JP2015129201A - Polyamic acid solution composition and polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamic acid solution composition comprising a polyamic acid having a 9,9'-diphenyl fluorene skeleton and having excellent film-forming property, and a polyimide film obtained from the composition.SOLUTION: A polyamic acid composition is provided, which is obtained from a monomer component comprising a tetracarboxylic acid component and a diamine component. The composition contains: as the tetracarboxylic acid component, an amide group-containing tetracarboxylic acid dianhydride represented by general formula (1) below by more than 50 mol%; and as the diamine component, a diamine having a 9,9'-diphenyl fluorene skeleton by more than 50 mol%. In formula (1), R represents an aromatic diamine residue having 1 to 4 benzene rings.

Description

  The present invention relates to a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and heat resistance, and a polyimide film obtained therefrom.

  Polyimides obtained from tetracarboxylic dianhydrides and diamines, especially aromatic polyimides, have excellent heat resistance, mechanical strength, electrical properties, solvent resistance, and other properties, so they are widely used in the electrical and electronic industries. Yes. In general, however, aromatic polyimides tend to be essentially yellowish brown due to intramolecular conjugation or charge transfer complex formation, and improvements are desired for some applications.

  As a method for improving the transparency of polyimide, for example, by introducing fluorine, imparting flexibility to the main chain, or introducing a bulky side chain, the formation of a charge transfer complex is inhibited and the transparency is expressed. A method has been proposed (Non-Patent Document 1). In addition, a method of expressing transparency by using a semi-alicyclic or fully alicyclic polyimide resin that does not form a charge transfer complex in principle has also been proposed (Patent Document 1, Patent Document 2, Patent Document 3, Non-patent document 2). In particular, using an alicyclic tetracarboxylic dianhydride and / or an alicyclic diamine as a monomer component and introducing fluorine into the molecule are effective methods for obtaining a transparent polyimide.

  In addition, a polyimide having a 9,9'-diphenylfluorene skeleton has also been proposed as a polyimide having high transparency and excellent heat resistance (Patent Documents 4 and 5). Since this polyimide has a cardo structure, it has a small optical anisotropy and is expected to be used in various applications. However, a polyamic acid solution composition having a fluorene skeleton generally tends to have insufficient film-forming properties, and a polyimide film having good characteristics may not be obtained.

JP 2002-348374 A JP 2005-15629 A JP 2002-161136 A JP 2009-235284 A JP 2010-235641 A

Polymer, 47, 2337 (2006) M.M. Hasegawa, High Perform. Polym. 13, S93-S106 (2001)

  The present invention has been made in view of the above situation, and provides a polyamic acid solution composition that contains a polyamic acid having a 9,9′-diphenylfluorene skeleton and is excellent in film formability. Furthermore, it aims at providing the polyimide film obtained from it.

（式中、Ｒはベンゼン環を１から４個有する芳香族ジアミン残基を表す。）
ジアミン成分として９，９’−ジフェニルフルオレン骨格を有するジアミンを５０モル％より多く含むことを特徴とするポリアミック酸組成物。
２． 一般式（１）のＲが下記（ｉ）から（ｉｖ）の構造から選ばれることを特徴とする前記項１に記載のポリアミック酸組成物。

３． ９，９’−ジフェニルフルオレン骨格を有するジアミンが９，９−ビス（４−アミノフェニル）フルオレンであることを特徴とする前記項１または２に記載のポリアミック酸組成物。
４． テトラカルボン酸成分として、さらに、９，９−ビス（３，４−ジカルボキシフェニル）フルオレン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物または１，２，３，４−シクロブタンテトラカルボン酸二無水物を含むことを特徴とする前記項１〜３のいずれかに記載のポリアミック酸組成物。
５． ジアミン成分としてとして、さらに、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビフェニルまたはｔｒａｎｓ−１，４−シクロヘキサンジアミンを含むことを特徴とする前記項１〜４のいずれかに記載のポリアミック酸組成物。 The present invention relates to the following matters.
1. A polyamic acid composition obtained from a tetracarboxylic acid component and a diamine component, wherein the tetracarboxylic acid component contains more than 50 mol% of an amide group-containing tetracarboxylic dianhydride represented by the following general formula (1): ,

(In the formula, R represents an aromatic diamine residue having 1 to 4 benzene rings.)
A polyamic acid composition comprising more than 50 mol% of a diamine having a 9,9′-diphenylfluorene skeleton as a diamine component.
2. 2. The polyamic acid composition according to item 1, wherein R in the general formula (1) is selected from the following structures (i) to (iv):

3. Item 3. The polyamic acid composition according to item 1 or 2, wherein the diamine having a 9,9'-diphenylfluorene skeleton is 9,9-bis (4-aminophenyl) fluorene.
4). As the tetracarboxylic acid component, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, or 1, Item 4. The polyamic acid composition according to any one of Items 1 to 3, further comprising 2,3,4-cyclobutanetetracarboxylic dianhydride.
5. Any one of Items 1 to 4, further comprising 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl or trans-1,4-cyclohexanediamine as a diamine component The polyamic acid composition described in 1.

