KR20150003355A - Polyamic acid solution composition and polyimide - Google Patents

Abstract

The present invention relates to a process for producing a tetracarboxylic acid comprising a tetracarboxylic acid component containing 50 mol% or more of a tetracarboxylic acid dianhydride containing a fluorine atom and a diamine component containing 50 mol% or more of a diamine containing a fluorine atom in a solvent A colloidal solution in which colloidal silica is dispersed in an organic solvent is added to the polyamic acid solution obtained by reacting the polyamic acid solution obtained in the above step so that the amount of silica is 1 to 100 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component To a polyamic acid solution composition.

Description

POLYAMIC ACID SOLUTION COMPOSITION AND POLYIMIDE < RTI ID = 0.0 >

The present invention relates to a polyamic acid solution composition which is excellent in transparency and is capable of obtaining a polyimide whose coefficient of linear expansion (CTE), particularly the coefficient of linear expansion at a high temperature, is controlled to be relatively low.

Polyimides obtained from tetracarboxylic acid dianhydrides and diamines are widely used in the fields of electric and electronic industries because of their excellent properties such as heat resistance, mechanical strength, electrical characteristics and solvent resistance. However, since the polyimide has poor solubility in an organic solvent, a solution composition (polyamic acid solution composition) in which a polyamic acid of a polyimide precursor is dissolved in a solvent is applied, for example, on the surface of a base material, To obtain polyimide by dehydration ring closure (imidization).

However, polyimides generally tend to be colored yellowish brown by intramolecular conjugation or formation of charge transfer complexes, and it is required to improve transparency depending on the application.

Patent Document 1 discloses a polyimide having excellent light transmittance, which is obtained from cyclopentane-1,2,3,4-tetracarboxylic acid dianhydride, which is an alicyclic tetracarboxylic acid dianhydride, and an aromatic diamine. However, polyimides using alicyclic tetracarboxylic acid dianhydrides and / or alicyclic diamines as monomer components tend to be inferior in heat resistance and chemical resistance as compared with aromatic polyimides.

Patent Document 2 discloses a polyimide having a fluorene skeleton and excellent transparency. However, the polyimide having a fluorene skeleton may not always have sufficient transparency. In addition, the polyimide having a fluorene skeleton tends to have a relatively high linear expansion coefficient.

Patent Document 3 discloses that 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4- (2,5-dioxotetrahydrofuran-3-yl) , 4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3 , 3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-bis (3-aminophenoxy) diphenyl sulfone, bis 4-aminophenyl) sulfone. The polyimide excellent in transparency is obtained from the aromatic diamine component. However, the polyimide does not necessarily have a sufficiently low coefficient of linear expansion in some cases. Particularly, the coefficient of linear expansion at a high temperature exceeding 200 캜 (for example, 300 캜 to 400 캜) is preferably controlled to be lower .

On the other hand, in Patent Document 4, a polyamide acid prepared so that the molecular chain terminal is an acid anhydride is reacted with a compound (coupling reagent) having a substituent capable of binding to a polymer such as 3-aminopropyltriethoxysilane, Then, a polyimide / silica hybrid material is obtained which is obtained by adding tetraethoxysilane to the reaction (heating imidization, a telephone reaction to silica). However, in this method, there is a case where the aminopropyl group is thermally decomposed when the heat is imidized, and the transmittance of the obtained polyimide is lowered.

Japanese Laid-Open Patent Publication No. 2010-30972 Japanese Patent Application Laid-Open No. 2010-235641 Japanese Published Patent Publication No. 2010-513591 Japanese Laid-Open Patent Publication No. 2006-312680

It is an object of the present invention to provide a polyamic acid solution composition which is excellent in transparency and which is capable of obtaining a polyimide whose coefficient of linear expansion is controlled to be relatively low, particularly at a high temperature.

The present invention relates to the followings.

1. A process for producing a tetracarboxylic acid comprising a tetracarboxylic acid component containing 50 mol% or more of tetracarboxylic acid dianhydride containing a fluorine atom and a diamine component containing 50 mol% or more of a diamine containing a fluorine atom in a solvent , A colloidal solution in which colloidal silica is dispersed in an organic solvent is added to the polyamic acid solution obtained by dissolving the colloidal silica in an organic solvent so that the amount of silica is 1 to 100 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component By weight of the polyamic acid solution composition.

2. The polyamic acid solution composition according to item 1 above, wherein the amount of silica to be added is 5 to 70 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component.

3. The polyamic acid solution composition according to any one of claims 1 to 2, wherein the silica has a particle diameter of 1 to 60 nm.

4. The polyimide obtained by heat-treating the polyamic acid solution composition has a light transmittance of not less than 70% at a wavelength of 400 nm in a film having a thickness of 10 占 퐉 and a linear expansion coefficient of 300 ppm to 400 占 폚 at 350 ppm / The polyamic acid solution composition according to any one of claims 1 to 3,

5. The polyamic acid solution composition according to item 4, wherein the polyimide obtained by heat-treating the polyamic acid solution composition has a coefficient of linear expansion of 250 ppm / ° C or less at 300 to 400 ° C.

