TW201529728A - Polyimide precursor composition, method of manufacturing polyimide, polyimide, polyimide film, and substrate - Google Patents

Abstract

The present invention relates to a polyimide precursor composition containing a polyimide precursor with a specific composition and an imidazole-based compound, wherein the imidazole-based compound content is less than 4 mol relative to 1 mol of the repeating unit of the polyimide precursor.

Description

Polyimine precursor composition, method for producing polyimine, polyimine, polyimide film and substrate

The present invention relates to a solution composition (polyimine precursor composition) containing a polyimine precursor which can obtain a polyimine which is more excellent in transparency, has a small coefficient of thermal expansion, and excellent in mechanical properties, and It relates to a method for producing polyimine. Further, the present invention relates to a polyimide, a polyimide film, and a substrate which are excellent in transparency, have a small linear thermal expansion coefficient, and are excellent in mechanical properties.

In recent years, with the advent of a highly information society, development of optical materials such as liquid crystal alignment films or protective films for color filters in the field of display devices such as optical fibers and optical waveguides in the field of optical communication has progressed. In particular, in the field of display devices, it has been actively explored that plastic substrates having superior lightness and flexibility in replacing glass substrates, or development of bendable and roundable displays are being actively carried out. Therefore, a higher performance optical material that can be used in such applications is sought.

The aromatic polyimine is inherently colored yellowish due to the formation of intramolecular conjugates or charge transport complexes. In order to suppress the coloring, for example, a fluorine atom is introduced intramolecularly, a bending property is imparted to the main chain, and a bulky group is introduced as a side chain or the like to hinder the formation of an intramolecular conjugate or a charge transport complex and to exhibit it. The method of transparency.

Further, it has also been proposed to use a semi-alicyclic or full-aliphatic polyimine which theoretically does not form a charge transporting complex to exhibit transparency. For example, Patent Documents 1 to 4 disclose a highly transparent semi-alicyclic polyamidene using an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine as a diamine component.

Patent Document 5 and Patent Document 6 disclose a polyimide using tetrahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid as a tetracarboxylic acid component. Non-Patent Document 1 discloses the use of (4arH, 8acH)-decahydro-1t, 4t:5c, 8c-dimethylnaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid as a polycarboxylic acid of a tetracarboxylic acid component, Non-Patent Document 2 discloses a polyimine which uses (4arH, 8acH)-decahydro-1t, 4t:5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid as a tetracarboxylic acid component.

However, in particular, in the field of display devices and the like, a polyimide having a higher transparency is required. Further, a semialicyclic polyimine which uses an alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid component and an aromatic diamine as a diamine component has high transparency, bending resistance, and high heat resistance. However, the general linear thermal expansion coefficient tends to be large. If the coefficient of thermal expansion of the polyimine is large and the difference in linear thermal expansion coefficient between the conductors such as metal is large, there is a problem that warpage increases when the circuit board is formed, and in particular, fine circuit formation processing such as display use is not performed. Easy to carry out.

On the other hand, Patent Document 7 discloses a polyimide which is formed by heating a coating liquid obtained by blending an imidazoline-based compound (poly-proline) with an imidazoline-based compound and/or an imidazole-based compound. More specifically, in Example 1, a polyamine obtained from 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether A solution obtained by adding 2,4-dimethylimidazoline to the acid solution was coated on the substrate and heated at 200 ° C for 1 hour to obtain an aromatic polyimide film having a film thickness of 1000 Å (0.1 μm). . In Example 2, 2-ethylimidazoline and 1,2-dimethyl are added to a solution of polyamic acid obtained from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether. The solution obtained by imidazole was coated on a substrate and heated at 150 ° C for 1 hour to obtain an aromatic polyimide film having a film thickness of 800 Å (0.08 μm). Patent Document 7 discloses that by adding an imidazoline-based compound and/or an imidazole-based compound, significant coloration of brownish brown can be avoided, and a liquid crystal display element having excellent transparency and high transparency can be obtained. However, the liquid crystal display element obtained by using the polyimide film (liquid crystal alignment film) of Example 1 had a light transmittance of 82% at a wavelength of 400 nm (polyimine film thickness: 0.1 μm), and the polyfluorene of Example 2 was used. The light transmittance of the liquid crystal display element obtained by the imine film (liquid crystal alignment film) at a wavelength of 400 nm was 83% (polyimine film thickness: 0.08 μm), and the polyimide did not have sufficient transparency.

Further, as a method for producing a low-transparency aromatic polyimine, Patent Document 8 discloses that a polyimide polyimide precursor resin and a polyimide resin such as imidazole or N-methylimidazole are hardened. The solution containing the polyamidiamine precursor resin obtained by dissolving the accelerator in an organic polar solvent is coated on a substrate, and then dried by heat treatment and formed into a polyimide layer by yttrium imidation at 280~ A method of forming a polyimine resin layer which is completed in the range of 380 ° C, and it is described that the coefficient of thermal linear expansion can be controlled to be low by using the curing accelerator. Patent Document 8 discloses that it is preferable to use a curing accelerator having a boiling point of more than 120 ° C, and it is preferred to select a boiling point not exceeding the upper limit temperature of the heat treatment, and it is described that a hardening accelerator having a boiling point of, for example, 400 ° C or more is used in the imine. The proportion of the polyimine resin layer remaining in the layer is high, and there is a tendency to affect the function of the polyimide layer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A-2002-146-A No. 2002-146. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -115378 [Non-patent literature]

[Non-Patent Document 1] Macromolecules, Vol. 27, No. 5, P1117-1123, 1994 [Non-Patent Document 2] Macromolecules, Vol. 32, No. 15, P4933-4939, 1999

[The subject 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 polyiminoimine precursor composition (a solution composition containing a polyimide precursor), and a polyimine of the same composition can be obtained. However, it is a polyimine which is more excellent in transparency and has a low coefficient of thermal expansion, or a polyimide which is excellent in transparency, a low coefficient of thermal expansion, and excellent in mechanical properties, and a method for producing a polyimide. [How to solve the problem]

The present invention relates to the following. A polyimine precursor composition comprising: a polyimine precursor comprising a repeating unit represented by the following chemical formula (1-1), and an imidazole compound, wherein the content of the imidazole compound is relative to the poly The repeating unit 1 of the quinone imine precursor is less than 4 moles;

【化1】 (In the formula, A is a divalent group having an aromatic ring, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 3 to 9 carbon atoms.) 1. The polyimine precursor composition, wherein the polyimine precursor contains a repeating unit represented by the following chemical formula (1-2);

[Chemical 2] (In the formula, A is a divalent group having an aromatic ring, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 3 to 9 carbon atoms.) 1. The polyimine precursor composition of 1. or 2. wherein A in the chemical formula (1-1) or the chemical formula (1-2) is a group represented by the following chemical formula (1-A);