6). 6. A polyamic acid solution composition obtained by dissolving the polyamic acid composition according to any one of items 1 to 5 in a solvent.
7). A polyimide film, wherein a light transmittance at 400 nm in a film having a thickness of 10 μm obtained by heat-treating the polyamic acid solution composition according to item 6 is 70% or more.
8). An electric device, an electronic device, an optical device, a display device, a touch panel, a solar cell, or an LED lighting device using the polyimide film according to Item 7.
9. A method of manufacturing a flexible device which is a display device or a light receiving device,
The step of applying the polyamic acid solution composition according to item 6 on a carrier substrate and heat-treating it to form a solid polyimide resin film, the step of forming a circuit on the polyimide resin film, and the circuit A process for peeling a polyimide resin film formed on the surface of the carrier substrate from the carrier substrate.
10. A flexible device which is a display device or a light receiving device manufactured by the method for manufacturing a flexible device according to Item 9.

According to the present invention, a polyamic acid solution composition containing a polyamic acid having a 9,9′-diphenylfluorene skeleton and excellent in film formability can be provided.
The polyimide obtained from the polyamic acid solution composition of the present invention, that is, the polyimide of the present invention is excellent in transparency and heat resistance, and has a small optical anisotropy. The polyimide of the present invention can be suitably used for an electric device, an electronic device, and an optical device. For example, a display device such as a liquid crystal display, an EL display, and electronic paper, a touch panel, a solar cell, a substrate for an LED lighting device, or It can be suitably used as a protective film. In particular, it can be suitably used as a substrate for flexible devices such as display devices such as liquid crystal displays, organic EL displays and electronic paper, and light receiving devices such as light receiving elements of thin film solar cells.

  The polyamic acid composition of the present invention is characterized by comprising a specific amide group-containing tetracarboxylic dianhydride and a diamine having a 9,9'-diphenylfluorene skeleton as main components.

（式中、Ｒはベンゼン環を１から４個有する芳香族ジアミン残基を表す。） The specific amide group-containing tetracarboxylic dianhydride used in the present invention is an amide group-containing tetracarboxylic dianhydride represented by the following general formula (1).

(In the formula, R represents an aromatic diamine residue having 1 to 4 benzene rings.)

  R in the general formula (1) is not particularly limited as long as it is an aromatic diamine residue containing 1 to 4 benzene rings, but as a more specific aromatic diamine, there is one benzene ring. P-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,5-diaminoxylene, 2,5-diaminodurene, 2-fluoro -1,4-phenylenediamine, 2-fluoro-1,3-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,3,5,6 -Tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2-chloro-1,4-phenyle Diamine, 2-chloro-1,3-phenylenediamine, 4-chloro-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2,3,5,6-tetrachloro-1, 4-phenylenediamine, 2,4,5,6-tetrachloro-1,3-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-trifluoromethyl-1,3-phenylenediamine, 4 -Trifluoromethyl-1,3-phenylenediamine, 2,5-bistrifluoromethyl-1,4-phenylenediamine, 2,3,5,6-tetrakistrifluoromethyl-1,4-phenylenediamine, 2,4 5,6-tetrakistrifluoromethyl-1,3-phenylenediamine and the like.

  When there are two benzene rings, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 2,2′-bis (trifluoro) Methyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) benzidine, 2,2 ′, 6,6′-tetrakis (trifluoromethyl) ) Benzidine, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octakis (trifluoromethyl) benzidine, 2,2′-difluorobenzidine, 3,3′-difluorobenzidine, 2,2 ', 5,5'-tetrafluorobenzidine, 2,2', 6,6'-tetrafluorobenzidine, 2,2 ', 3,3', 5, ', 6,6'-octafluorobenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2', 5,5'-tetrachlorobenzidine, 2,2 ', 6,6' -Tetrachlorobenzidine, 2,2 ', 3,3', 5,5 ', 6,6'-octachlorobenzidine, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, o-tolidine, m-tolidine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 2,2′-bis (4-aminophenyl) hexafluoro Lopan, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2 ′-(3,4-diaminodiphenyl) hexafluoropropane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane 4,4′-methylenebis (2-methylaniline), 4,4′-methylenebis (3-methylaniline), 4,4′-methylenebis (2-ethylaniline), 4,4′-methylenebis (3-ethyl) Aniline), 4,4′-methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2,6-diethylaniline), 4,4′-oxybis (3-trifluoromethylaniline), 3, 3′-oxybis (4-trifluoromethylaniline), 4,4′-oxybis (2,3,5,6-tetrafluoroaniline), 4,4 Examples include '-thiobis (2,3,5,6-tetrafluoroaniline), 4,4'-diaminobenzanilide, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide.