6. The fluorine-containing tetracarboxylic acid dianhydride is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,

Wherein the fluorine atom-containing diamine is 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and / or 2,2'-bis (3-amino- The polyamic acid solution composition according to any one of items 1 to 5, wherein the polyamic acid solution is hexafluoropropane.

7. A method for producing the polyamic acid solution composition according to any one of claims 1 to 6,

Reacting a tetracarboxylic acid component containing 50 mol% or more of a tetracarboxylic acid dianhydride containing a fluorine atom and a diamine component containing 50 mol% or more of a diamine containing a fluorine atom in a solvent, A step of producing a mixed acid solution,

A colloidal solution obtained by dispersing colloidal silica in an organic solvent is added to the obtained polyamic acid solution such that the amount of silica is 1 to 100 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component, Wherein the polyamic acid solution composition has a mixing process.

8. A polyimide obtained by subjecting the polyamic acid solution composition according to any one of items 1 to 6 to heat treatment.

9. An electric device, an electronic device, an optical device, a display device, a touch panel, a solar cell, or an LED lighting device including the polyimide according to the item 8 above.

10. A manufacturing method of a flexible device which is a display device or a light receiving device,

A step of applying the polyamic acid solution composition described in any one of items 1 to 6 on a carrier substrate and subjecting it to heat treatment to form a solid polyimide resin film, a step of forming a circuit on the polyimide resin film, And a step of peeling the polyimide resin film having the circuit formed on its surface from the carrier substrate.

11. 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 10 above.

According to the present invention, it is possible to provide a polyamic acid solution composition which is excellent in transparency and is capable of obtaining polyimide whose coefficient of linear expansion, particularly, the coefficient of linear expansion at high temperature (for example, the coefficient of linear expansion at 300 to 400 캜) have.

The polyimide obtained from the polyamic acid solution composition of the present invention, that is, the polyimide of the present invention has high transparency and is controlled to have a relatively low coefficient of linear expansion, particularly a coefficient of linear expansion at high temperature (for example, a coefficient of linear expansion of 300 to 400 ° C) have. The polyimide of the present invention can be preferably used for an electric device, an electronic device, and an optical device. Examples of the polyimide include a display device such as a liquid crystal display, an EL display, and an electronic paper, a touch panel, a solar cell, , A protective film, or the like. In particular, it can be preferably used as a substrate for a flexible device such as a liquid crystal display, an organic EL display, a display device such as an electronic paper, and a light receiving device such as a light receiving element of a thin film solar cell.

The polyamic acid in the polyamic acid solution composition of the present invention contains 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more of tetracarboxylic acid dianhydride containing fluorine atom , More preferably 80 mol% or more, particularly preferably 90 mol% or more, of the tetracarboxylic acid component containing the fluorine atom and the tetracarboxylic acid component containing the fluorine atom in an amount of 50 mol% or more, Or more of the diamine component. The tetracarboxylic acid component includes tetracarboxylic acid derivatives such as tetracarboxylic acid and tetracarboxylic acid dianhydride.

Therefore, the polyamic acid of the present invention is composed of a repeating unit represented by the following formula (1).

[Chemical Formula 1]

A in the formula (1) is a chemical structure derived from a tetracarboxylic acid component, which is a tetravalent group obtained by removing a carboxyl group from a tetracarboxylic acid, and B is a chemical structure derived from a diamine component. With the proviso that not less than 50 mol%, preferably not less than 75 mol%, more preferably not less than 80 mol%, particularly preferably not less than 90 mol% of A is derived from a tetracarboxylic acid containing a fluorine atom And more preferably 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more of B is a quaternary group in which the amino group is removed from a diamine containing a fluorine atom The

Examples of the fluorine atom-containing tetracarboxylic acid dianhydride used in the present invention include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride represented by the following formula (2) (6FDA), 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- Methyl] propylidene] diphthalic acid anhydride, 1H-diburo [3,4-b: 3 ', 4'-i] xantene-1,3,7,9 (11H) Bis (trifluoromethyl) pyromellitic acid dianhydride, 4- (trifluoromethyl) pyromellitic dianhydride, 1, 3-bis (trifluoromethyl) pyromellitic dianhydride, , 4-difluoropyromellitic acid dianhydride, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene 2 It may include water. Among them, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride can be preferably used.

(2)

The tetracarboxylic acid dianhydrides containing fluorine atoms may be used alone or in combination of two or more.

Examples of the fluorine atom-containing diamine used in the present invention include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2, 2'-TFMB), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) represented by the following formula (4), 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'- 4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'- Tetrafluoroaniline), 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-TFMB), 4,4'-diamino- 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 triflouide, (Trifluoromethyl) diphenyl ether, and the like. Among them, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane are preferably used Can be used.

(3)

[Chemical Formula 4]

The diamine containing a fluorine atom may be used alone or two or more thereof may be used.

The polyamic acid of the present invention may be obtained by using other tetracarboxylic acid component and / or other diamine component within a range not hindering the characteristics of the present invention. For example, in 100 mol% of the total tetracarboxylic acid component, 50 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less, A tetracarboxylic acid component and 50 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less, of the diamine component in 100 mol% Or more of other diamine components.