[化3] (wherein m represents an integer of 0 to 3, n represents an integer of 0 to 3, and m and n are each independently; and Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, and a trifluoro group. In the group consisting of methyl groups, Q and R each independently represent a direct bond or a group selected from the group consisting of: -NHCO-, -CONH-, -COO-, -OCO- One of the groups). 4. The polyimine precursor composition according to any one of items 1 to 3, wherein the polyimine obtained from the polyimide precursor precursor composition has a thickness of 10 μm and is transparent at a wavelength of 400 nm. The light rate is 75% or more. 5. The polyimine precursor composition according to any one of items 1 to 4, wherein the content of the imidazole-based compound is 0.05 mol or more relative to the repeating unit 1 of the polyimine precursor. Moel below. 6. The polyimine precursor composition according to any one of items 1 to 5, wherein the imidazole compound is 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, Any of 2-phenylimidazole, imidazole, or benzimidazole. A method for producing a polyimine, which is characterized in that the polyimide composition precursor composition according to any one of 1. to 6. is heat-treated at a maximum heating temperature of more than 350 ° C, and is polymerized. The quinone imine precursor is imidized. 8. The method for producing a polyimine according to 7., comprising the steps of: coating a polyimide composition precursor composition according to any one of 1. to 6. on a substrate; The polyimine precursor composition is subjected to heat treatment at a maximum heating temperature of more than 350 ° C to imidize the polyimine precursor. 9. The method for producing a polyimine of 7, or 8. wherein the heat treatment has a maximum heating temperature of more than 400 °C. A polyimine which is produced by the method for producing a polyimine according to any one of items 7. to 9. 11. The polyimine of 10., wherein the film having a thickness of 10 μm has a light transmittance of 75% or more at a wavelength of 400 nm. A polyimine film produced by the method for producing a polyimine according to any one of items 7. to 9. A substrate for a display, a touch panel, or a solar cell, which comprises a polyimine such as 10. or 11. or a polyimide film such as 12. [Effects of the Invention]

According to the present invention, it is possible to obtain a polyimine having excellent transparency and a low coefficient of thermal expansion even if it is a polyimide having the same composition, or having superior transparency, a low coefficient of thermal expansion, and excellent mechanical properties. A polyimine precursor composition of polyimine (a solution composition containing a polyimide precursor) and a method for producing a polyimide.

The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention has high transparency and a low coefficient of thermal expansion, and is easy to form a fine circuit, and can be suitably used for forming a display. The substrate. Moreover, the polyimine of the present invention can also be suitably used for forming a substrate for a touch panel or a solar cell.

The polyimine precursor composition of the present invention comprises a polyimine precursor containing at least one of the repeating units represented by the above formula (1-1), and an imidazole compound, and the content of the imidazole compound is relative to the polyazide. The repeating unit 1 of the amine precursor is less than 4 moles.

The polyimine obtained from the polyimine precursor containing at least one of the repeating units represented by the above formula (1-1), that is, the semialicyclic polyimine, has high transparency. In the case of such a highly transparent polyimine, it is not preferable to use an additive which causes coloring. However, the imidazole compound is added to the polyimine precursor by a ratio of less than 4 moles, preferably 0.05 moles to 2 moles, relative to the repeating unit 1 mole of the polyimide precursor. The composition, the transparency of the obtained polyimine, is further improved, and the linear thermal expansion coefficient of the obtained polyimine is reduced. That is, according to the present invention, a polyimine having a higher transparency and a lower coefficient of linear thermal expansion can be obtained from a polyimide intermediate precursor of the same composition.

Further, in order to obtain a highly transparent polyimine, it is generally considered that the polyimine precursor is heat-treated at a relatively low temperature to complete the oxime imidization, but according to the present invention, even if the maximum heating temperature is exceeded The heat treatment of 350 ° C, and more preferably more than 400 ° C, the ruthenium imide of the polyimide precursor can still produce a highly transparent polyimide. As a result, the maximum heating temperature for the heat treatment of the hydrazine imidation may be a high temperature exceeding 350 ° C, and particularly preferably a high temperature exceeding 400 ° C, so that the mechanical properties of the obtained polyimine are improved. That is, according to the present invention, a polyimide having high transparency, a low coefficient of thermal expansion coefficient, and excellent mechanical properties can be obtained.

As described above, the polyimine precursor composition of the present invention includes a polyimine precursor containing at least one of the repeating units represented by the above formula (1-1). As the polyimine precursor, a polyimine precursor containing a repeating unit represented by the above formula (1-2) is preferred.

However, the above chemical formula (1-1) and the aforementioned chemical formula (1-2), one of the acid groups and the amine group at the 2- or 3-position of the decahydro-1,4:5,8-dimethylnaphthalene ring are reacted to form a guanamine bond (-CONH-), the other is a group represented by COOX _{1 which does} not form a guanamine bond, and one of the acid groups at the 6 or 7 position reacts with an amine group to form a guanamine bond (-CONH-) The other is the group represented by -COOX _{2 which does} not form a guanamine bond. That is, the above chemical formula (1-1) and the above chemical formula (1-2) have four structural isomers, that is, all of the following include: (i) the 2-position has a group represented by -COOX ₁ , and the 3-position has -CONH - indicates the base, and 6 has a base represented by -COOX ₂ , 7 has a base represented by -CONH-A-; (ii) 3 has a base represented by -COOX ₁ , and 2 has a -CONH- And 6 positions have a base represented by -COOX ₂ , and 7 positions have a base represented by -CONH-A-; (iii) 2 positions have a base represented by -COOX ₁ , and 3 positions have a base represented by -CONH-, and The 7-position has a base represented by -COOX ₂ , and the 6-position has a base represented by -CONH-A-; (iv) 3 positions have a base represented by -COOX ₁ , 2 have a base represented by -CONH-, and 7 have -COOX ₂ represents the base and 6 bits have the base of -CONH-A-.

The A in the chemical formula (1-1) and the chemical formula (1-2) is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms.

Further, the polyimine precursor preferably contains the chemical formula (1-1) of the group represented by the above formula (1-A), and more preferably at least one of the repeating units represented by the chemical formula (1-2).

In other words, the polyimine precursor system includes trihydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid, etc., more preferably (4arH, 8acH)-decahydrogen. -1t, 4t: 5c, 8c-dimethyl bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, etc. (tetracarboxylic acid, etc., representing tetracarboxylic acid, and tetracarboxylic dianhydride, tetracarboxylic acid decyl ester a tetracarboxylic acid component of a tetracarboxylic acid derivative such as a tetracarboxylic acid ester or a tetracarboxylic cerium chloride, and a diamine component including an aromatic ring, more preferably a group represented by the chemical formula (1-A) of the A system. A polyimine precursor obtained from a diamine component of a diamine component of a repeating unit of the chemical formula (1-1) or the chemical formula (1-2).

As the tetracarboxylic acid component which imparts the repeating unit of the above chemical formula (1-1), decahydro-1,4:5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic acid or the like can be used. A single type can also be used in combination. As the tetracarboxylic acid component imparting the repeating unit of the above chemical formula (1-2), (4arH, 8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2t, 3t, 6c, 7c- can be used. A plurality of tetracarboxylic acids and the like may be used alone or in combination.

The diamine component to which the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) is added preferably contains a diamine which imparts a base represented by the above formula (1-A).