  When there are three benzene rings, p-terphenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino When there are four benzene rings, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- ( 4-aminophenoxy) phenyl) sulfone, 2,2′-bis (4- (4-aminophenoxy) phenyl) propane, 2,2′-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2 , 2′-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 4,4′-sulfonylbis (4-phenylenesulfanyl) Diphosphate), 3,3'-sulfonyl bis (p- phenylene sulfide sulfonyl aniline), and the like.

R in the general formula (1) is preferably an aromatic diamine residue containing one or two benzene rings, particularly an aromatic diamine residue selected from the following (i) to (iv): Preferably there is.

  The tetracarboxylic acid component in the polyamic acid composition of the present invention is mainly composed of the above-mentioned amide group-containing tetracarboxylic dianhydride, and specifically, it is preferably contained in an amount of more than 50 mol%, preferably 60 mol%. It is more preferable to include the above, and it is particularly preferable to include 70 mol% or more.

  Examples of the diamine containing a 9,9′-diphenylfluorene skeleton used in the present invention include 9,9-bis (4-aminophenyl) fluorene (BAFL), 9.9-bis [ (4-aminophenoxy) phenyl] fluorene and the like. The diamine may have, for example, an alkyl group such as a methyl group or an ethyl group, or a substituent such as fluorine.

  The diamine component in the polyamic acid composition of the present invention is mainly composed of the diamine containing the 9,9′-diphenylfluorene skeleton as described above. Specifically, the diamine component preferably contains more than 50 mol%, preferably 60 mol%. It is more preferable to include the above, and it is particularly preferable to include 70 mol% or more.

  The tetracarboxylic acid component used in the present invention further contains an alicyclic tetracarboxylic dianhydride, a tetracarboxylic dianhydride containing a fluorine atom, a tetracarboxylic dianhydride having a fluorene skeleton, and a sulfur atom. One or more selected from the group consisting of tetracarboxylic dianhydrides and tetracarboxylic dianhydrides containing silicon atoms are included in a total amount of 50 mol% or less, preferably 30 mol% or less. Also good.

  Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) represented by the following formula (3), 1,2,4,5. -Cyclohexanetetracarboxylic dianhydride, dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-2 Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3; 5,6-tetracarboxylic dianhydride, 4, And 8-ethano-1H, 3H-benzo [1,2-c: 4,5-c ′] difuran 1,3,5,7-tetron.

  Examples of the tetracarboxylic dianhydride containing a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) represented by the following formula (4), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′-(hexafluoroisopropylidene) diphthalic anhydride, 5,5 ′-[2,2,2-trifluoro-1- [ 3- (trifluoromethyl) phenyl] ethylidene] diphthalic anhydride, 5,5 ′-[2,2,3,3,3-pentafluoro-1- (trifluoromethyl) propylidene] diphthalic anhydride, 1H -Difuro [3,4-b: 3 ', 4'-i] xanthene-1,3,7,9 (11H) -tetron, 5,5'-oxybis [4,6,7-trifluoro-pyromelli Acid anhydride], 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 4- (trifluoromethyl) pyromellitic dianhydride, 1,4-difluoropyromellitic dianhydride, 1, 4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride etc. are mentioned.

  Examples of the tetracarboxylic dianhydride containing the fluorene skeleton include 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF) represented by the following formula (5). .

  Examples of the tetracarboxylic dianhydride containing a sulfur atom include 4,4'-thiodiphthalic dianhydride.

  Examples of the tetracarboxylic dianhydride containing the above elementary atoms include 4,4 '-(dimethylsiladiyl) diphthalic dianhydride.

  The diamine component used in the present invention further includes at least one selected from the group consisting of alicyclic diamines, diamines containing fluorine atoms, diamines containing sulfur atoms, and diamines containing silicon atoms in total. 50 mol% or less, preferably 30 mol% or less. In place of these, aliphatic diamines such as 1,6-hexamethylenediamine and 1,10-decamethylenediamine can also be used.