Other tetracarboxylic acid components that can be used include, for example, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride , Dicyclohexyl-3,3 ', 4,4'-tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-2 anhydride, 2,3,4-cyclobutanetetracarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 4,8- 1H, 3H-benzo [1,2-c: 4,5-c '] difuran 1,3,5,7-tetorone, alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride, Tetracarboxylic dianhydrides including a fluorene skeleton such as 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF), and sulfur atoms such as 4,4'-thiodiphthalic dianhydride , Tetracarboxylic acid dianhydride containing 4,4'- (dimethylsilyl) diphthalic acid dianhydride, and the like. A tetracarboxylic acid dianhydride, a 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, a 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, diphenylsulfonetetracarboxylic acid 2-anhydride, p-terphenyltetracarboxylic acid dianhydride, m-terphenyltetracarboxylic acid dianhydride, and the like.

Examples of other diamine components that can be used include trans-1,4-cyclohexanediamine (CHDA), cis-1,4-cyclohexanediamine, 1,3-bis (aminomethyl) Alicyclic diamines such as bis (aminomethyl) cyclohexane, 1,3-adamantanediamine, 1,3-bis (4-aminophenyl) adamantane and 1,3-cyclohexanediamine, , Fluorene skeletons such as aliphatic diamines such as 1,10-decamethylene diamine, 9,9-bis (4-aminophenyl) fluorene (BAFL) and 9.9-bis [ Diamine, 4,4'-diaminodiphenylsulfide and 2,2'-diaminodiphenylsulfide; diamines containing a sulfur atom such as 4,4- (dimethylsiladi) diaminobenzene , And diamines containing silicon atoms such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'- Minodiphenylmethane, 2,4-toluenediamine, 3, Dihydroxy-4,4'-diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, and 2,4-diaminotoluene.

The polyamic acid of the present invention can be obtained as a polyamic acid solution (or 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 占 폚 or lower, preferably 80 占 폚 or lower, in order to substantially equimolarize the tetracarboxylic acid component and the diamine component and to suppress the imidization reaction. Usually, the reaction temperature is 25 ° C to 100 ° C, preferably 40 ° C to 80 ° C, more preferably 50 ° C to 80 ° C, and the reaction time is about 0.1 to 24 hours, preferably 2 To about 12 hours. By setting the reaction temperature and the reaction time within the above range, a solution composition of polyamic acid having a high molecular weight can be efficiently obtained. The reaction can also be carried out in an air atmosphere, but is usually carried out preferably under an inert gas atmosphere, preferably under a nitrogen gas atmosphere.

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

The solvent to be used for preparing the polyamic acid is not particularly limited, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, Amide solvents such as pyrrolidone, N-ethyl-2-pyrrolidone and N-vinyl-2-pyrrolidone,? -Butyrolactone,? -Valerolactone,? -Valerolactone, Cyclic ester solvents such as lactone, -caprolactone and -methyl- -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, Phenol-based solvents such as 3-chlorophenol and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide and the like. In addition, other general organic solvents such as alcohol solvents such as methanol and ethanol and organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cell Methyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, But are not limited to, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, N-methylcaprolactam, hexamethylphosphorotriamide, bis (2-methoxyethoxy) ethyl ether, 1,4-dioxane, dimethyl sulfoxide, dimethyl sulfone, di Phenyl ether, diphenyl sulfone, tetramer Also urea, anisole, terpene, mineral spirit, petroleum naphtha solvent, biodegradable methyl lactate, ethyl lactate, butyl lactate may be used. The organic solvent to be used may be one kind or two kinds or more.

The polyamic acid solution composition of the present invention contains at least the polyamic acid of the present invention and a solvent. The solvent is not particularly limited as long as the polyamic acid is dissolved, and the same solvent as the solvent used for preparing the polyamic acid can be mentioned. The solvent may be a mixture of two or more species.

The polyamic acid solution composition of the present invention may further contain 1 to 100 parts by mass, preferably 5 to 90 parts by mass, more preferably 10 to 90 parts by mass of silica relative to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component It is contained in a negative amount. In one embodiment, it is preferable that the polyamic acid solution composition further contains silica in an amount of 5 to 70 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. By adding silica in this amount, the coefficient of linear expansion (for example, the coefficient of linear expansion at 300 to 400 캜) at a high temperature can be lowered while maintaining high transparency of the polyimide obtained from the polyamic acid solution composition. It is also possible to control the coefficient of linear expansion of the polyimide obtained, particularly at high temperatures, by the amount of silica added.

From the viewpoints of the transparency of the obtained polyimide and the dispersibility of silica, the silica used in the present invention preferably has a particle diameter measured by a dynamic light scattering method of 200 nm or less, more preferably 1 to 60 nm, particularly preferably 1 To 50 nm, and more preferably 10 to 30 nm.

