomer components and the precursor of polyimide The physical energy can be dissolved, and any kind of solvent can be used without any problem, and its structure is not particularly limited. Solvents include amine solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, and δ-valerolide Cyclic ester solvents such as esters, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate, propylene carbonate, and triethylene glycol Alcohol solvents, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane, dimethyl Chiayi and other ideal. In addition, other general organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyperidine, butyl cyperidine, 2 -Methyl cyperidine acetate, ethyl cyperidine acetate, butyl cyperidine acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethyl Dimethyl glycol ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits, Petroleum brain solvents and the like can also be used. A plurality of solvents may be used in combination.

In the present invention, the logarithmic viscosity of the polyfluorene imide precursor is not particularly limited, and the logarithmic viscosity in an N, N-dimethylacetamide solution at a concentration of 0.5g / dL at 30 ° C is 0.2dL / g or more, more It is preferably 0.3 dL / g or more, particularly preferably 0.4 dL / g or more. When the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide has excellent mechanical strength or heat resistance.

The polyimide precursor composition of the present invention contains a polyimide precursor and an imidazole-based compound, and the imidazole-based compound can be added to the polyimide precursor solution or solution composition obtained according to the aforementioned manufacturing method to prepare the polyimide precursor. If necessary, the solvent may be removed or added, and a desired component other than the imidazole-based compound may be added. In addition, a tetracarboxylic acid component (tetracarboxylic dianhydride, etc.), a diamine component, and an imidazole-based compound are added to a solvent, and the tetracarboxylic acid component and the diamine component are reacted in the presence of the imidazole-based compound to obtain the present invention. Polyimide precursor composition (a solution composition containing a polyimide precursor and an imidazole-based compound).

The imidazole-based compound used in the present invention is not particularly limited as long as it is a compound having an imidazole skeleton. By adding an imidazole-based compound, polyimide having a small phase difference in the thickness direction can be obtained.

In an embodiment, the imidazole-based compound is preferably a compound having a boiling point at 1 atmosphere of less than 340 ° C, preferably 330 ° C or lower, more preferably 300 ° C or lower, and particularly preferably 270 ° C or lower. By adding an imidazole compound having a boiling point of less than 340 ° C at 1 atmosphere, preferably 330 ° C or lower, more preferably 300 ° C or lower, and even more preferably 270 ° C or lower, polyfluorene having higher transparency may be obtained in some cases. amine.

The imidazole-based compound used in the present invention is not particularly limited, and examples thereof include 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, imidazole, and benzimidazole. 1,2-dimethylimidazole (boiling point at 1 atmosphere: 205 ° C), 1-methylimidazole (boiling point at 1 atmosphere: 198 ° C), 2-methylimidazole (boiling point at 1 atmosphere: 268 ° C), imidazole ( A boiling point of 1 atmosphere: 256 ° C) and the like are preferable, and 1,2-dimethylimidazole and 1-methylimidazole are particularly preferable. The imidazole-based compound may be used singly or in combination.

In the present invention, the content of the imidazole-based compound of the polyfluorene imide precursor composition is less than 4 mols relative to the repeating unit of the polyfluorene imide precursor. If the content of the imidazole-based compound is 1 mol or more with respect to 1 mol of the repeating unit of the polyimide precursor, the storage stability of the polyimide precursor composition becomes poor. The content of the imidazole-based compound is preferably 0.05 mol or more with respect to 1 mol of the repeating unit of the polyimide precursor, and it is preferably 2 mol or less with respect to 1 mol of the repeating unit of the polyimide precursor. Better. Here, 1 mole of the repeating unit of the polyfluorene imide precursor corresponds to 1 mole of the tetracarboxylic acid component.

The polyfluorene imide precursor composition of the present invention usually contains a solvent. The solvent used in the polyfluorene imide precursor composition of the present invention is not a problem as long as it can dissolve the polyfluorene imide precursor, and its structure is not particularly limited. As the solvent, amine solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, γ-butyrolactone, and γ-pentyl Cyclic ester solvents such as esters, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethyl carbonate and propylene carbonate, Glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, Cyclopentamidine, dimethyl sulfene and the like. Furthermore, other general organic solvents can be used, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyperidine, butyl cyperidine , 2-methylcythrethacetate, ethylcythrethacetate, butylcythrethacetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, Diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits , Petroleum brain solvent. Moreover, you may use these in combination of multiple types. As the solvent of the polyfluorene imide precursor composition, a solvent used when preparing a polyfluorene imine precursor can be directly used.