  Examples of the alicyclic diamine include trans-1,4-cyclohexanediamine (CHDA), cis-1,4-cyclohexanediamine, and 1,3-bis (aminomethyl) cyclohexane represented by the following formula (6). 1,4-bis (aminomethyl) cyclohexane, 1.3-adamantanediamine, 1,3-bis (4-aminophenyl) adamantane, 1,3-cyclohexanediamine, and the like.

  Examples of the diamine containing a fluorine atom include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFMB) represented by the following formula (7), 2 , 3,5,6-tetrafluoro-1,4-diaminobenzene, 2,4,5,6-tetrafluoro-1,3-diaminobenzene, 2,3,5,6-tetrafluoro-1,4- Benzene (dimethanamine), 2,2′-difluoro- (1,1′-biphenyl) -4,4′-diamine, 2,2 ′, 6,6′-tetrafluoro- (1,1′-biphenyl)- 4,4′-diamine, 4,4′-diaminooctafluorobiphenyl, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-oxybis (2,3,5,6-tetrafluoroaniline) ) 3 3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (3,3′-TFMB), 4,4′-diamino-2,2′-bis (trifluoromethyl) diphenyl ether, 1,4- Bis [4-amino-2- (trifluoromethyl) phenoxy] benzene, 2,2-bis [4- [4-amino-2- (trifluoromethyl) phenoxy] hexafluoropropane, 3,5-diaminobenzene trif Loride, 4,4-diamino-2- (trifluoromethyl) diphenyl ether, and the like.

  Examples of the diamine containing a sulfur atom include 4,4'-diaminodiphenyl sulfide and 2,2'-diaminodiphenyl sulfide.

  Examples of the diamine containing a silicon atom include 4,4- (dimethylsiladiyl) diaminobenzene.

  In the present invention, other tetracarboxylic acid components and / or other diamine components may be used within a range not impairing the characteristics of the present invention, preferably within a range of about 10 mol% or less. Examples of other tetracarboxylic acid components that can be used include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, diphenylsulfone tetracarboxylic dianhydride An anhydride, p-terphenyl tetracarboxylic dianhydride, m-terphenyl tetracarboxylic dianhydride, etc. are mentioned. Examples of other diamine components that can be used include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,4- Examples include toluenediamine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, and 2,4-diaminotoluene.

  The polyamic acid composition of the present invention can be obtained as a polyamic acid solution composition by reacting a tetracarboxylic acid component and a diamine component in a solvent.

  This reaction is carried out at a relatively low temperature of, for example, 100 ° C. or less, preferably 80 ° C. or less, in order to suppress the imidization reaction using approximately equimolar amounts of the tetracarboxylic acid component and the diamine component. Although it does not limit, reaction temperature is 25 to 100 degreeC normally, Preferably it is 40 to 80 degreeC, More preferably, it is 50 to 80 degreeC, Reaction time is about 0.1 to 24 hours, Preferably It is preferably about 2 to 12 hours. By setting the reaction temperature and reaction time within the above ranges, a high molecular weight polyamic acid solution composition can be efficiently obtained. The reaction can be carried out in an air atmosphere, but usually it is suitably carried out in an inert gas atmosphere, preferably in a nitrogen gas atmosphere.

  The molar ratio of the tetracarboxylic acid component to the diamine component [tetracarboxylic acid component / diamine component] is preferably about 0.90 to 1.10, more preferably about 0.95 to 1.05.

  Although it does not specifically limit as a solvent used when preparing a polyamic acid, For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N Amide solvents such as ethyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc. Cyclic ester solvents, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, phenol solvents such as 4-chlorophenol, acetophenone, 1, 3-Dimethyl-2-imidazo Jin Won, sulfolane, and dimethyl sulfoxide. Furthermore, other common organic solvents such as alcohol solvents such as methanol and ethanol, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl Cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve 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, N-methylcaprolactam, hexamethylphosphorotriamide, bis ( -Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, diphenyl sulfone, Tetramethylurea, anisole, terpenes, mineral spirits, petroleum naphtha solvents, biodegradable methyl lactate, ethyl lactate, butyl lactate and the like can also be used. The organic solvent to be used may be one type or two or more types.

  In the present invention, the logarithmic viscosity of the polyamic acid is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, preferably 0.4 dL. / G or more is preferable. When the logarithmic viscosity is 0.2 dL / g or more, the molecular weight of the polyamic acid is high, and the resulting polyimide has excellent mechanical strength and heat resistance.