In the polyamic acid solution composition of the present invention, a tetracarboxylic acid component and a diamine component are reacted in a solvent to obtain a polyamic acid solution (or a polyamic acid solution composition), and silica is added to the polyamic acid solution composition, And the diamine component in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total amount of the diamine component.

In the present invention, from the viewpoint of the molecular weight of the obtained polyimide, a colloidal solution obtained by dispersing colloidal silica in an organic solvent is added to a polyamic acid solution obtained by reacting a tetracarboxylic acid component and a diamine component in a solvent, To thereby prepare a polyamic acid solution composition.

Examples of the solvent for the colloidal silica include, but are not limited to, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), propylene glycol monomethyl ether acetate (PMA) (NPC), ethylene glycol (EG), isopropanol (IPA), methanol, methyl ethyl ketone, methyl isobutyl ketone, xylene, n-butanol and propylene glycol monomethyl ether. The solvent of the colloidal silica is preferably selected according to the solvent of the polyamic acid solution so as to obtain the desired physical properties, and is preferably a solvent highly compatible with the polyamic acid solution. Depending on the choice of solvent, transparency and / or linear expansion coefficient of the obtained polyimide may change.

The organic solvent to be used may be one kind or two or more kinds.

The amount of the colloidal silica to be added is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass .

In the polyamic acid solution composition of the present invention, other additive components such as a filler other than silica may be added, if necessary. From the viewpoints of the transparency of the obtained polyimide and the dispersibility of the filler, it is preferable that the added filler has a particle diameter of 200 nm or less, more preferably 50 nm or less. For example, various inorganic fillers such as titanium oxide and zirconium oxide can be used.

In the present invention, the logarithmic viscosity of the polyimide precursor (polyamic acid) is not particularly limited, but the logarithmic viscosity of the polyimide precursor (polyamic acid) in an N-methyl-2-pyrrolidone solution at a concentration of 0.5 g / g or more, and preferably 0.4 dl / g or more. When the logarithmic viscosity is 0.2 dl / g or more, the molecular weight of the polyimide precursor is high, and the mechanical strength and heat resistance of the obtained polyimide are excellent.

In the polyamic acid solution composition of the present invention, the solid content concentration due to the polyamic acid is not particularly limited, but is preferably 5% by mass to 45% by mass, more preferably 7% by mass relative to the total amount of the polyimide precursor and the solvent % To 40% by mass, and more preferably 9% by mass to 30% by mass. When the solid concentration is lower than 5 mass%, the productivity and handling during use may be deteriorated. When the solid concentration is higher than 45 mass%, the fluidity of the solution may be lost.

The solution viscosity of the polyamic acid solution composition of the present invention at 30 캜 is not particularly limited, but is preferably 1000 Pa · sec or less, more preferably 0.1 to 500 Pa · sec, still more preferably 0.1 to 300 Pa · sec, and particularly preferably 0.1 to 200 Pa · sec. If the solution viscosity exceeds 1000 Pa · sec, the flowability is lost and it may become difficult to uniformly coat the metal or glass. If the solution viscosity is lower than 0.1 Pa · sec, Cratering or the like may occur. In addition, it may be difficult to obtain a polyimide having high properties or a substrate for a polyimide flexible device.

As described above, the polyamic acid solution composition of the present invention can obtain polyimide having excellent transparency and controlled coefficient of linear expansion, particularly, coefficient of linear expansion at a relatively low temperature.

In the polyamic acid solution composition of the present invention, for example, the polyimide can be preferably obtained by removing the solvent by a heat treatment and imidizing (dehydrating ring closure). The heat treatment conditions are not particularly limited, but they may be dried at a temperature in the range of 50 to 150 占 폚 and 150 to 250 占 폚, and then heat-treated at a temperature of 300 占 폚 to 400 占 폚, preferably 350 占 폚 to 400 占 폚 .

This heating treatment can be preferably carried out under normal pressure, but may be carried out under reduced pressure in order to remove the solvent efficiently. It is also possible to perform defoaming treatment by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the temperature of the heat treatment is suddenly raised, a problem such as foaming may occur, and polyimide having good characteristics may not be obtained.

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

The method of imidization is not particularly limited, and a known method of heat imidization or chemical imidization can be suitably applied.

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 탆 is formed, a polyimide having a light transmittance of 400 nm or more, 70% or more, more preferably 75% or more, and further 80% or more can be obtained.

The polyimide obtained from the polyamic acid solution composition of the present invention is particularly controlled to have a relatively low coefficient of linear expansion at a high temperature exceeding 200 캜. According to the present invention, for example, the coefficient of linear expansion at 300 to 400 캜 is 350 ppm / Or less, more preferably 250 ppm / ° C or less, further preferably 10 to 200 ppm / ° C.

According to the present invention, it is possible to provide a polyimide film having a light transmittance of not less than 70% at a wavelength of 400 nm in a film having a thickness of 10 占 퐉, a coefficient of linear expansion at 300 to 400 占 폚 not higher than 350 ppm / 占 폚, Can be obtained. A polyamic acid solution composition capable of obtaining polyimide excellent in transparency and controlled at a low coefficient of linear expansion, particularly at high temperature, has not existed in the past.