In the present invention, the total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass relative to the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. A ratio above% is ideal. The total amount of the tetracarboxylic acid component and the diamine component is usually 60% by mass or less, and preferably 50% by mass or less with respect to the total amount of the solvent, the tetracarboxylic acid component, and the diamine component. This concentration is approximately close to the solid content concentration of the polyimide precursor. If the concentration is too low, the film thickness of the polyimide film obtained when the polyimide film is produced, for example, may become difficult to control.

In the present invention, the viscosity (rotary viscosity) of the varnish of the polyimide precursor is not particularly limited. The rotational viscosity measured by using an E-type rotational viscometer at a temperature of 25 ° C and a shear rate of 20sec ^-1 is 0.01 to 1000Pa‧sec. More ideal, 0.1 ~ 100Pa‧sec is more ideal. If necessary, thixotropy may be imparted. The viscosity in the above range is easy to handle during coating or film formation. In addition, the eye hole is suppressed, the uniformity is excellent, and a good coating film can be obtained.

The varnish of the polyfluorene imide precursor of the present invention may be added with chemical fluorimide (anhydride such as acetic anhydride or amine compounds such as pyridine and isoquinoline), antioxidants, fillers (inorganic materials such as silicon dioxide) as needed. Particles, etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), release agents, and the like.

The polyfluorene imide of the present invention can be obtained by subjecting the polyfluorene imine precursor composition of the present invention to fluoridation (ie, subjecting the polyfluorene imide precursor to a dehydration ring-closing reaction). The method of fluorene imidization is not particularly limited, and a known method of thermal fluorination or chemical fluorination can be preferably used. The form of the obtained polyimide includes films, laminates of polyimide films and other substrates, coating films, powders, beads, shaped bodies, foams, and varnishes.

In the present invention, the polyfluorene imine precursor composition is preferably subjected to a heat treatment at a maximum heating temperature exceeding 350 ° C. to thereby fluorinate the polyfluorene imine precursor. The maximum heating temperature for the heat treatment for amidine imidization is more than 380 ° C, and more preferably more than 400 ° C. The mechanical properties of the polyimide obtained by using the highest heating temperature of the heat treatment with amidine imidization is a temperature exceeding 350 ° C, more preferably a temperature exceeding 380 ° C, and even more preferably a temperature exceeding 400 ° C. improve. The upper limit of the maximum heating temperature of the heat treatment is not particularly limited, but is usually preferably 500 ° C or lower.

For example: the polyimide precursor composition of the present invention is cast-coated on a substrate, and the polyimide precursor composition on the substrate is heated at a temperature exceeding 350 ° C, and more preferably If the temperature exceeds 380 ° C, it is particularly preferable to perform a heat treatment at a temperature exceeding 400 ° C to subject the polyfluorene imine precursor to sulfamidation, thereby making it possible to ideally produce a polyfluorene. The heating curve is not particularly limited and can be selected as appropriate, but considering the productivity, the heat treatment time should preferably be short.

In addition, the polyimide precursor composition of the present invention is cast-coated on a substrate, and preferably dried at a temperature range of 180 ° C or lower to form a polyimide precursor composition on the substrate. Film, and the obtained polyimide precursor composition film was peeled from the substrate, and the end portion of the film was fixed in a state where the maximum heating temperature exceeded 350 ° C. The heat treatment is more preferably carried out at a temperature of more than 380 ° C., and more preferably at a temperature of more than 400 ° C., so that the polyfluorene imine precursor can be fluorinated, and polyfluorene can also be produced ideally.

An example of a more specific production method of the polyimide (polyimide film / base material laminate or polyimide film) of the present invention will be described later.

The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention is not particularly limited, and the linear thermal expansion coefficient of 150 ° C to 250 ° C is preferably 60 ppm / K when it is formed into a film Below, more preferably 50 ppm / K or less, still more preferably 45 ppm / K or less, even more preferably 40 ppm / K or less, and even more preferably 35 ppm / K or less. If the coefficient of linear thermal expansion is large, the difference between the coefficient of linear thermal expansion and a conductor such as a metal is large, and there may be problems such as increased warpage when forming a circuit board.

The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention is not particularly limited, and the total light transmittance of a film having a thickness of 10 μm (average light transmittance at a wavelength of 380 nm to 780 nm) It is preferably at least 86%, more preferably at least 87%, and even more preferably at least 88%. When the display is used for applications such as low total light transmittance, it is necessary to strengthen the light source, which may cause problems such as energy consumption.

In particular, when the light-transmitting polyimide film is used in a display application or the like, the polyimide film is preferably one having high transparency. The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention is not particularly limited, and the transmittance of a film having a thickness of 10 μm at a wavelength of 400 nm is preferably 75% or more, more preferably It is more than 80%, more preferably more than 80%, even more preferably 81% or more, and even more preferably 82% or more.