  In the polyamic acid solution composition of the present invention, the solid content concentration resulting from the polyamic acid composition is not particularly limited, but is preferably 5% by mass to 45% with respect to the total amount of the polyamic acid and the solvent. It is suitable that it is 7 mass%, More preferably, it is 7 mass%-40 mass%, More preferably, it is 9 mass%-30 mass%. When the solid content concentration is lower than 5% by mass, productivity and handling during use may be deteriorated, and when it is higher than 45% by mass, the fluidity of the solution may be lost.

  The solution viscosity at 30 ° C. of the polyamic acid solution composition of the present invention is not particularly limited, but is preferably 1000 Pa · sec or less, more preferably 0.1 to 500 Pa · sec, and still more preferably 0.1 to 300 Pa · sec. sec, particularly preferably 0.1 to 200 Pa · sec is suitable for handling. If the solution viscosity exceeds 1000 Pa · sec, the fluidity may be lost, and uniform application to metal or glass may be difficult, and if it is lower than 0.1 Pa · sec, the solution may be applied to metal or glass. Sagging or repelling may occur at the time of application, and it may be difficult to obtain a polyimide with high characteristics or a substrate for a polyimide flexible device.

  The polyamic acid solution composition of the present invention includes at least the polyamic acid composition of the present invention and a solvent. The solvent is not particularly limited as long as the polyamic acid composition can be dissolved, and examples thereof include the same solvents as those used when preparing the polyamic acid composition. The solvent may be a mixture of two or more.

  The polyamic acid solution composition of the present invention can further contain one or more selected from the group consisting of alkoxysilane compounds and silanol compounds. By adding an alkoxysilane compound and / or a silanol compound, the film forming property of the polyamic acid solution composition may be improved. Moreover, film transmittance, heat resistance, thermal dimensional stability, and the like may be improved.

  As the alkoxysilane compound used in the present invention, those having a methyl group or an ethyl group as an alkoxy group are preferable.

  In addition, from the viewpoint of transparency and heat resistance of the polyimide obtained, the alkoxysilane compound and silanol compound used in the present invention preferably have one or two phenyl groups.

  Examples of the alkoxysilane compound and silanol compound used in the present invention include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, dimethoxysilanediol, diethoxysilanediol, and tetramethoxy. Examples thereof include silane and tetraethoxysilane. An alkoxysilane compound and a silanol compound may use 1 type, or may use 2 or more types together.

  The total addition amount of the alkoxysilane compound and the silanol compound is preferably 20 parts by mass or more, and particularly preferably 50 parts by mass or more with respect to 100 parts by mass of the monomer component.

  When an alkoxysilane compound is added, an acid catalyst such as oxalic acid and a base catalyst, water, and the like can be added as needed for hydrolysis of the alkoxysilane compound.

  The polyamic acid solution composition containing an alkoxysilane compound and / or a silanol compound is obtained by reacting a tetracarboxylic acid component and a diamine component in a solvent to obtain a polyamic acid solution composition, and then adding an alkoxysilane compound and / or It can manufacture by adding a silanol compound. Further, a tetracarboxylic acid component, a diamine component, an alkoxysilane compound and / or a silanol compound are added to the solvent, and the tetracarboxylic acid component and the diamine component are reacted in the solvent in the presence of the alkoxysilane compound and / or the silanol compound. Can also be manufactured.

  In the polyamic acid solution composition of the present invention, other additive components such as a filler can be added as necessary. From the viewpoint of transparency of the obtained polyimide and dispersibility of the filler, the filler to be added preferably has a particle size of 200 nm or less, more preferably 50 nm or less. Various inorganic fillers such as silica fine particles, titanium oxide, and zirconium oxide can be used.

  The polyamic acid solution composition of the present invention can suitably obtain a polyimide by, for example, removing the solvent by heat treatment and imidizing (dehydrating ring closure). The heat treatment conditions are not particularly limited, but after drying in a temperature range of 50 ° C to 150 ° C and 150 ° C to 250 ° C, heat treatment is further performed at a temperature of 300 ° C to 400 ° C, preferably 350 ° C to 400 ° C. Is preferred.

  This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the solvent. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, problems such as foaming may occur and polyimide having good characteristics may not be obtained.

  The imidization reaction can also be performed by chemically reacting a polyamic acid, which is a polyamic acid, with a dehydrating reagent in the presence of a catalyst such as pyridine or triethylamine.