The diamine component of the repeating unit of the chemical formula (1-1) or the chemical formula (1-2) which is a group represented by the above-mentioned chemical formula (1-A) is an aromatic ring, and when a plurality of aromatic rings are present, The aromatic rings are directly bonded to each other independently, and are linked by a guanamine bond or an ester bond. The position at which the aromatic rings are bonded to each other is not particularly limited, and a linear structure is obtained by bonding with an amine group or an aromatic ring based on a 4-position bond, and the obtained polyimine will become a low-line thermal expansion. Further, the aromatic ring may be substituted with a methyl group or a trifluoromethyl group. Further, the substitution position is not particularly limited.

The diamine component of the repeating unit of the chemical formula (1-1) or the chemical formula (1-2) which imparts the group represented by the above formula (1-A) is not particularly limited, and examples thereof include p-phenylenediamine and m-phenylenediamine. , o-toluidine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine , m-toluidine, 4,4'-diaminobenzophenone, 3,4'-diaminophenyl benzophenone, N,N'-bis(4-aminophenyl)-p-xylylene Indoleamine, N,N'-p-phenylene bis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl) Terephthalate, biphenyl (4-aminophenyl) ester of biphenyl-4,4'-dicarboxylate, p-phenylene bis(p-aminobenzoate), bis(4-amino group) Phenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4-aminobenzoic acid Ester) and the like may be used singly or in combination of two or more. Among these, p-phenylenediamine, m-toluidine, 4,4'-diaminobenzidine, 4-aminophenoxy-4-diaminobenzoate, 2,2' - bis(trifluoromethyl)benzidine, benzidine, N,N'-bis(4-aminophenyl)terephthalamide, biphenyl-4,4'-dicarboxylic acid bis(4- Aminophenyl) esters are preferred, and p-phenylenediamine, 4,4'-diaminophenylbenzophenone, and 2,2'-bis(trifluoromethyl)benzidine are more preferred. By using p-phenylenediamine, 4,4'-diaminobenzoquinone and 2,2'-bis(trifluoromethyl)benzidine as the diamine component, the polyimine obtained has high heat resistance. With high light transmittance. These diamines may be used singly or in combination of two or more.

a diamine which imparts a diamine component of A in the above chemical formula (1-1) or the above chemical formula (1-2) (that is, a repeating unit which imparts the above chemical formula (1-1) or the aforementioned chemical formula (1-2) As the component, a diamine other than the diamine component of the structure of the above-mentioned chemical formula (1-A) of the A system may be used in combination. As the other diamine component, other aromatic or aliphatic diamines can be used. For example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-double (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, bis(4-aminophenyl)anthracene, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-double ((Aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl碸, bis(4-(3-aminophenoxy)diphenyl)anthracene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 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-two Base-2-t-butylcyclohexane, 1,4-diamino-2-t-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane Alkane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diamine Oxyxybicycloheptane, diaminomethoxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, Bis(Aminocyclohexyl)isopropylidene 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindane 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiropyrene, etc., such derivatives, may be used alone A variety of combinations can also be used. Among these, 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-double (4-Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl is preferred, especially 4,4'-bis(4-aminophenoxy)biphenyl It is better.

The polyimine precursor of the present invention is a chemical formula represented by the above formula (1-A) in the repeating unit 100 mol% represented by the above chemical formula (1-1) or the above chemical formula (1-2). The total ratio of the repeating unit represented by (1-1) or the chemical formula (1-2) is preferably 50% by mole or more, more preferably 70% by mole or more, still more preferably 90% by mole or more, and particularly preferably 100% by mole. In the case where the ratio of the repeating unit represented by the chemical formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A) is smaller than 50 mol%, the polyimine obtained may be obtained. The coefficient of linear thermal expansion increases.

In an embodiment, the properties of the obtained polyimine are given to 100 mol% of the diamine component of the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2), and the above chemical formula is imparted ( The total proportion of the diamine component of the structure of 1-A) is preferably 70 mol% or less, more preferably 80 mol% or less, still more preferably 90 mol% or less. For example, other diamines such as a diamine having an ether bond (-O-) such as 4,4'-oxydiphenylamine or 4,4'-bis(4-aminophenoxy)biphenyl are given the above chemical formula. (1-1) or 100 parts by mole of the diamine component of the repeating unit of the above chemical formula (1-2), for example, preferably 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol. It is preferably used in an amount of less than or equal to 0%, more preferably less than 10% by mole.

As described above, in the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), the above chemical formula (1-1) or the aforementioned chemical formula (1-2) A of A is preferably the above chemical formula (1-A). In other words, the diamine component to which the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) is imparted is preferably a chemical formula (1-1) or a chemical formula which imparts a group represented by the above-mentioned chemical formula (1-A) of the A system. The diamine component of the repeating unit of (1-2) is preferred. By giving the diamine component of the above formula (1-1) or A in the above chemical formula (1-2) (that is, giving a repeating unit of the above chemical formula (1-1) or the aforementioned chemical formula (1-2) The diamine component is a diamine component which imparts a repeating unit of the formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A), and the heat resistance of the obtained polyimine is improved.

In a certain embodiment, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) may preferably contain the above-mentioned chemical formula (1-A) of the A system. At least two kinds of repeating units of the chemical formula (1-1) or the chemical formula (1-2) which are represented are preferred. In other words, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2) may preferably contain the chemical formula (1-1) which imparts a group represented by the above formula (1-A). At least two kinds of diamine components of the repeating unit of the chemical formula (1-2) are preferred. By giving the diamine component of the above chemical formula (1-1) or A in the above chemical formula (1-2) (that is, giving the repeating unit of the above chemical formula (1-1) or the aforementioned chemical formula (1-2) The amine component) contains at least two kinds of diamine components which impart a structure of the above-mentioned chemical formula (1-A) of the A system, and the obtained polyimine can achieve a balance between high transparency and low-line thermal expansion property (that is, it can be obtained) Polyimine with high transparency and low coefficient of thermal expansion.

In this embodiment, for example, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), which gives the aforementioned chemical formula (1-1) or The diamine component of A in the above chemical formula (1-2) (that is, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2)) contains the above-mentioned chemical formula (1). The structure of the -A) has at least two kinds of diamine components, and one of them is preferably 4,4'-diaminobenzophenone. The diamine component which imparts A to the above chemical formula (1-1) or the above chemical formula (1-2) contains at least two kinds of diamine components which impart the structure of the above chemical formula (1-A), and one of them is 4 4'-diaminophenyl benzophenone can obtain a polyimine which has high heat resistance and high heat resistance in addition to high transparency and low linear thermal expansion.

In one embodiment, the polyimine precursor of the present invention comprising the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2), which imparts the aforementioned chemical formula (1-1) or the aforementioned chemical formula The diamine component of A in (1-2) (that is, the diamine component which imparts the repeating unit of the above chemical formula (1-1) or the above chemical formula (1-2)) preferably contains a selected from 2, 2'- It is preferred that at least one of bis(trifluoromethyl)benzidine and p-phenylenediamine and 4,4'-diaminobenzophenone are preferred. By combining these diamine components, polyimine which achieves both high transparency, low-line thermal expansion property, and heat resistance can be obtained.