In addition, a film made of polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention depends on the application, and the film thickness is preferably 0.1 μm to 250 μm, and more preferably 1 μm to 150 μm, more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the polyfluorene imide film is used in a light-transmitting application, if the polyfluorine imide film is too thick, there is a possibility that the light transmittance may decrease.

The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention is not particularly limited, and the heat resistance index of the polyimide film, that is, a 1% weight reduction temperature is preferably 395 ° C. Above, more preferably 430 ° C or more, even more preferably 440 ° C or more, and even more preferably 470 ° C or more. If the formation of a polyimide on a polyimide is equivalent to the formation of a gas barrier film on the polyimide, etc., if the heat resistance is low, the polyimide and the barrier film may be caused by the decomposition of the polyimide. Swelling caused by the dissipated gas.

The polyimide (polyimide of the present invention) obtained from the polyimide precursor composition of the present invention is not particularly limited, and the phase difference in the thickness direction of the polyimide film is preferably 1,000 nm or less, more preferably 800 nm. Hereinafter, it is more preferably 700 nm or less, and even more preferably 600 nm or less. If the phase difference in the thickness direction is large, the color of transmitted light may not be displayed correctly, and there may be problems of color bleeding and a narrow viewing angle.

The polyimide obtained from the polyimide precursor composition of the present invention, that is, the polyimide of the present invention, has a small phase difference in the film thickness direction, and has excellent transparency, bending resistance, and high heat resistance. And has a very low coefficient of linear thermal expansion, it can be ideally used for transparent substrates for displays, transparent substrates for touch panels, or substrates for solar cells.

Hereinafter, an example of a method for manufacturing a polyimide film / substrate laminate or a polyimide film using the polyimide precursor composition of the present invention will be described. It is not limited to the following methods.

The varnish of the polyimide precursor of the present invention is cast on a substrate such as ceramic (glass, silicon, alumina), metal (copper, aluminum, stainless steel), heat-resistant plastic film (polyimide), and Dry in vacuum, inert gas such as nitrogen, or in the air using hot air or infrared at a temperature range of 20 to 180 ° C, preferably 20 to 150 ° C. Next, the obtained polyimide precursor film is on the substrate, or the polyimide precursor film is peeled off from the substrate, and the end portion of the film is fixed. In a vacuum, inertness such as nitrogen In the gas or air, use hot air or infrared at about 200 ~ 500 ° C, preferably the maximum heating temperature is more than 350 ° C, more preferably more than 380 ° C, and even more preferably more than 400 ° C. A polyimide film / substrate laminate or a polyimide film can be produced. In addition, in order to prevent the obtained polyfluorene imide film from being oxidatively deteriorated, it is preferable to carry out the heating of the polyfluorene imine in a vacuum or in an inert gas. Here, the thickness of the polyimide film (polyimide film / polyimide film layer in the case of a polyimide film / substrate laminate) is preferably 1 to 250 μm, and more preferably 1 for the transportability of the subsequent steps. ~ 150μm.

In addition, for the fluorene imidization reaction of the polyfluorene imine precursor, the heating fluorene imidization as described in the foregoing heat treatment may be replaced by using a polyfluorene imine precursor in a tertiary amine such as pyridine or triethylamine. Chemical treatment such as immersion in a solution containing a dehydration cyclization reagent such as acetic anhydride is performed in the presence. In addition, these dehydration cyclization reagents can be put into a polyimide precursor composition (varnish) in advance, stirred, and cast and dried on a substrate to prepare a partially fluorinated polyamidine. The imine precursor can be further subjected to the heat treatment as described above to obtain a polyimide film / substrate laminate or a polyimide film.

The polyimide film / base material laminate or polyimide film obtained in this way can form a flexible conductive substrate by forming a conductive layer on one or both sides.

The flexible conductive substrate can be obtained, for example, by the following method. That is, as the first method, the polyimide film is not peeled from the base material of the polyimide film / substrate laminate, and the polyimide film surface is sputtered, vapor-deposited, printed, or the like. Form a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, etc.), and manufacture a conductive laminate of a conductive layer / polyimide film / base material. Then, if necessary, the conductive layer / polyimide film laminate is peeled from the substrate, and a transparent and flexible conductive substrate composed of the conductive layer / polyimide film laminate can be obtained.

As a second method, the polyimide film can be peeled off from the base material of the polyimide film / substrate laminate to obtain a polyimide film, and the polyimide film surface can be the same as the first method. Similarly, a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, etc.) is formed to obtain a conductive layer / polyimide film laminate, or a conductive layer / polyimide A transparent and flexible conductive substrate made of a film laminate / conductive layer.

In the first and second methods, if necessary, before forming a conductive layer on the surface of the polyimide film, a gas barrier layer such as water vapor or oxygen may be formed by sputtering, vapor deposition, or gel-sol method. An inorganic layer such as a light adjustment layer.