  In addition, the method of imidation is not specifically limited, The well-known thermal imidation or chemical imidation method can be applied suitably.

  The polyimide obtained from the polyamic acid solution composition of the present invention has high transparency. According to the present invention, for example, when a film having a film thickness of 10 μm is used, a polyimide having a light transmittance at a wavelength of 400 nm of 70% or more, further 75% or more, and further 80% or more can be obtained.

  In addition, the thickness of the film made of the polyimide of the present invention can be appropriately selected according to the use, and is preferably about 1 μm to 100 μm, more preferably about 1 μm to 50 μm.

  Since the polyimide obtained from the polyamic acid solution composition of the present invention has high transparency, it can be suitably used for electrical devices, electronic devices, and optical devices that require transparency, such as liquid crystal displays, It can be suitably used as a display device such as an EL display or electronic paper, a touch panel, a solar cell, a substrate of an LED lighting device, or a protective film. In particular, it can be suitably used as a substrate for flexible devices such as display devices such as liquid crystal displays, organic EL displays and electronic paper, and light receiving devices such as light receiving elements of thin film solar cells.

  In addition, the polyamic acid solution composition of the present invention may contain other additive components depending on the use of the obtained polyimide.

  The polyamic acid solution composition of the present invention can be particularly suitably used as a polyamic acid resin composition for flexible device substrates.

  In the method for producing a flexible device of the present invention, a polyamic acid solution composition is applied or sprayed onto the surface of a substrate to form a coating film comprising a polyamic acid solution composition layer, and the polyamic acid solution composition is heated. The substrate for polyimide flexible device is obtained by processing.

  In the present invention, the polyamic acid solution composition can suitably obtain a substrate for a polyimide flexible device by removing the solvent by heat treatment and imidizing (dehydrating ring closure). The heat treatment conditions are not particularly limited, but after drying in a temperature range of 50 ° C to 150 ° C and 150 ° C to 250 ° C, heat treatment is further performed at a temperature of 300 ° C to 400 ° C, preferably 350 ° C to 400 ° C. Is preferred.

  This heat treatment can be suitably performed under normal pressure, but may be performed under reduced pressure in order to efficiently remove the solvent. Further, defoaming may be performed by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the heat treatment temperature is suddenly increased, defects such as foaming may occur and a good flexible device substrate may not be obtained.

  In the method for producing a flexible device of the present invention, a polyamic acid resin composition (polyamic acid solution composition) is applied onto a carrier substrate as a support, and heat-treated to form a solid polyimide resin film. After the circuit is formed on the polyimide resin film, the polyimide resin film having the circuit formed on the surface is peeled from the carrier substrate.

  The polyamic acid solution composition can be applied by any method that can form a coating film having a uniform thickness on a carrier substrate (support). For example, application by die coating, spin coating, or screen printing is possible.

  A coating film made of a polyamic acid solution composition is formed on a carrier substrate, heat-treated at a relatively low temperature to remove the aqueous solvent, and a self-supporting film (in the state where the film does not flow, polymerization is performed with removal of the aqueous solvent). And a part of the imidization reaction is proceeding), and then the self-supporting membrane is left as it is, or it is peeled off from the base material as necessary to heat-treat and dehydrate and imidize the flexible device. A substrate for use can be suitably obtained. “Water solvent removal” or “dehydration / imidization” used here does not mean that only water solvent removal or only dehydration / imidation proceeds in the step. A considerable amount of dehydration and imidization proceeds even in the water solvent removal step, and removal of the residual water solvent proceeds also in the dehydration and imidization step.

  The polyamic acid solution composition of the present invention may contain other additive components depending on the application of the polyimide flexible device substrate to be obtained. Moreover, the polyimide flexible device board | substrate obtained may laminate | stack another resin layer further.

  In the method for manufacturing a flexible device of the present invention, the polyimide resin film preferably has a thickness of 1 to 20 μm. When the thickness is less than 1 μm, the polyimide resin film cannot maintain sufficient resistance, and when used as a flexible device substrate, it may not withstand stress and may be destroyed. On the other hand, when the thickness of the polyimide resin film exceeds 20 μm, it is difficult to reduce the thickness of the flexible device. In order to reduce the film thickness while maintaining sufficient resistance as a flexible device, the thickness of the polyimide resin film is more preferably 2 to 10 μm.