The thickness of the film made of the polyimide of the present invention can be appropriately selected depending on the use, and is preferably about 1 to 100 mu m, more preferably about 1 to 50 mu m.

The polyimide obtained from the polyamic acid solution composition of the present invention has high transparency and therefore can be suitably used for electric devices, electronic devices and optical devices requiring transparency. Examples of the polyimide include liquid crystal displays, EL displays, electronic papers, etc. A touch panel, a solar cell, a substrate of a LED lighting device, a protective film, or the like. In particular, it can be preferably used as a substrate for a flexible device such as a liquid crystal display, an organic EL display, a display device such as an electronic paper, and a light receiving device such as a light receiving element of a thin film solar cell.

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 preferably used as a polyimide precursor composition for a flexible device substrate.

In the method for producing a flexible device of the present invention, a polyamic acid solution composition is applied or sprayed on the surface of a substrate to form a coating film comprising a polyamic acid solution composition layer, and the polyamic acid solution composition is subjected to heat treatment to form a polyimide flexible device Thereby obtaining a substrate for use.

In the present invention, the polyamic acid solution composition is preferably subjected to imidization (dehydration ring closure) while removing the solvent by heat treatment, thereby obtaining a substrate for polyimide flexible devices. The heat treatment conditions are not particularly limited, but they may be dried at a temperature in the range of 50 to 150 占 폚 and 150 to 250 占 폚, and then heat-treated at a temperature of 300 占 폚 to 400 占 폚, preferably 350 占 폚 to 400 占 폚 .

This heating treatment can be preferably carried out under normal pressure, but may be carried out under reduced pressure in order to remove the solvent efficiently. It is also possible to perform defoaming treatment by heat treatment at a relatively low temperature under reduced pressure in the initial stage. If the temperature of the heat treatment is suddenly raised, there arises a problem such as foaming and a good substrate for a flexible device may not be obtained in some cases.

In the method of manufacturing a flexible device of the present invention, a polyimide precursor composition (polyamic acid solution composition) is coated on a carrier substrate as a support and subjected to heat treatment to form a solid polyimide resin film, After the circuit is formed, the polyimide resin film on which the circuit is formed is peeled from the carrier substrate.

The application of the polyamic acid solution composition can be applied as long as it is a method capable of forming 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, and the solvent is removed by heat treatment at a relatively low temperature to form a self-supporting film (a state in which no flow of the film occurs, The substrate for a flexible device can be preferably obtained by a method of dehydrating and imidizing the self-supporting film in a state of being as it is, or in a state of being peeled off from the substrate if necessary. The term " solvent removal " or " dehydration / imidization " used herein does not mean that only solvent removal or dehydration / imidization proceeds in the respective steps. The dehydration and imidization proceeds to a considerable extent in the solvent removal process, and the removal of the remaining solvent proceeds in the dehydration and imidization process.

The polyamic acid solution composition of the present invention may contain other additive components depending on the use of the resulting substrate for a polyimide flexible device. The resulting substrate for a polyimide flexible device may be a laminate of another resin layer.

In the method of manufacturing a flexible device of the present invention, the thickness of the polyimide resin film is preferably 1 to 20 占 퐉. When the thickness is less than 1 占 퐉, the polyimide resin film can not maintain sufficient resistance, and may fail to withstand stress when used as a flexible device substrate. Further, if the thickness of the polyimide resin film exceeds 20 m, it becomes difficult to reduce the thickness of the flexible device. In order to make the film thinner while maintaining sufficient resistance as a flexible device, the thickness of the polyimide resin film is more preferably 2 to 10 mu m.

In the method of manufacturing a flexible device of the present invention, a circuit necessary for a display device or a light receiving device is formed on a polyimide resin film formed as described above. This process differs depending on the type of device. For example, in the case of manufacturing a TFT liquid crystal display device, a TFT of, for example, amorphous silicon 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. On top of this, the structure necessary for the liquid crystal display may be formed by a known method. The polyimide resin film obtained in the present invention is excellent in various characteristics such as heat resistance and toughness, so that the method of forming a circuit or the like is not particularly limited.

As described above, the polyimide resin film having a circuit or the like formed on its surface is peeled from the carrier substrate. The peeling method is not particularly limited, and for example, peeling can be performed by irradiating a laser or the like from the carrier substrate side. Since the polyimide resin film obtained by the present invention has high flexibility and toughness, it is also possible to simply peel the polyimide resin film from the carrier substrate (support).

Examples of the flexible device in the present invention include a display device such as a liquid crystal display, an organic EL display, and an electronic paper, and a light receiving device such as a solar cell and a CMOS. The present invention is particularly suitable for application to a device that is thinned and imparts flexibility.

Example

Hereinafter, the present invention will be described in further detail with reference to Examples. The present invention is not limited to the following examples.

The abbreviations of the compounds used in the following examples are as follows.

6FDA: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride

2,2'-TFMB: 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl

6FAP: 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

The method of measuring the characteristics used in the following examples is shown below.