The conductive layer can be formed into a circuit by a photolithography method, various printing methods, or inkjet methods.

The substrate of the present invention is a circuit having a conductive layer on the surface of a polyimide film composed of the polyimide of the present invention, if necessary, through a gas barrier layer or an inorganic layer. This substrate is flexible, has high transparency, bendability, and heat resistance, and has a very low coefficient of linear thermal expansion up to high temperatures or excellent solvent resistance, so it is easy to form fine circuits. Therefore, the substrate can be ideally used as a substrate for a display, a touch panel, or a solar cell.

That is, it is ideal to use this substrate to further form transistors (inorganic transistors, organic transistors) by vapor deposition, various printing methods, or inkjet methods, and to produce flexible thin-film transistors, and use them as liquid crystals for display devices. Element, EL element, photovoltaic element. [Example]

Hereinafter, the present invention will be further described according to examples and comparative examples. The present invention is not limited to the following examples.

The evaluation of each of the following examples was performed by the following method.

＜ Evaluation of polyimide precursor solution (varnish) ＞ [Storage stability] Store the varnish at 23 ° C. After 3 days, it will be rated as ○ if it has a fluid and homogeneous state. After 3 days, it will be cloudy or gelled. Is ×.

<Evaluation of polyimide film> [400nm light transmittance, total light transmittance] Using an ultraviolet-visible spectrophotometer / V-650DS (manufactured by Japan Spectroscopy), a polyimide film having a film thickness of about 10 μm was measured at 400 nm. Light transmittance and total light transmittance (average transmittance at 380nm ~ 780nm). The measured light transmittance and total light transmittance at 400 nm were 10%, and the Lambert-Beer law was used to calculate the light transmittance and total light transmittance at 400 nm when the thickness was 10 μm. The formula is as follows.

Log ₁₀ ((T ₁ +10) / 100) = 10 / L × (Log ₁₀ ((T ₁ '+10) / 100)) Log ₁₀ ((T ₂ +10) / 100) = 10 / L × (Log ₁₀ ( (T ₂ '+10) / 100)) T ₁ : Transmittance of a polyimide film with a thickness of 10 μm at a reflectance of 10% at 400 nm (%) T ₁ ': Measured transmittance at 400 nm ( %) T ₂ : total light transmittance (%) of a polyimide film having a thickness of 10 μm at a reflectance of 10% T ₂ ′: measured total light transmittance (%) L: measured polyacrylate Film thickness of amine film (μm)

[Coefficient of elasticity, elongation at break point] A polyimide film with a film thickness of about 10 μm is punched into a dumbbell shape of the IEC450 standard. As a test piece, TENSILON manufactured by ORIENTEC Corporation is used. / min, measuring the initial modulus of elasticity and elongation at break.

[Linear Thermal Expansion Coefficient (CTE)] A polyimide film having a thickness of about 10 μm was cut into a strip having a width of 4 mm and used as a test piece. TMA / SS6100 (manufactured by SII Technology Co., Ltd.) was used. The length is 15mm, the load is 2g, the heating rate is 20 ° C / min, and the temperature is raised to 500 ° C. From the obtained TMA curve, obtain a linear expansion coefficient of 150 ° C to 250 ° C.

[1% weight reduction temperature] A polyimide film having a film thickness of 10 μm was used as a test piece, and a calorimeter measuring device (Q5000IR) manufactured by TA Instruments was used in a nitrogen gas stream at a heating rate of 10 ° C./min from 25 ° C. The temperature was raised to 600 ° C. Determine the 1% weight reduction temperature from the obtained weight curve.

[Phase difference in film thickness direction (R _th )] A polyimide film having a film thickness of 10 μm was used as a test piece, and a phase difference measurement device (KOBRA-WR) manufactured by Oji Instruments Co., Ltd. was used. Determination of the retardation of the film. From the obtained phase difference, a phase difference in the thickness direction of a film having a film thickness of 10 μm was determined.

The abbreviations and purity of the raw materials used in the following examples are as follows.