In this embodiment, the diamine component which imparts A to the above chemical formula (1-1) or the above chemical formula (1-2) (that is, gives the aforementioned chemical formula (1-1) or the aforementioned chemical formula (1-2) The diamine component of the repeating unit) preferably contains 4,4'-diaminophenylbenzophenone 20 mol% or more, 80 mol% or less, and contains p-phenylenediamine and 2,2'-double Any one or both of (trifluoromethyl)benzidine is preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% or more of 4,4'-diaminobenzophenidine. 70 mol% or less, and more preferably 30 mol% or more and 70 mol% or less of either or both of p-phenylenediamine and 2,2'-bis(trifluoromethyl)benzidine, especially Preferably, it contains 4,4'-diaminophenylbenzophenone 40 mol% or more, 60 mol% or less, and contains p-phenylenediamine and 2,2'-bis(trifluoromethyl)benzidine. One or both of them are 40% or more and 60% by mole or less.

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

As the tetracarboxylic acid component to be imparted to other repeating units, other aromatic or aliphatic tetracarboxylic acids can be used. For example: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene -1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2, 3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)phosphonium anhydrate, meta-triphenyl-3, 4,3',4'-tetracarboxylic dianhydride, conjugated triphenyl-3,4,3',4'-tetracarboxylic dianhydride, biscarboxyphenyldimethyl decane, bisdicarboxyphenoxy Phenyl sulfide, sulfonyl diphthalic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane-1,2 , 4,5-tetracarboxylic acid, [1,1'-linked (cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-linked (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'-sulfonyl bis(cyclo) Hexane-1,2-dicarboxylic acid), 4, 4'-(Dimethyldecanediyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl)bis(cyclohexane-1 ,2-dicarboxylic acid), octahydropentene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane-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, bicyclo[2.2.2] Oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5癸-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo[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-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid and the like, and the acid dianhydride may be used singly or in combination. Among these, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, norbornane -2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane 5,5'',6,6''-tetracarboxylic acid, (4arH,8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid and other derivatives, such acid dianhydride, considering the easy production of polyimine and the heat resistance of the obtained polyimine The idea of excellent sex is ideal. These acid dianhydrides may be used singly or in combination of two or more.

The diamine component to which the other repeating unit is added may be exemplified as the diamine component which imparts a repeating unit of the chemical formula (1-1) or the chemical formula (1-2) represented by the above formula (1-A). amine.

As the diamine component to which other repeating units are imparted, other aromatic or aliphatic diamines can be used. For example: 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-double (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, bis(4-aminophenyl)anthracene, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-double ((Aminophenoxy)phenyl)propane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl碸, bis(4-(3-aminophenoxy)diphenyl)anthracene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 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-two Base-2-t-butylcyclohexane, 1,4-diamino-2-t-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane Alkane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diamine Oxyxybicycloheptane, diaminomethoxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, Bis(Aminocyclohexyl)isopropylidene 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindane 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiropyrene, etc., such derivatives, may be used alone A variety of combinations can also be used.

In one embodiment, the polyimine precursor preferably has a repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) in an amount of 50 mol% or more in all repeating units. More preferably, it is 70 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%. When the ratio of the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) is 50 mol% or more, the film formability is improved and the linear thermal expansion coefficient of the obtained polyimine is extremely small. Further, from the viewpoint of the total light transmittance, the repeating unit represented by the above chemical formula (1-1) or the above chemical formula (1-2) may be preferably 50 mol% or more in all the repeating unit 100 mol%. 99 mol% or less, more preferably 60 mol% or more to 95 mol% or less, and particularly preferably 70 mol% or more to 95 mol% or less.

When the tetracarboxylic acid component and the diamine component include an isomer, the isomer may be used for polymerization or the like, or the isomer may be used in the form of a mixture for polymerization or the like.

In the polyimine precursor of the present invention, X ₁ and X _{2 of the} above chemical formula (1-1) and the above chemical formula (1-2) are each independently hydrogen, and have a carbon number of 1 to 6, preferably a carbon number of 1. Any of an alkyl group of ~3 or an alkylene group of 3 to 9 carbon atoms. X ₁ and X ₂ can change the type of the functional group and the introduction ratio of the functional group by the production method described later.

When X ₁ and X ₂ are hydrogen, the production of polyimine is likely to be easy.

Further, when X ₁ and X ₂ are carbon atoms of 1 to 6, preferably an alkyl group having 1 to 3 carbon atoms, the polyimide precursor has a tendency to be excellent in storage stability. In this case, X ₁ and X _{2 are} preferably a methyl group or an ethyl group.

Further, when X ₁ and X ₂ are alkanofluorene having 3 to 9 carbon atoms, the solubility of the polyimine precursor tends to be excellent. In this case, X ₁ and X _{2 are} preferably a trimethylindenyl group or a tert-butyldimethylindenyl group.

The introduction ratio of the functional group is not particularly limited, and in the case of introducing an alkyl group or an alkyl fluorenyl group, X ₁ and X ₂ may each be 25% or more, preferably 50% or more, and more preferably 75% or more of an alkyl group or an alkyl group.矽基.

The polyimine precursor of the present invention, depending on the chemical structure taken by X ₁ and X ₂ , can be classified into: 1) poly-proline (X ₁ and X ₂ are hydrogen), 2) polyphthalate ( At least a portion of X ₁ and X ₂ are alkyl groups, and 3) 4) polydecyl phthalate (at least a portion of X ₁ and X ₂ is an alkane group). Further, the polyimine precursor of the present invention can be easily produced in terms of its classification according to the following production method. However, the method for producing the polyimine precursor of the present invention is not limited to the following production methods.

1) Polylysine The polyimine precursor of the present invention may be a slightly more molar, preferably a diamine, by using a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent. The molar ratio of the component to the tetracarboxylic acid component [molar number of the diamine component / mole number of the tetracarboxylic acid component] is from 0.90 to 1.10, more preferably from 0.95 to 1.05, for example, below 120 ° C. The reaction is carried out at a low temperature in a state in which hydrazine imidation is inhibited, and is preferably obtained in the form of a composition of a polyimide precursor solution.

It is not limited, and more specifically, the diamine may be dissolved in an organic solvent, and tetracarboxylic dianhydride may be slowly added in a stirred state in the solution, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C. A polybendimimine precursor is obtained from 1 to 72 hours. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the oxime imidization proceeds due to heat, so that the polyimide precursor may not be stably produced. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method tends to increase the molecular weight of the polyimide precursor, which is preferable. Further, the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be reversed, and it is preferable from the viewpoint of reducing precipitates.

Further, when the molar ratio of the tetracarboxylic acid component to the diamine component is an excess of the diamine component, a carboxylic acid derivative in an amount corresponding to an excess of the molar amount of the diamine component may be added as needed, and the tetracarboxylic acid may be added. The molar ratio of the component to the diamine component is approximately equal to the equivalent. Here, the carboxylic acid derivative is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide precursor solution, that is, does not substantially involve molecular chain elongation, or a tricarboxylic acid and an anhydride thereof as a terminal stopper. Dicarboxylic acid and its anhydride are ideal.

2) Polyphthalate causes tetracarboxylic dianhydride to react with any alcohol to obtain a diester dicarboxylic acid, and then reacts with a chlorination reagent (sulfurium chloride, grass chloroform, etc.) to obtain a diester dicarboxylate. Chlorine. The diester dicarboxyfluorene chloride and the diamine are stirred at -20 to 120 ° C, preferably at -5 to 80 ° C for 1 to 72 hours to obtain a polyimine precursor. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the ruthenium is imidized by heat, and the polyimide precursor may not be stably produced. Further, the diester dicarboxylic acid and the diamine can be easily dehydrated and condensed using a phosphorus-based condensing agent or a carbodiimide condensing agent, and the polyimine precursor can be easily obtained.