(Solid concentration)

The solid content concentration of the polyamic acid solution is a value and a polyamic acid solution was dried at 350 ℃ 30 minutes, calculated from weight W ₂ after the weight W ₁ before drying and the drying by the following equation.

Solid content concentration (% by weight) = (W ₂ / W ₁ ) × 100

(Logarithmic viscosity)

The sample solution was diluted to a concentration of 0.5 g / dl (solvent: N-methyl-2-pyrrolidone) based on the solid concentration. This diluted solution was diluted with water at 30 占 폚, 100 was used to measure the dropping time (T ₁ ). The logarithmic viscosity was calculated from the following equation by using the water drop time (T ₀ ) of the blank water.

Logarithmic viscosity = {ln (T ₁ / T ₀ )} / 0.5

(Coefficient of linear expansion (CTE))

A polyimide film having a thickness of 10 占 퐉 was cut into a test piece having a width of 4 mm to prepare a test piece and a test piece having a chuck length of 15 mm, a load of 2 g and a temperature raising rate of 20 占 폚 / min using a TMA / SS6100 (manufactured by SII Co., min to 400 < 0 > C. From the obtained TMA curve, the coefficient of linear expansion from 50 캜 to 200 캜 and from 300 캜 to 400 캜 was obtained.

(Light transmittance)

The transmittance of the polyimide film at a wavelength of 400 nm was measured using a spectrophotometer U-2910 (manufactured by Hitachi High-Technologies Corporation). Then, the transmittance at a film thickness of 10 mu m was calculated using a Lambert-Beer Law.

[Referential Example 1]

440 g of N-methyl-2-pyrrolidone as a solvent was added to a reaction vessel made of glass having an inner volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, and 25.12 g (0.0785 mol) of 2,2'- ) And 34.88 g (0.0785 mol) of 6 FDA were added and stirred at 50 DEG C to obtain a polyamic acid solution having a solid concentration of 11.43% and an inherent viscosity of 0.60.

[Comparative Example 1]

The polyamic acid solution obtained in Reference Example 1 was coated on a base glass plate by a bar coater and heated at 120 캜 for 60 minutes, 150 캜 for 30 minutes, 200 캜 for 30 minutes and 400 캜 for 1 minute To form a polyimide film having a thickness of 10 mu m on the glass plate. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 1.

[Example 1]

A solution of colloidal silica (DMAc-ST, manufactured by Nissan Chemical Industries, Ltd., solid content of silica particles: 20 wt%; particle of silica, manufactured by NISSAN CHEMICAL INDUSTRIAL CO., LTD.) Was prepared by adding colloidal solution of colloidal silica dispersed in N, N-dimethylacetamide to the polyamic acid solution obtained in Reference Example 1 Diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica added is 2 parts by mass based on 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 1.

[Example 2]

15 g of a colloidal solution (DMAc-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in N, N-dimethylacetamide was added to the polyamic acid solution obtained in Reference Example 1 and stirred to prepare a polyamic acid solution composition ≪ / RTI > The amount of silica to be added is 5 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 1.

[Example 3]

60 g of a colloidal solution (DMAc-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in N, N-dimethylacetamide was added to the polyamic acid solution obtained in Reference Example 1 and stirred to prepare a polyamic acid solution composition ≪ / RTI > The amount of silica to be added is 20 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 1.

[Example 4]

120 g of a colloidal solution (DMAc-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in N, N-dimethylacetamide was added to the polyamic acid solution obtained in Reference Example 1 and stirred to prepare a polyamic acid solution composition ≪ / RTI > The amount of silica added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 1.

[Example 5]

A colloid solution (PMA-ST, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD., Solid content of silica particles: 30 wt%, particle diameter of silica: silica sol, manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD.) Was prepared by adding colloidal silica in which colloidal silica was dispersed in propylene glycol monomethyl ether acetate to polyamic acid solution obtained in Reference Example 1 : 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 20 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 6]

80 g of a colloidal solution (PMA-ST, manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD.) In which colloidal silica was dispersed in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 1 and stirred to prepare a polyamic acid solution composition . The amount of silica added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 7]

120 g of a colloidal solution (PMA-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 1 and stirred to prepare a polyamic acid solution composition . The amount of silica added is 60 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 8]

A colloidal solution (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd .; silica particle solids concentration: 30 wt%; manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in ethylene glycol mono-n-propyl ether was added to the polyamic acid solution obtained in Reference Example 1. Silica particle diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 9]

120 g of a colloidal solution (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in ethylene glycol mono-n-propyl ether was added to the polyamic acid solution obtained in Reference Example 1 and stirred, To obtain a mixed acid solution composition. The amount of silica added is 60 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 10]

A colloidal solution (EG-ST, manufactured by Nissan Chemical Industries, Ltd., solid content of silica particles: 20 wt%; particle diameter of silica: 10 to 20 占 퐉) having colloidal silica dispersed in ethylene glycol was added to the polyamic acid solution obtained in Reference Example 1 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 11]

180 g of a colloidal solution (EG-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in ethylene glycol was added to the polyamic acid solution obtained in Reference Example 1 and stirred to obtain a polyamic acid solution composition. The amount of silica added is 60 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Example 12]

A colloid solution (IPA-ST, manufactured by Nissan Chemical Industries, Ltd., solid content of silica particles: 30 wt%, particle diameter of silica: 10 to 20 nm, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in isopropanol was added to the polyamic acid solution obtained in Reference Example 1 ), And the mixture was stirred to obtain a polyamic acid solution composition. The amount of silica added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 2,2'-TFMB).