[Diamine component] tra-DACH: trans-1,4-diaminocyclohexane [purity: 99.1% (GC analysis)] DABAN: 4,4'-diaminobenzidine aniline [purity: 99.90 % (GC analysis)] PPD: p-phenylenediamine [purity: 99.9% (GC analysis)] 4,4'-ODA: 4,4'-oxydiphenylamine [purity: 99.9% (GC analysis)] BAPB: 4,4'-bis (4-aminophenoxy) biphenyl [purity: 99.93% (HPLC analysis)] [tetracarboxylic acid component] s-BPDA: 3,3 ', 4,4'-biphenyltetra Carboxylic dianhydride [purity 99.9% (H-NMR analysis)] a-BPDA: 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride [purity 99.6% (H-NMR analysis)] PMDA-HS : 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)] CpODA-tee: trans-inward-inward-norbornane-2-spiro-α-cyclopentane Ketone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride CpODA-cee: cis-inward-inward-norbornane-2-spiro -α-cyclopentanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride CpODA: a mixture of CpODA-tee and CpODA-cee PACDA: N, N '-(1,4-phenylene) bis (1,3-dioxo octahydrobenzofuran-5-carboxyfluorenamine)

[Solvent] NMP: N-methyl-2-pyrrolidone

Table 1-1 describes the tetracarboxylic acid components used in Examples and Comparative Examples, Table 1-2 describes the diamine components used in Examples and Comparative Examples, and Table 1-3 describes the imidazole and imidazoline compounds used in Examples and Comparative Examples. Of the structural formula.

【Table 1-1】

[Table 1-2]

[Table 1-3]

[Synthesis Example 1] In a reaction vessel substituted with nitrogen, 90.91 g (0.4 mol) of DABAN and 64.88 g (0.6 mol) of PPD were added; 2835.90 g of N-methyl-2-pyrrolidone was added. The total mass of the monomers (the sum of the diamine component and the carboxylic acid component) was 16% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, CpODA (R) 384.38 g (1.0 mol) was added slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish A) was obtained.

[Synthesis Example 2] In a reaction vessel substituted with nitrogen, 90.91 g (0.4 mol) of DABAN and 54.07 g (0.5 mol) of PPD and 36.84 g (0.1 mol) of BAPB were added; N-methyl-2-pyrrolidone was added 2972.56 g. This amount is an amount such that the total mass of the monomers (the sum of the diamine component and the carboxylic acid component) is 16% by mass, and the mixture is stirred at room temperature for 1 hour. To this solution, 384.38 g (1.0 mol) of CpODA was added slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish B) was obtained.

[Synthesis Example 3] 22.73 g (0.100 mole) of DABAN was added to a reaction container substituted with nitrogen; 3,211.16 g of N-methyl-2-pyrrolidone was added, and this amount was based on the total mass of the monomer (diamine component) The total amount with the carboxylic acid component) was 16% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 38.44 g (0.100 mole) of CpODA was added slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish C) was obtained.

[Synthesis Example 4] In a reaction vessel substituted with nitrogen, 15.91 g (0.070 mole) of DABAN and 3.24 g (0.030 mole) of PPD were added; 302.35 g of N-methyl-2-pyrrolidone was added, and this amount was made by feeding The total mass of the monomers (the sum of the diamine component and the carboxylic acid component) was 16% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 38.44 g (0.100 mole) of CpODA was added slowly. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish D).

[Synthesis Example 5] 11.36 g (0.050 mol) of DABAN and 4.34 g (0.040 mol) of PABA and 2.00 g (0.010 mol) of 4,4'-ODA were added to a reaction vessel substituted with nitrogen; N-formaldehyde was added 294.74 g of 2--2-pyrrolidone, the amount of which was set to a total mass of the monomers (the sum of the diamine component and the carboxylic acid component) of 16% by mass, and stirred at room temperature for 1 hour. To this solution, 38.44 g (0.100 mole) of CpODA was added slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish E) was obtained.

[Synthesis Example 6] In a reaction vessel substituted with nitrogen, 20.02 g of 4,4'-ODA (0.100 mol) was added; 207.21 g of N-methyl-2-pyrrolidone was added, and this amount was the total amount of monomers fed. The mass (the sum of a diamine component and a carboxylic acid component) was 17 mass%, and it stirred at room temperature for 1 hour. To this solution was added 22.41 g (0.100 mmol) of PMDA-HS slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish F) was obtained.

[Synthesis Example 7] 22.73 g (0.100 mole) of DABAN was added to a reaction vessel substituted with nitrogen; 296.29 g of N-methyl-2-pyrrolidone was added, and this amount was based on the total mass of the monomer (diamine component) The total amount with the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 51.35 g (0.100 mole) of PACDA was added slowly. After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (varnish G) was obtained.

[Synthesis Example 8] In a reaction vessel substituted with nitrogen, 10.81 g of tra-DACH (0.100 mol) was added; 29.5.64 g of N-methyl-2-pyrrolidone was added, and this amount was based on the total mass of the monomers fed (2 The sum of the amine component and the carboxylic acid component) is an amount of 12% by mass. Stir at room temperature for 1 hour. To this solution, s-BPDA 28.69 g (0.0975 mol) and a-BPDA 0.74 g (0.0025 mol) were slowly added. Stir at 50 ° C for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish H).