  In the method for producing a flexible device of the present invention, a circuit necessary for a display device or a light receiving device is formed on the polyimide resin film formed as described above. This process varies depending on the type of device. For example, when manufacturing a TFT liquid crystal display device, an amorphous silicon TFT, for example, is formed on a polyimide resin film. The TFT includes a gate metal layer, a silicon nitride gate dielectric layer, and an ITI pixel electrode. Further, a structure necessary for a liquid crystal display can be formed by a known method. Since the polyimide resin film obtained in the present invention is excellent in various properties such as heat resistance and toughness, the method for forming a circuit or the like is not particularly limited.

  The polyimide resin film having the circuit and the like formed on the surface as described above is peeled off from the carrier substrate. There is no restriction | limiting in particular in the peeling method, For example, it can peel by irradiating a laser etc. from the carrier substrate side. Since the polyimide resin film obtained by the present invention has high flexibility and toughness, it can be physically peeled off from the carrier substrate (support).

  Examples of the flexible device in the present invention include display devices such as liquid crystal displays, organic EL displays, and electronic paper, and light receiving devices such as solar cells and CMOS. The present invention is particularly suitable for application to a device that is desired to be thin and flexible.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

Abbreviations of the compounds used in the following examples are as follows.
H-TAC (DDS): N, N ′-(sulfonylbis (1,4-phenylene)) bis (1,3-dioxooctahydrobenzofuran-5-carboxamide)
H-TAC (PPD): N, N ′-(1,4-phenylene) bis (1,3-dioxooctahydrobenzofuran-5-carboxamide)
H-TAC (ODA): N, N ′-(oxybis (1,4-phenylene)) bis (1,3-dioxooctahydrobenzofuran-5-carboxamide)
H-TAC (TFMB): N, N ′-(2,2′-bis (trifluoromethyl)-[1,1′-biphenyl] -4,4′-diyl) bis (1,3-dioxoocta Hydrobenzofuran-5-carboxamide)
s-BPDA: 3,3′4,4′-tetracarboxylic dianhydride BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 6FDA: 2,2-bis (3,4 -Dicarboxyphenyl) hexafluoropropane dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride BAFL: 9,9-bis (4-aminophenyl) fluorene 2,2′-TFMB: 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl ODA: 4,4′-diaminodiphenyl ether CHDA: trans-1,4-cyclohexanediamine PTMS: phenyltrimethoxy Silane

A method for measuring the characteristics used in the following examples is shown below.
(Solid content concentration)
The solid content concentration of the polyamic acid solution is a value obtained by drying the polyamic acid solution at 350 ° C. for 30 minutes and obtaining the weight W1 before drying and the weight W2 after drying by the following formula.

    Solid content concentration (% by weight) = {(W1-W2) / W1} × 100

(Light transmittance)
The transmittance of the polyimide film at 400 nm was measured using a spectrophotometer U-2910 (manufactured by Hitachi High-Tech). And the transmittance | permeability in film thickness of 10 micrometers was computed using the Lambert-Beer method (Lambert-Beer Law).

(Film forming property evaluation)
The film formed was evaluated by visual observation. When cracking occurred in the entire film formed, x, when cracking occurred from 30% to 10% of the film area, Δ, film area 10 The film-forming property was evaluated as “◯” when cracking occurred only in less than%, and “◎” when cracking was hardly generated.
(Rth measurement)
Thickness direction phase difference Rth was measured using phase difference measuring device KOBRA-WR (made by Oji Scientific Instruments).

[Example 1] H-TAC (DDS) / BAFL
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet pipe, and 21.8444 g (0.0627 mol) of BAFL and H- TAC (DDS) 38.1556 g (0.0627 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content of 11.55%.
This polyamic acid solution is applied onto a base glass plate by a bar coater, and the coating film is heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min and heated at 350 ° C. for 5 minutes. The polyimide film having a thickness of 10 μm was formed on the glass plate.
After the film forming property of the obtained polyimide film was evaluated, the film was peeled from the glass plate, and transmittance measurement and Rth measurement were performed. The results are shown in Table 1.

[Example 2] H-TAC (DDS) / 6FDA / BAFL = 7/3/10
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas introduction / discharge pipe, and BAFL was added to 23.0319 g (0.0661 mol) and H- TAC (DDS) 28.1608 g (0.0661 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid concentration of 11.52%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

[Example 3] H-TAC (DDS) / CBDA / BAFL = 7/3/10
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, 25.0877 g (0.0720 mol) of BAFL and H- TAC (DDS) 30.6744 g (0.0504 mol) and CBDA (0.0216) were added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.48%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