Since the polyimide precursor obtained by this method is stable, it can also be reprecipitated by adding a solvent such as water or alcohol.

3) Polydecyl phthalate (indirect method) The diamine is previously reacted with a guanylating agent to obtain a guanidinated diamine. The thiolated diamine is purified by distillation or the like as needed. And dissolving the fluorinated diamine in a dehydrated solvent, adding tetracarboxylic dianhydride while stirring, stirring at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours. A polyimine precursor can be obtained. When the reaction is carried out at 80 ° C or higher, the molecular weight changes depending on the temperature history at the time of polymerization, and the ruthenium is imidized by heat, and the polyimide precursor may not be stably produced.

The thiolating agent to be used herein is preferably a non-chlorinated thiolizing agent, which does not require purification of the fluorinated diamine. A sulfhydrylating agent free of chlorine atoms, such as N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, hexamethyldifluorene Azane. From the viewpoint of not containing a fluorine atom, N, O-bis(trimethyldecyl)acetamide or hexamethyldioxane is preferred.

Further, in the thiolation reaction of a diamine, an amine-based catalyst such as pyridine, piperidine or triethylamine may be used to promote the reaction. This catalyst can be directly used as a polymerization catalyst as a polyimide precursor.

4) Polydecyl phthalate (direct method) The polyphthalic acid solution obtained by the method of 1) is mixed with a thiolizing agent, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72. In a few 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 at the time of polymerization, and the ruthenium imidization due to heat may not stably produce the polyimide precursor.

When the thiolating agent to be used herein is a chlorine-free thiolating agent, it is not necessary to refine the thiolated polyamic acid or the obtained polyimine. Examples of the sulfhydrylating agent containing no chlorine atom include N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, hexamethyl group. Dioxane. From the viewpoint of not containing a fluorine atom, N, O-bis(trimethyldecyl)acetamide or hexamethyldioxane is preferred.

The above production method can be suitably carried out in an organic solvent, and as a result, a solution or a solution composition containing a polyimide precursor can be easily obtained.

a solvent used in the preparation of a polyimide precursor, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl Aprotic solvents such as acetyl-2-imidazolidone and dimethyl hydrazine are preferred, especially N,N-dimethylacetamide, but only the raw material monomer component and the resulting polyimine precursor can It can be dissolved, and any kind of solvent can be used without problems, and the structure is not particularly limited. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ- is used. a cyclic ester solvent such as valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, a carbonate solvent such as ethyl carbonate or propylene carbonate, or triethylene glycol a diol solvent such as a diol solvent, m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, or cyclopentane, Dimethyl hydrazine and the like are preferred. Furthermore, other common organic solvents, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl cycas, 2 -Methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethyl Diol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, decene, ore, Petroleum brain solvents and the like can also be used. Further, the solvent may be used in combination of a plurality of types.

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

The polyimine precursor composition of the present invention contains a polyimide intermediate and an imidazole compound, and can be prepared by adding an imidazole compound to a polyamidene precursor solution or solution composition obtained by the above production method. Further, a solvent may be removed or added as needed, and a desired component other than the imidazole compound may be added. Further, the tetracarboxylic acid component (such as tetracarboxylic dianhydride) and the diamine component and the imidazole compound may be added to the solvent, and the tetracarboxylic acid component and the diamine component may be reacted in the presence of the imidazole compound to obtain the present invention. The polyimide precursor composition (containing a solution composition of a polyimide precursor and an imidazole compound).

The imidazole compound used in the present invention is not particularly limited as long as it has an imidazole skeleton. By adding an imidazole-based compound, a polyimine having a higher transparency and a lower coefficient of linear thermal expansion can be obtained.

The imidazole 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. The imidazole compound may be used alone or in combination of two or more.

In the present invention, the content of the imidazole compound of the polyimide precursor composition is less than 4 moles relative to the repeating unit 1 of the polyimide intermediate. When the content of the imidazole-based compound is 4 mol or more with respect to the repeating unit 1 of the polyimine precursor, the storage stability of the polyimine precursor composition is deteriorated. The content of the imidazole compound is preferably 0.05 mol or more with respect to the repeating unit 1 molar of the polyimide precursor, and is preferably 2 mol or less with respect to the repeating unit 1 of the polyimine precursor. Preferably. Here, the repeating unit 1 of the polyimine precursor is corresponding to the tetracarboxylic acid component 1 mole.

The polyimine precursor composition of the present invention usually contains a solvent. The solvent used in the composition of the polyimine precursor of the present invention is not particularly limited as long as the polyimide precursor can be dissolved without any problem. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, γ-butyrolactone or γ-valerolactone is used. , a cyclic ester solvent such as δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, a carbonate solvent such as ethyl carbonate or propyl carbonate, and the like a diol solvent such as ethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone or 1,3-dimethyl-2-imidazolidinone, or a ring Ding, dimethyl adenine, etc. are ideal. Furthermore, other general organic solvents can also be used, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl cyanobacteria. Sodium, 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone acetate, 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, decene, Mineral concentrate, petroleum brain solvent, etc. Also, these combinations can be used in various combinations. Further, as the solvent of the polyimine precursor composition, a solvent used in the preparation of the polyimide precursor can be used as it is.

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% based on the total amount of the solvent and the tetracarboxylic acid component and the diamine component. The ratio of mass% or more is ideal. In addition, the total amount of the tetracarboxylic acid component and the diamine component is preferably 60% by mass or less, preferably 50% by mass or less, based on the total amount of the solvent and the tetracarboxylic acid component and the diamine component. This concentration is approximately close to the solid content concentration of the polyimide precursor, and if the concentration is too low, the film thickness of the polyimide film obtained when, for example, a polyimide film is sometimes difficult to control.

In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide precursor is not particularly limited, and the rotational viscosity measured at a temperature of 25 ° C and a shear rate of 20 sec ^-1 is 0.01 to 1000 Pa·sec using an E-type rotational viscometer. Ideally, 0.1 to 100 Pa·sec is more desirable. Further, thixotropy can also be imparted as needed. The viscosity in the above range is easy to handle when coating or film formation, and the eye hole is suppressed, and the leveling property is excellent, and a good coating film can be obtained.

The varnish of the polyimide precursor of the present invention may be added with a chemical sulfhydrylating agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, or a filler (such as cerium oxide), if necessary. Coupling agents such as particles, dyes, pigments, decane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agents (flow aids), strippers, and the like.

The polyimine of the present invention can be obtained by subjecting a polybendimimine precursor composition of the present invention to the ruthenium imidization (that is, subjecting the polyimine precursor to a dehydration ring-closure reaction). The method for the imidization of hydrazine is not particularly limited, and a known thermal hydrazine imidation or chemical hydrazylation method can be preferably used. The form of the obtained polyimine is preferably a film, a laminate of a polyimide film and another substrate, a coating film, a powder, a bead, a molded body, a foam, a varnish, or the like.