[Example 1] 0.05 g (0.5 mmol) of 1,2-dimethylimidazole and 0.05 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. 33.76 g of varnish A obtained in Synthesis Example 1 (relative to the molecular weight of the repeating unit of the polyimide precursor in varnish A, 10 mmol) was added to this solution, and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyamidine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.05 mol relative to 1 mol of the repeat unit of the polyimide precursor.

A polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to perform heat treatment. Imidization to obtain a colorless and transparent polyfluorene imide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 2] 0.15 g (1.6 mmol) of 1,2-dimethylimidazole and 0.15 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. 33.76 g of varnish A obtained in Synthesis Example 1 (relative to the molecular weight of the repeating unit of the polyimide precursor in varnish A, 10 mmol) was added to this solution, and the mixture was stirred at room temperature for 3 hours to obtain a uniform and Viscous polyimide precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.16 mol relative to 1 mol of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 3] 0.19 g of 1,2-dimethylimidazole (2.0 mmol) and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 4] 0.96 g (10.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole was 1.0 mole relative to the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 5] 1.92 g (20.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to a reaction container to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 2.0 mol relative to the repeat unit of the polyfluorene imide precursor of 1 mol.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane is coated on a glass substrate and in a nitrogen environment (oxygen concentration of 200 ppm or less), and then heated directly from the room temperature to 410 ° C on the glass substrate to perform thermal sulfide Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 6] 0.04 g (0.5 mmol) of 1-methylimidazole and 0.04 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1-methylimidazole is 0.05 mol relative to 1 mole of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane is coated on a glass substrate and in a nitrogen environment (oxygen concentration of 200 ppm or less), and then directly heated on a glass substrate from room temperature to 410 ° C to perform thermal sulfonimine. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 7] 0.08 g (1.0 mmol) of 1-methylimidazole and 0.08 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated from the feed amount, the 1-methylimidazole is 0.1 mol relative to 1 mole of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 8] 0.16 g (2.0 mmol) of 1-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1-methylimidazole is 0.2 mol relative to 1 mole of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane is coated on a glass substrate and in a nitrogen environment (oxygen concentration of 200 ppm or less), and then directly heated on a glass substrate from room temperature to 410 ° C to perform thermal sulfonimine. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 9] 0.33 g (4.0 mmol) of 1-methylimidazole and 0.33 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated from the feed amount, the 1-methylimidazole was 0.4 mol relative to 1 mole of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 10] 0.16 g (2.0 mmol) of 2-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated from the feed amount, the 2-methylimidazole was 0.2 mol relative to 1 mole of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 11] 0.14 g (2.0 mmol) of imidazole and 0.14 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the imidazole is 0.2 mol relative to 1 mole of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 12] 0.29 g (2.0 mmol) of 2-phenylimidazole and 0.29 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 2-phenylimidazole was 0.2 mol with respect to 1 mol of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 13] 0.24 g (2.0 mmol) of benzimidazole and 0.24 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the benzimidazole was 0.2 mol relative to 1 mo of the repeat unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane is coated on a glass substrate and in a nitrogen environment (oxygen concentration of 200 ppm or less), and then directly heated on a glass substrate from room temperature to 410 ° C to perform thermal sulfonimine. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Comparative Example 1] The varnish A obtained in Synthesis Example 1 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen environment (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Comparative Example 2] 1.92 g (40.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole was 4.0 mol relative to the repeat unit of the polyimide precursor at 1 mol. If the obtained polyimide precursor solution is stored at 23 ° C, until the third day, the polyimide precursor solution will gel.

[Reference Example 1] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.76 g of varnish A obtained in Synthesis Example 1 (the molecular weight of the repeating unit of the polyimide precursor in varnish A was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous Polyimide precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 350 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration below 200 ppm), and then heated. Imidization to obtain a colorless and transparent polyfluorene imide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results of measuring the characteristics of the polyfluorene imide film are shown in Table 2-1.

[Example 14] 0.05 g (0.5 mmol) of 1,2-dimethylimidazole and 0.05 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.05 mol relative to 1 mol of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Example 15] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.1 mol relative to the repeat unit of the polyfluorene imide precursor of 1 mol.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Example 16] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Example 17] 0.16 g (2.0 mmol) of 1-methylimidazole and 0.16 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1-methylimidazole is 0.2 mol relative to 1 mole of the repeating unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 3] The varnish B obtained in Synthesis Example 2 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 4] 0.10 g (1.0 mmol) of 2-ethyl-2-imidazoline and 0.20 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 2-ethyl-2-imidazoline was 0.1 mol relative to 1 mol of the repeat unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 5] 0.20 g (2.0 mmol) of 2-ethyl-2-imidazoline and 0.40 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyimide precursor in varnish B was 10 mmol), and the varnish gelled. After stirring directly at room temperature for 3 hours, a homogeneous polyimide precursor solution could not be obtained. Calculated from the feed amount, the 2-ethyl-2-imidazoline was 0.2 mol relative to 1 mole of the repeating unit of the polyimide precursor.