The polyamic acid solution composition was coated on a substrate glass plate by a bar coater and the coated film was heat treated at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, A polyimide film having a thickness of 10 占 퐉 was formed on a glass plate.

Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 2.

[Referential Example 2]

440 g of N-methyl-2-pyrrolidone as a solvent was added to a reaction vessel made of glass having an inner volume of 500 ml equipped with a stirrer and a nitrogen gas inlet / outlet tube, 27.11 g (0.0740 mol) of 6FAP, 32.89 g (0.0740 mol) of FDA was added and stirred at 50 DEG C to obtain a polyamic acid solution having a solid concentration of 11.47% and a logarithmic viscosity of 0.19.

[Comparative Example 2]

The polyamic acid solution obtained in Reference Example 2 was coated on a base glass plate by a bar coater and heated at 120 DEG C for 60 minutes, 150 DEG C for 30 minutes, 200 DEG C for 30 minutes and 400 DEG C for 1 minute To form a polyimide film having a thickness of 10 mu m on the glass plate. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 13]

A colloidal solution (PMA-ST, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD .; silica particle solids concentration: 30 wt%, silica particle diameter: 10 mm) obtained by dispersing colloidal silica in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 2 To 15 nm) was added and stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 14]

A colloidal solution (PMA-ST, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD .; silica particle solids concentration: 30 wt%, silica particle diameter: 10 mm) obtained by dispersing colloidal silica in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 2 To 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica added is 80 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 15]

A colloidal solution (MEK-ST-40, manufactured by Nissan Chemical Industries, Ltd., silica particle solid concentration: 40 wt%, silica particle diameter: 15 nm; no surface modification) was added and stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 16]

(MEK-AC-2101, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD .; solid content of silica particles: 30 wt%; silica particles having a diameter of 10 to 30 μm) dispersed in colloidal silica in methyl ethyl ketone was added to the polyamic acid solution obtained in Reference Example 2, 15 nm; with surface modification) was added and stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 17]

A colloid solution (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd .; solid content concentration of silica particles: 30 wt%), in which colloidal silica was dispersed in ethylene glycol mono-n-propyl ether was added to the polyamic acid solution obtained in Reference Example 2. Silica particle diameter 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 3.

[Example 18]

A colloidal solution (IPA-ST-30, manufactured by Nissan Chemical Industries, Ltd., silica particle solid concentration: 30 wt%; silica particle diameter 10 to 15 nm, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in isopropanol was added to the polyamic acid solution obtained in Reference Example 2 ), And the mixture was stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 4.

[Example 19]

(IPA-ST-S, manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD., Silica particle solid concentration: 25 wt%, silica particle diameter: 8 to 10 nm) prepared by dispersing colloidal silica in isopropanol in polyamic acid solution obtained in Reference Example 2 ), And the mixture was stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 4.

[Example 20]

(IPA-ST-S, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD .; solid content of silica particles: 15 wt%; silica particles having a particle diameter of 9 to 15 nm (manufactured by Nissan Kagaku Kogyo KK) in which colloidal silica was dispersed in isopropanol in polyamic acid solution obtained in Reference Example 2 ), And the mixture was stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 4.

[Example 21]

A colloidal solution (EG-ST, silica particle solid concentration: 20 wt%, silica particle diameter 10 to 15 nm, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica was dispersed in ethylene glycol was added to the polyamic acid solution obtained in Reference Example 2, Was added and stirred to obtain a polyamic acid solution composition. The added amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 4.

[Comparative Example 3]

214 g of the polyamic acid solution obtained in Reference Example 2 was added to the polyamic acid solution obtained in Reference Example 1 and stirred to obtain a polyamic acid solution composition. The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 22]

214 g of the polyamic acid solution obtained in Reference Example 2 and a colloidal solution of colloidal silica dispersed in propylene glycol monomethyl ether acetate (PMA-ST, manufactured by Nissan Chemical Industries, Ltd., silica 114 g of a solid particle concentration of 30 wt% and a silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 23]

214 g of the polyamic acid solution obtained in Reference Example 2 and a colloidal solution of colloidal silica dispersed in propylene glycol monomethyl ether acetate (PMA-ST, manufactured by Nissan Chemical Industries, Ltd., silica 228 g of a solid particle concentration of 30 wt% and a silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 80 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 24]

500 g of the polyamic acid solution obtained in Reference Example 2 and a colloidal solution (manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD., PMA-ST: silica (trade name, manufactured by Nissan Chemical Industries, Ltd.)) in which colloidal silica was dispersed in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 1 160 g of solid particle concentration: 30 wt%, silica particle diameter 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 25]