In the present invention, it is preferred that the polyimide precursor composition is heat-treated at a maximum heating temperature of more than 350 ° C to impart a ruthenium imide to the polyimide precursor. The maximum heating temperature for the heat treatment of hydrazine imidization is preferably more than 380 ° C, more preferably more than 400 ° C. The mechanical properties of the polyimine obtained by setting the maximum heating temperature by heat treatment with hydrazide to a temperature exceeding 350 ° C, more preferably more than 380 ° C, and particularly preferably more than 400 ° C. improve. The upper limit of the maximum heating temperature of the heat treatment is not particularly limited, and is usually preferably 500 ° C or less.

For example, the polyimine precursor composition of the present invention is further coated and coated on a substrate, and the polyamidene precursor composition on the substrate is heated at a maximum temperature of more than 350 ° C, more preferably more than 380. It is preferable to carry out heat treatment at a temperature of more than 400 ° C at a temperature of more than 400 ° C to imidize the polyimide precursor to ruthenium, and it is preferable to produce a polyimide. Further, the heating curve is not particularly limited and may be appropriately selected, but the productivity is considered, and the time of the heat treatment is preferably short.

Further, the polyimine precursor composition of the present invention is further coated on a substrate, preferably dried at a temperature of 180 ° C or lower, and a polyimide composition precursor composition is formed on the substrate. a film, and the film of the obtained polyimide precursor composition is peeled off from the substrate, and the state of fixing the end of the film is at a maximum heating temperature of more than 350 ° C, more preferably more than 380 ° C, particularly preferably The polyimine is also preferably produced by heat treatment at a temperature exceeding 400 ° C to imidize the polyimine precursor.

More specifically, an example of a method for producing a polyimine (polyimine film/substrate laminate or polyimide film) of the present invention will be described later.

The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and when it is formed into a film, the linear thermal expansion coefficient at 150 ° C to 250 ° C can preferably be 40 ppm / Below K, it is more preferably 35 ppm/K or less, still more preferably 30 ppm/K or less, and particularly preferably 25 ppm/K or less. If the coefficient of thermal expansion of the wire is large, and the coefficient of thermal expansion coefficient between the conductors such as metal is large, a problem such as an increase in warpage may occur when the circuit board is formed.

The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and the total light transmittance (average transmittance of a wavelength of 380 nm to 780 nm) of a film having a thickness of 10 μm. It is preferably 86% or more, more preferably 87% or more, and still more preferably 88% or more. When it is used for a display or the like, if the total light transmittance is low, the light source must be reinforced, and there is a problem that energy is consumed.

In particular, when it is used for light transmission of a polyimide film such as a display, it is desirable that the polyimide film has high transparency. The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and the film having a thickness of 10 μm can preferably have a light transmittance of at least 75% at a wavelength of 400 nm. Preferably, the amount is more than 80%, more preferably more than 80%, and even more preferably 81% or more, and particularly preferably 82% or more.

Further, the film composed of the polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention preferably has a film thickness of from 0.1 μm to 250 μm, more preferably 1 μm, depending on the use. ~150 μm, more preferably 1 μm to 50 μm, and particularly preferably 1 μm to 30 μm. When the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance is lowered.

The polyimine (the polyimine of the present invention) obtained from the polyimine precursor composition of the present invention is not particularly limited, and a 1% weight loss temperature which is an index of heat resistance of the polyimide film is preferred. It is 470 ° C or higher, more preferably 480 ° C or higher, and even more preferably 485 ° C or higher, and particularly preferably 490 ° C or higher. When a gas barrier film or the like is formed on a polyimide, such as a crystal on a polyimine, if the heat resistance is low, a decomposition of the polyimide may be caused between the polyimide and the barrier film. The swelling caused by the fugitive gas.

The polyimine obtained from the polyimine precursor composition of the present invention, that is, the polyimine of the present invention, has excellent properties such as high transparency, bending resistance, high heat resistance and has a very low coefficient of thermal expansion. Therefore, it is preferably used for a transparent substrate for a display, a transparent substrate for a touch panel, or a substrate for a solar cell.

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

The polyimine precursor composition (varnish) of the present invention is cast on a base such as ceramic (glass, bismuth, alumina), metal (copper, aluminum, stainless steel), heat-resistant plastic film (polyimine), and the like. The material is dried in a vacuum, a passive gas such as nitrogen, or a hot air or infrared light in the air at a temperature of 20 to 180 ° C, preferably 20 to 150 ° C. Next, the obtained polyimide precursor precursor film is peeled off from the substrate on the substrate, or the polyimide film precursor film is peeled off from the substrate, and the end portion of the film is fixed, and a vacuum such as nitrogen is blunt. In the gas, or in the air, hot air or infrared rays are used at about 200 to 500 ° C, more preferably at a maximum heating temperature of more than 350 ° C, more preferably more than 380 ° C, and more preferably at a temperature exceeding 400 ° C. A polyimide film/substrate laminate or a polyimide film can be produced. Further, in order to prevent oxidative degradation of the obtained polyimide film, it is preferred to heat the oxime in a vacuum or in a passive gas. The thickness of the polyimide film (polyimine film layer in the case of the polyimide film/substrate laminate) is preferably from 1 to 250 μm, more preferably 1 for the transportability of the subsequent step. ~150μm.

Further, the hydrazine imidization reaction of the polyimine precursor may be carried out by heating the hydrazine as described above by heating, instead of using the polyimine precursor to a quaternary amine such as pyridine or triethylamine. In the presence of a chemical treatment such as immersion in a solution containing a dehydrating cyclization reagent such as acetic anhydride. Further, the dehydrated cyclization reagent may be previously introduced into a polyamidene precursor composition (varnish) and stirred, and cast and dried on a substrate to prepare a partially yttrium-polymerized polypene. The imine precursor is further subjected to heat treatment as described above to obtain a polyimide film/substrate laminate or a polyimide film.

The polyimide film/substrate laminate or the polyimide film obtained in this manner 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 a first method, the polyimide film is not peeled off from the substrate of the polyimide film/substrate laminate, and sputtering, vapor deposition, printing, etc. are used on the surface of the polyimide film. A conductive layer of a conductive material (metal, metal oxide, conductive organic substance, conductive carbon, or the like) is formed, and a conductive layer/polyimine film/substrate conductive laminate is produced. Then, if necessary, the conductive layer/polyimine film laminate is peeled off from the substrate, and a transparent and flexible conductive substrate composed of a conductive layer/polyimine film laminate can be obtained.

As a second method, the polyimide film can be peeled off from the substrate of the polyimide film/substrate laminate to obtain a polyimide film, and the surface of the polyimide film is first and In the same manner, a conductive layer of a conductive material (metal, metal oxide, conductive organic substance, conductive carbon, or the like) is formed, and a conductive layer/polyimine film laminate or a conductive layer/polyfluorene is obtained. A transparent and flexible conductive substrate composed of an amine film laminate/conductive layer.

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

Further, the conductive layer can be appropriately formed by a photolithography method, a method such as various printing methods, or an inkjet method.

The substrate of the present invention is a circuit having a conductive layer by interposing a gas barrier layer or an inorganic layer on the surface of the polyimide film composed of the polyimine of the present invention as needed. This substrate is flexible, has high transparency, bendability, and heat resistance, and has an extremely low linear thermal expansion coefficient up to a high temperature or an excellent solvent resistance, so that a fine circuit can be easily formed. Therefore, the substrate can be suitably used as a substrate for a display, a touch panel, or a solar cell.