[Comparative Example 6] 0.49 g (5.0 mmol) of 2-ethyl-2-imidazoline and 0.98 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol), and the varnish gelled. Even if it was stirred directly at room temperature for 3 hours, a homogeneous polyimide precursor solution could not be obtained. Calculated from the feed amount, the 2-ethyl-2-imidazoline was 0.5 mol relative to 1 mole of the repeating unit of the polyimide precursor.

[Comparative Example 7] 0.25 g (3.0 mmol) of 2-methyl-2-imidazoline and 0.25 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 2-methyl-2-imidazoline is 0.3 mol with respect to 1 mol of the repeating unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 8] 0.44 g (3.0 mmol) of 2-phenylimidazoline and 0.44 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.39 g of varnish B2 obtained in Synthesis Example 2 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish B was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 2-phenylimidazoline was 0.3 mol with respect to 1 mol of the repeating unit of the polyimide precursor.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of this polyimide film are shown in Table 2-2.

[Example 18] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 38.23 g of varnish C obtained in Synthesis Example 3 (the molecular weight of the repeating unit of the polyfluorene imide precursor in varnish C was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.1 mol relative to the repeat unit of the polyfluorene imide precursor of 1 mol.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 9] The varnish C obtained in Synthesis Example 3 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen environment (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Example 19] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.99 g of varnish D obtained in Synthesis Example 4 (the molecular weight of the repeating unit of the polyimide precursor in varnish D was 10 mmol) and stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.1 mol relative to the repeat unit of the polyfluorene imide precursor of 1 mol.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane is coated on a glass substrate and in a nitrogen environment (oxygen concentration of 200 ppm or less), and then directly heated on a glass substrate from room temperature to 410 ° C to perform thermal sulfonimine. Into a colorless and transparent polyfluoreneimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 10] The varnish D obtained in Synthesis Example 4 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Example 20] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 35.09 g of varnish E obtained in Synthesis Example 5 (the molecular weight of the repeating unit of the polyimide precursor in varnish E was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.1 mol relative to the repeat unit of the polyfluorene imide precursor of 1 mol.

A polyimide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to perform hot dilation. Amination to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 11] The varnish E obtained in Synthesis Example 5 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 410 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Example 21] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 24.97 g of varnish F obtained in Synthesis Example 6 (the molecular weight of the repeating unit of the polyimide precursor in varnish F was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 400 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then heated. Imidization to obtain a colorless and transparent polyfluorene imide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 12] The varnish F obtained in Synthesis Example 6 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 400 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Example 22] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 37.04 g of varnish G obtained in Synthesis Example 7 (the molecular weight of the repeating unit of the polyimide precursor in varnish G was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 350 ° C. on a glass substrate under a nitrogen atmosphere (oxygen concentration below 200 ppm), and then heated. Imidization to obtain a colorless and transparent polyfluorene imide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 13] The varnish G obtained in Synthesis Example 7 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 350 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Example 23] 0.19 g (2.0 mmol) of 1,2-dimethylimidazole and 0.19 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a uniform solution. To this solution was added 33.53 g of varnish H obtained in Synthesis Example 8 (the molecular weight of the repeating unit of the polyimide precursor in varnish H was 10 mmol), and the mixture was stirred at room temperature for 3 hours to obtain a uniform and viscous polymer.醯 imine precursor solution. Calculated from the feed amount, the 1,2-dimethylimidazole is 0.2 mol relative to 1 mol of the repeating unit of the polyimide precursor.

The polyfluorene imide precursor solution obtained by filtering through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 370 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), and then heated. Imidization to obtain a colorless and transparent polyfluorene imide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

[Comparative Example 14] The varnish H obtained in Synthesis Example 8 filtered through a PTFE filter membrane was coated on a glass substrate, and heated directly from room temperature to 370 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). Thermal ammonium imidization to obtain a colorless and transparent polyimide film / glass laminate. Next, the obtained polyimide film / glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of about 10 μm.

The results obtained by measuring the properties of the polyfluoreneimide film are shown in Table 2-3.