Example 4 H-TAC (DDS) / BAFL / 2, 2′-TFMB = 10/7/3
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 15.4150 g (0.0442 mol) of BAFL, 2, 2 '-TFMB (6.0716 g, 0.0190 mol) and H-TAC (DDS) 38.4648 g (0.0632 mol) were added, and the mixture was stirred at 50 ° C to obtain a polyamic acid having a solid content of 11.54%. A solution was obtained.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

[Example 5] H-TAC (DDS) / BAFL / CHDA = 10/7/3
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, 16.48882 g (0.0473 mol) of BAFL, and 2 CHDA. 3158 g (0.0203 mol) and H-TAC (DDS) 41.1427 g (0.0676 mol) were added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.51%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

[Example 6] H-TAC (PPD) / BAFL
440 g of N-methyl-2-pyrrolidone is added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.5755 g (0.0734 mol) of BAFL and H-TAC are added. (PPD) 34.3850 g (0.0734 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.47%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

Example 7 H-TAC (ODA) / BAFL
440 g of N-methyl-2-pyrrolidone is added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 22.9970 g (0.0660 mol) of BAFL and H-TAC are added. (ODA) 36.9963 g (0.0660 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.52%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

[Example 8] H-TAC (TFMB) / BAFL
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet pipe, and BAFL was added to 20.3141 g (0.0583 mol) and H-TAC. (TFMB) 39.6761 g (0.0583 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.58%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

[Comparative Example 1] PMDA / BAFL
440 g of N-methyl-2-pyrrolidone is added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas introduction / discharge pipe, and 36.90 g (0.1059 mol) of BAFL and PMDA are added. 23.10 g (0.1059 mol) was added, and the mixture was stirred at 50 ° C. to obtain a polyamic acid solution having a solid concentration of 11.24%.
In the same manner as in Example 1, this polyamic acid solution was applied onto a substrate glass plate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, and 200 ° C. for 10 minutes. Heat treatment was performed at 350 ° C. for 5 minutes for 5 minutes, but no polyimide film was obtained.

[Comparative Example 2] CBDA / BAFL
440 g of N-methyl-2-pyrrolidone was added as a solvent to a glass reaction vessel having an internal volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet pipe, and 38.3981 g (0.1102 mol) of BAFL and 21.6113 g of CBDA were added. (0.1102 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content of 11.21%.
The polyamic acid solution was applied onto a glass substrate as in Example 1 by a bar coater, and the coating film was heated from 50 ° C. to 350 ° C. at a heating rate of 5 ° C./min. A heat treatment was carried out at 5 ° C. for 5 minutes to form a polyimide film having a thickness of 10 μm on the glass plate.
And it carried out similarly to Example 1, and performed film forming property evaluation and the transmittance | permeability measurement of the obtained polyimide film. The results are shown in Table 1.

Claims (10)

A polyamic acid composition obtained from a tetracarboxylic acid component and a diamine component, wherein the tetracarboxylic acid component contains more than 50 mol% of an amide group-containing tetracarboxylic dianhydride represented by the following general formula (1): ,

(In the formula, R represents an aromatic diamine residue having 1 to 4 benzene rings.)
A polyamic acid composition comprising more than 50 mol% of a diamine having a 9,9′-diphenylfluorene skeleton as a diamine component. 2. The polyamic acid composition according to claim 1, wherein R in the general formula (1) is selected from the following structures (i) to (iv).

The polyamic acid composition according to claim 1 or 2, wherein the diamine having a 9,9'-diphenylfluorene skeleton is 9,9-bis (4-aminophenyl) fluorene. As the tetracarboxylic acid component, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, or 1, The polyamic acid composition according to claim 1, comprising 2,3,4-cyclobutanetetracarboxylic dianhydride. The diamine component further includes 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl or trans-1,4-cyclohexanediamine. The polyamic acid composition described in 1. A polyamic acid solution composition obtained by dissolving the polyamic acid composition according to claim 1 in a solvent. A polyimide film characterized by having a light transmittance at 400 nm of a film having a thickness of 10 μm obtained by heat-treating the polyamic acid solution composition according to claim 6 of 70% or more. An electric device, an electronic device, an optical device, a display device, a touch panel, a solar cell, or an LED lighting device using the polyimide film according to claim 7. A method of manufacturing a flexible device which is a display device or a light receiving device,
A step of applying the polyamic acid solution composition according to claim 6 on a carrier substrate and performing a heat treatment to form a solid polyimide resin film, a step of forming a circuit on the polyimide resin film, and the circuit A process for peeling a polyimide resin film formed on the surface of the carrier substrate from the carrier substrate. A flexible device which is a display device or a light receiving device manufactured by the method for manufacturing a flexible device according to claim 9.