In other words, it is preferable to further form a transistor (inorganic transistor, organic transistor) by vapor deposition, various printing methods, or an inkjet method, and to manufacture a flexible thin film transistor, and to use it as a liquid crystal for a display device. Element, EL element, photoelectric element. [Examples]

The present invention will be further described below by way of examples and comparative examples. Further, the present invention is not limited to the following embodiments.

The evaluation of the following examples was carried out in the following manner.

<Evaluation of Polyimine Precursor Solution (Varnish)> [Storage Stability] The varnish was stored at 23 ° C, and it was evaluated as ○ after 3 days, and it was white turbid or gelled after 3 days. Then rated as ×.

<Evaluation of Polyimine Film> [400 nm Transmittance, Total Light Transmittance] Using a UV-visible spectrophotometer/V-650DS (manufactured by JASCO Corporation), a polyimide film having a film thickness of about 10 μm was measured at 400 nm. Light transmittance and total light transmittance (average transmittance from 380 nm to 780 nm). The transmittance at 400 nm and the total light transmittance were measured to have a reflectance of 10%, and the light transmittance at 400 nm and the total light transmittance at a thickness of 10 μm were calculated using the Lambert-Beer law. 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 having 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 reflectance of 10% and a thickness of 10 μm T ₂ ': measured total light transmittance (%) L: measured polyfluorene Film thickness of amine film (μm)

[Elasticity coefficient, elongation at break point] A polyimide film having a film thickness of about 10 μm was punched into a dumbbell shape of IEC450, and used as a test piece. TENSILON manufactured by ORIENTEC Co., Ltd. was used, and the length between the chucks was 30 mm, and the stretching speed was 2 mm. /min, the initial elastic modulus and the elongation at break were measured.

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

[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 INSTRUMENT Co., Ltd. was used in a nitrogen gas stream at a temperature rising rate of 10 ° C/min from 25 ° C. Warm up to 600 °C. A 1% weight reduction temperature was obtained from the obtained weight curve.

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

[Diamine component] DABAN: 4,4'-diaminobenzoquinone [Purification: 99.90% (GC analysis)] PPD: p-phenylenediamine [Purity: 99.9% (GC analysis)] BAPB: 4, 4 '-bis(4-aminophenoxy)biphenyl [purity: 99.93% (HPLC analysis)] [tetracarboxylic acid component] DNDAxx: (4arH, 8acH)-decahydro-1t, 4t: 5c, 8c-two A bridge naphthalene-2t, 3t, 6c, 7c-tetracarboxylic dianhydride [purity in the case of DNDAxx: 99.2% (GC analysis)]

[Imidazole/Imidazoline Compound] 1,2-Dimethylimidazole 1-Methylimidazole 2-Methylimidazole 2-Phenylimidazole Imidazole Benzimidazole 2-Ethyl-2-imidazoline

[Solvent] NMP: N-methyl-2-pyrrolidone DMAc: N,N-dimethylacetamide

Table 1-1 shows the tetracarboxylic acid components used in the examples and comparative examples, the diamine components used in the examples and comparative examples in Table 1-2, and the imidazole/imidazoline compounds used in the examples and comparative examples in Table 1-3. The structural formula.

【Table 1-1】

[Table 1-2]

[Table 1-3]

[Synthesis Example 1] To a reaction vessel substituted with nitrogen, DABAN 11.36 g (0.050 mol) and PPD 5.41 g (0.050 mol) were added; and N-methyl-2-pyrrolidone 187.99 g was added, which was such that the feed was made. The total mass of the monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish A).

[Synthesis Example 2] To a reaction vessel substituted with nitrogen, DABAN 11.36 g (0.050 mol) and PPD 5.41 g (0.050 mol) were added; and N,N-dimethylacetamide was added to 187.99 g, which was The total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish B).

[Synthesis Example 3] DABAN 6.82 g (0.030 mol) and PPD 4.33 g (0.040 mol) and BAPB 11.05 g (0.030 mol) were added to a nitrogen-substituted reaction vessel; N-methyl-2-pyrrolidone was added thereto. 209.70 g, which is an amount of the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) of 20% by mass, and stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish C).

[Synthesis Example 4] DABAN 15.91 g (0.070 mol) and BAPB 11.05 g (0.030 mol) were added to a nitrogen-substituted reaction vessel; N-methyl-2-pyrrolidone 228.76 g was added, which was used to feed The total mass of the monomer (the sum of the diamine component and the carboxylic acid component) was 20% by mass, and the mixture was stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. After stirring at room temperature for 12 hours, a uniform and viscous polyimide precursor solution (varnish D) was obtained.

[Synthesis Example 5] In a reaction vessel substituted with nitrogen, DABAN 9.09 g (0.040 mol) and PPD 4.33 g (0.040 mol) and BAPB 7.37 g (0.020 mol) were added; N-methyl-2-pyrrolidone was added. 204.06g, which is an amount of the total mass of the feed monomer (the sum of the diamine component and the carboxylic acid component) of 20% by mass, and stirred at room temperature for 1 hour. DNDAxx 30.23 g (0.100 mol) was slowly added to this solution. Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (varnish E).

[Example 1] 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 homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 0.1 equivalent, based on the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 2] 0.38 g (4.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. In this solution, Synthesis Example 1 was added to 23.2 g of the obtained varnish A (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in varnish A), and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 0.4 equivalents based on the amount of the feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 3] 1,6 g (10.0 mmol) of 1,2-dimethylimidazole and 0.48 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 1.0 equivalent, based on the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 4] 1.92 g (20.0 mmol) of 1,2-dimethylimidazole and 0.48 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish A obtained in Synthesis Example 1 (molecular weight of the repeating unit of the polyimine precursor in the varnish A, 10 mmol) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 2.0 equivalents, calculated from the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide 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 applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 5] 0.10 g (1.0 mmol) of 1,2-dimethylimidazole and 0.10 g of N,N-dimethylacetamide were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish B obtained in Synthesis Example 2 (molecular weight of 10 ppm of the repeating unit of the polyimine precursor in the varnish B) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was 0.1 equivalent, based on the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 6] 0.38 g (4.0 mmol) of 1,2-dimethylimidazole and 0.38 g of N,N-dimethylacetamide were added to a reaction vessel to obtain a homogeneous solution. To the solution, 23.50 g of the varnish B obtained in Synthesis Example 2 (molecular weight of 10 ppm of the repeating unit of the polyimine precursor in the varnish B) was added, and the mixture was stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 0.4 equivalents based on the amount of the feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Comparative Example 2] The varnish B obtained in Synthesis Example 2 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 7] 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 homogeneous solution. To the solution, 26.21 g of the varnish C obtained in Synthesis Example 3 (molecular weight with respect to the repeating unit of the polyimine precursor in varnish C, 10 mmol) was added, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Comparative Example 3] The varnish C obtained in Synthesis Example 3 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 8] 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 homogeneous solution. To the solution was added 28.60 g of the varnish D obtained in Synthesis Example 4 (molecular weight of 10 ppm with respect to the repeating unit of the polyimine precursor in varnish D), and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Comparative Example 4] The varnish D obtained in Synthesis Example 4 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless 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 measurement results of the properties of this polyimide film are shown in Table 2-1.