From the results shown in Tables 2-1 to 2-3, it can be seen that the imidazole-based compounds (1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, benzo Polyimide obtained from a polyimide precursor composition of imidazole or imidazole) has a small phase difference in thickness direction (Examples 1 to 13 and Comparative Example 1, Examples 14 to 17 and Comparative Example 3, and Example 18 And Comparative Example 9, Example 19 and Comparative Example 10, Example 20 and Comparative Example 11, Example 21 and Comparative Example 12, Example 22 and Comparative Example 13, Example 23 and Comparative Example 14). It was also found that when 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, or imidazole was used, the transmittance also improved (Examples 1 to 11 and Comparative Examples 1 and 14 to 17). And Comparative Example 3, Example 18 and Comparative Example 9, Example 19 and Comparative Example 10, Example 20 and Comparative Example 11, Example 21 and Comparative Example 12, Example 22 and Comparative Example 13, Example 23 and Comparison Example 14). In addition, it can be seen that if the content of the imidazole-based compound is less than 4 moles relative to the repeating unit of the polyimide precursor, the storage stability is also excellent (Examples 1 to 13 and Comparative Example 2). Regarding the mechanical properties, the maximum elongation temperature at which the heat treatment with fluorene imidization is used exceeds 350 ° C. and the temperature is 410 ° C., the elongation at the break point increases (Example 3 and Reference Example 1).

As described above, the polyimide obtained from the polyimide precursor composition of the present invention has a small phase difference in the thickness direction, and has excellent light transmittance, mechanical properties, and a low linear thermal expansion coefficient. The polyimide film of the present invention can be preferably used as a transparent substrate for forming a colorless, transparent and fine circuit in display applications and the like. [Industrial availability]

According to the present invention, it is possible to provide a polyimide which is excellent in transparency and has a smaller thickness direction retardation even in the same composition, or a small thickness direction retardation, excellent transparency, and excellent mechanical properties. Polyimide precursor composition (a polyimide precursor-containing solution composition) of polyimide, and a method for producing polyimide. The polyimide obtained from the polyimide precursor composition has high transparency, small phase difference in thickness direction, and low linear thermal expansion coefficient, and is easy to form fine circuits, and is particularly suitable for forming displays and touch panels. Substrate for solar cells.

no.

Claims (12)

A polyfluorene imide precursor composition comprising: a repeating unit represented by the following chemical formula (1) or a repeating unit represented by the following chemical formula (2); and other than the repeating units represented by the chemical formulas (1) and (2) The content of the repeating unit is less than 30 mole% of the polyimide precursor; and the imidazole-based compound; the content of the imidazole-based compound is 1 mole relative to the repeating unit of the polyimide precursor. More than 1 mole and less than 1 mole; (Wherein X ₁ is a tetravalent group having an alicyclic structure, Y ₁ is a divalent group having an aromatic ring, and R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbons, or carbon (Number of 3 to 9 alkylsilyl groups) (Wherein X ₂ is a tetravalent group having an aromatic ring, Y ₂ is a divalent group having an alicyclic structure, and R ₃ and R ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbons, or carbon Number 3 to 9). For example, the polyimide precursor composition of the first patent application range, wherein the polyimide obtained from the polyimide precursor composition has a light transmittance of a thickness of 10 μm at a wavelength of 400 nm of 75%. the above. For example, the polyimide precursor composition of the first patent application scope, wherein the content of the repeating units other than the repeating units represented by the chemical formulae (1) and (2) of the polyimide precursor is relative to All repeating units are 10 mol% or less. For example, the polyimide precursor composition according to item 1 or 2 of the patent application scope, wherein the boiling point of the imidazole-based compound at 1 atmosphere does not reach 340 ° C. For example, the polyimide precursor composition according to item 1 or 2 of the application, wherein the imidazole compound is 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-benzene Any of imidazole, imidazole, or benzimidazole. A method for producing polyimide, characterized in that the polyimide precursor composition according to any one of claims 1 to 5 is subjected to a heat treatment at a temperature exceeding 350 ° C, and the polyimide is heated. The precursor was imidized. For example, the manufacturing method of polyimide according to the scope of the patent application No. 6 includes the following steps: coating the polyimide precursor composition according to any of the scope of the patent applications No. 1 to 5 on the substrate; And the polyimide precursor composition on the substrate is subjected to a heat treatment at a temperature exceeding 350 ° C. to thereby polyimide the precursor. For example, the manufacturing method of polyimide according to item 6 or 7 of the patent scope, wherein the temperature of the heat treatment exceeds 400 ° C. A polyimide is manufactured by using a method for producing polyimide according to any one of claims 6 to 8. For example, the polyimide of item 9 in the scope of the patent application, wherein a film having a thickness of 10 μm has a light transmittance of 75% or more at a wavelength of 400 nm. A polyimide film is obtained by manufacturing the polyimide film into a film shape by using the method for producing a polyimide according to any one of claims 6 to 8. A substrate for a display, a touch panel, or a solar cell, which is characterized in that it contains a polyimide film such as item 9 or 10 of the patent application scope, or a polyimide film such as item 11 of the patent application scope.