500 g of the polyamic acid solution obtained in Reference Example 2 and a colloidal solution (manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD., PMA-ST: silica (trade name, manufactured by Nissan Chemical Industries, Ltd.)) in which colloidal silica was dispersed in propylene glycol monomethyl ether acetate was added to the polyamic acid solution obtained in Reference Example 1 320 g of solid particle concentration: 30 wt%, silica particle diameter 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 80 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 26]

214 g of the polyamic acid solution obtained in Reference Example 1 and a colloidal solution of colloidal silica dispersed in propylene glycol monomethyl ether acetate (PMA-ST, manufactured by Nissan Chemical Industries, Ltd., silica 114 g of a solid particle concentration of 30 wt% and a silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

[Example 27]

56 g of the polyamic acid solution obtained in Reference Example 1 and a colloidal solution of colloidal silica dispersed in propylene glycol monomethyl ether acetate (PMA-ST, manufactured by NISSAN CHEMICAL INDUSTRIES, LTD .; silica 89 g of a solid particle concentration of 30 wt% and a silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The amount of silica to be added is 40 parts by mass with respect to 100 parts by mass of the monomer component (6 FDA + 6 FAP + 2,2'-TFMB).

The polyamic acid solution composition was coated on a base glass plate by a bar coater and the coating film was subjected to heat treatment at 120 占 폚 for 60 minutes, 150 占 폚 for 30 minutes, 200 占 폚 for 30 minutes and 400 占 폚 for 1 minute, Thereby forming a polyimide film having a thickness of 10 mu m. Then, the polyimide film was peeled off from the glass plate, and the coefficient of linear expansion and light transmittance of the polyimide film were measured. The results are shown in Table 5.

According to the present invention, it is possible to provide a polyamic acid solution composition which is excellent in transparency and is capable of obtaining polyimide whose coefficient of linear expansion is controlled to be relatively low, particularly at a high temperature.

The polyimide obtained by heat-treating the polyamic acid solution composition of the present invention has high transparency and can be preferably used for electric devices, electronic devices, and optical devices because of its relatively low coefficient of linear expansion and particularly low coefficient of linear expansion at high temperatures. For example, a display device such as a liquid crystal display, an EL display, an electronic paper, a touch panel, a solar cell, a substrate of a LED lighting device, or a protective film. In particular, it can be preferably used as a substrate for a flexible device such as a liquid crystal display, an organic EL display, a display device such as an electronic paper, and a light receiving device such as a light receiving element of a thin film solar cell.

Claims (11)

Obtained by reacting a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride containing a fluorine atom in an amount of 50 mol% or more and a diamine component containing a fluorine atom-containing diamine in an amount of 50 mol% or more in a solvent Wherein a colloidal solution obtained by dispersing colloidal silica in an organic solvent is added to a polyamic acid solution such that the amount of silica is 1 to 100 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component, Lt; / RTI > The method according to claim 1,
Wherein the amount of silica to be added is 5 to 70 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. 3. The method according to any one of claims 1 to 2,
Wherein the silica has a particle diameter of 1 to 60 nm. 4. The method according to any one of claims 1 to 3,
Characterized in that the polyimide obtained by heat treatment of the polyamic acid solution composition has a light transmittance of not less than 70% at a wavelength of 400 nm in a film having a thickness of 10 占 퐉 and a linear expansion coefficient of 300 ppm to 400 占 폚 at 350 ppm / By weight of the polyamic acid solution composition. 5. The method of claim 4,
Wherein the polyimide obtained by heat-treating the polyamic acid solution composition has a coefficient of linear expansion of 250 ppm / 占 폚 or less at 300 to 400 占 폚. 6. The method according to any one of claims 1 to 5,
Wherein the fluorine atom-containing tetracarboxylic acid dianhydride is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
Wherein the fluorine atom-containing diamine is 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and / or 2,2'-bis (3-amino- ) Hexafluoropropane. ≪ / RTI > A method for producing the polyamic acid solution composition according to any one of claims 1 to 6,
A tetracarboxylic acid component containing 50 mol% or more of a tetracarboxylic acid dianhydride containing a fluorine atom and a diamine component containing 50 mol% or more of a diamine containing a fluorine atom in a solvent, A step of producing a mixed acid solution,
A colloidal solution obtained by dispersing colloidal silica in an organic solvent is added to the obtained polyamic acid solution such that the amount of silica is 1 to 100 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component, Wherein the polyamic acid solution composition has a mixing process. A polyimide obtained by subjecting the polyamic acid solution composition according to any one of claims 1 to 6 to heat treatment. An electronic device, an electronic device, an optical device, a display device, a touch panel, a solar cell, or an LED lighting device including the polyimide according to claim 8. A manufacturing method of a flexible device which is a display device or a light receiving device,
A process for forming a solid polyimide resin film by applying the polyamic acid solution composition according to any one of claims 1 to 6 onto a carrier substrate and subjecting the film to a heat treatment to form a circuit on the polyimide resin film And a step of peeling the polyimide resin film formed on the surface of the circuit from the carrier substrate. A flexible device which is a display device or a light receiving device manufactured by the manufacturing method of a flexible device according to claim 10.