[Example 9] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimide intermediate precursor was 0.2 equivalents based on the amount of the feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Example 10] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1-methylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Example 11] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 2-methylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Example 12] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of imidazoles was 0.2 equivalents relative to the repeating unit of the polyamidene precursor, 1 mole, calculated from the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Example 13] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 2-phenylimidazole is 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Example 14] 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 homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of benzimidazole is 0.2 equivalents relative to the repeating unit of the polyamidene precursor, 1 mole, calculated from the amount of feed.

The polyimine precursor solution filtered through the PTFE filter membrane is coated on a glass substrate, and heated to a temperature of 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) to carry out thermal yttrium imine. The colorless transparent polyimide film/glass laminate was obtained. 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 5] The varnish E obtained in Synthesis Example 5 filtered through a PTFE filter membrane was applied onto a glass substrate, and heated directly from room temperature to 440 ° C on a glass substrate under a nitrogen atmosphere (oxygen concentration: 200 ppm or less). The enthalpy imidization was carried out to obtain a colorless 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 measurement results of the properties of this polyimide film are shown in Table 2-2.

[Comparative Example 6] 0.10 g (1.0 mmol) of 2-ethyl-2-imidazoline and 0.90 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, the varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in the varnish E) was added, and the varnish was gelated. Even after stirring at room temperature for 3 hours, a uniform polyimide precursor solution was not obtained. The molar number of 2-ethyl-2-imidazoline was 0.1 equivalent based on the amount of the feed, relative to the repeat unit of the polyimine precursor.

[Comparative Example 7] 0.20 g (2.0 mmol) of 2-ethyl-2-imidazoline and 1.80 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. To the solution, the varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of 10 mmol of the repeating unit of the polyimine precursor in the varnish E) was added, and the varnish was gelated. Even after stirring at room temperature for 3 hours, a uniform polyimide precursor solution was not obtained. The molar number of 2-ethyl-2-imidazoline was 0.2 equivalents based on the amount of the feed, relative to the repeat unit of the polyimine precursor.

[Comparative Example 8] 1.85 g (40.0 mmol) of 1,2-dimethylimidazole and 0.50 g of N-methyl-2-pyrrolidone were added to a reaction vessel to obtain a homogeneous solution. The varnish E 25.51 g obtained in Synthesis Example 5 (molecular weight of the repeating unit of the polyimine precursor in varnish E was 10 mmol) was added to the solution, and stirred at room temperature for 3 hours to obtain uniformity. A viscous polyimide precursor solution. The molar number of 1,2-dimethylimidazole relative to the repeating unit of the polyimine precursor was calculated to be 4.0 equivalents based on the amount of the feed. If the obtained polyimide intermediate precursor solution was stored at 23 ° C, the polyimine precursor solution gelled until the third day.

[Table 2-2]

From the results shown in Tables 2-1 to 2-2, it is understood that the polyimine obtained from the polyimide composition containing the imidazole compound has excellent transparency and a small coefficient of thermal expansion (Examples 1-4). Comparative Example 1, Examples 5 to 6 and Comparative Example 2, Example 7 and Comparative Example 3, Example 8 and Comparative Example 4, Examples 9 to 14 and Comparative Example 5). Further, it was found that the content of the imidazole-based compound was not more than 4 mol with respect to the repeating unit 1 of the polyimine precursor, and the storage stability was also excellent (Example 9 and Comparative Example 8).

As described above, the polyimine obtained from the polyimine precursor composition of the present invention has excellent light transmittance, mechanical properties, and a low linear thermal expansion coefficient, and the polyimine film of the present invention can be suitably used as A transparent substrate that is colorless and transparent and can form a fine circuit for display purposes. [Industry Utilization]

According to the present invention, it is possible to provide a polyimine which has better transparency and a low coefficient of thermal expansion even if it is a polyimide of the same composition, or has excellent transparency, a low coefficient of thermal expansion, and excellent mechanical properties. A polyimine precursor composition of a polyimine (a solution composition containing a polyimide precursor) and a method for producing a polyimide. The polyimine obtained by the polyimine precursor composition has high transparency and a low coefficient of thermal expansion, and is easy to form a fine circuit, and is particularly suitable for use in displays, touch panels, solar cells, and the like. Formation of a substrate.

Claims (13)

A polyamidiene precursor composition characterized by comprising: a polyimine precursor comprising a repeating unit represented by the following chemical formula (1-1), and an imidazole compound; the content of the imidazole compound is relative to the polyazide The repeating unit 1 of the amine precursor is less than 4 moles; (In the formula, A is a divalent group having an aromatic ring, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 9 carbon atoms). The polyimine precursor composition of claim 1, wherein the polyimine precursor comprises a repeating unit represented by the following chemical formula (1-2); (In the formula, A is a divalent group having an aromatic ring, and X ₁ and X ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylene group having 3 to 9 carbon atoms). The polyimine precursor composition according to claim 1 or 2, wherein the chemical formula (1-1) or the chemical formula (1-2) is a group represented by the following chemical formula (1-A) ; 【化3】 (wherein m represents an integer of 0 to 3, n represents an integer of 0 to 3, and m and n are each independently; and Y ₁ , Y ₂ , and Y ₃ each independently represent a hydrogen atom, a methyl group, and a trifluoro group. In the group consisting of methyl groups, Q and R each independently represent a direct bond or a group selected from the group consisting of: -NHCO-, -CONH-, -COO-, -OCO- One of the groups). The polyimine precursor composition according to claim 1 or 2, wherein the polyimine obtained from the polyimide precursor composition has a transmittance of a film having a thickness of 10 μm at a wavelength of 400 nm. More than 75%. The polyimine precursor composition according to claim 1 or 2, wherein the content of the imidazole compound is 0.05 mol or more and 2 mol or less per mol of the repeating unit 1 of the polyimide intermediate precursor. . The polyimine precursor composition according to claim 1 or 2, wherein the imidazole compound is 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-benzene Any of imidazole, imidazole, or benzimidazole. A method for producing a polyimine, which is characterized in that the polyimide composition precursor according to any one of claims 1 to 6 is heat-treated at a maximum heating temperature of more than 350 ° C, and The polybendimimine precursor is imidized. The method for producing a polyimine of claim 7, comprising the steps of: coating a polyimide composition precursor composition according to any one of claims 1 to 6 on a substrate; The polyimine precursor composition on the substrate is heat-treated at a maximum heating temperature of more than 350 ° C to imidize the polyimide precursor. The method for producing a polyimine of claim 7 or 8, wherein the heat treatment has a maximum heating temperature of more than 400 °C. A polyimine which is produced by the method for producing a polyimine according to any one of claims 7 to 9. The polyimine of claim 10, wherein the film having a thickness of 10 μm has a light transmittance of 75% or more at a wavelength of 400 nm. A polyimine film produced by the method for producing a polyimine according to any one of claims 7 to 9. A substrate for a display, a touch panel, or a solar cell, which comprises a polyimine film according to claim 10 or 11 or a polyimide film according to claim 12 of the patent application.