JPWO2013161970A1 - Polyamic acid solution composition and polyimide - Google Patents

Abstract

The present invention uses a tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride 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. Colloidal silica is added to the organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. The present invention relates to a polyamic acid solution composition to which a dispersed colloidal solution is added.

Description

  The present invention relates to a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and having a linear expansion coefficient (CTE), particularly a linear expansion coefficient controlled at a relatively low temperature.

  Polyimides obtained from tetracarboxylic dianhydrides and diamines are widely used in the electrical and electronic industries because of their excellent properties such as heat resistance, mechanical strength, electrical properties, and solvent resistance. However, since polyimide has poor solubility in an organic solvent, usually, a solution composition (polyamic acid solution composition) in which a polyimide precursor polyamic acid is dissolved in a solvent is applied onto a substrate surface, for example, and then A polyimide is obtained by heating at a high temperature to cause dehydration ring closure (imidization).

  However, polyimides generally tend to be essentially yellowish brown due to intramolecular conjugation or charge transfer complex formation, and improved transparency is required for some applications.

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

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

  Patent Document 3 includes 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3. Aromatic dianhydride components including 4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-bis Selected from (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′-bis (3-aminophenoxy) diphenylsulfone, bis (3-aminophenyl) sulfone and bis (4-aminophenyl) sulfone A polyimide having excellent transparency obtained from an aromatic diamine component containing one or more of them is disclosed. However, this polyimide may not necessarily have a sufficiently low linear expansion coefficient, and the linear expansion coefficient at a high temperature exceeding 200 ° C. (for example, 300 ° C. to 400 ° C.) is controlled to be lower. It is desirable.

  On the other hand, Patent Document 4 discloses a compound having a substituent capable of binding to a polyamic acid prepared so that the molecular chain terminal is an acid anhydride and a polymer such as 3-aminopropyltriethoxysilane (coupling). A polyimide / silica hybrid material obtained by reacting with (reagent) and then reacting by adding tetraethoxysilane (heat imidization / conversion to silica) is disclosed. However, in this method, the aminopropyl group may be thermally decomposed during thermal imidization, and the transmittance of the resulting polyimide may be reduced.

JP 2010-30972 A JP 2010-235641 A Special table 2010-513591 gazette JP 2006-31680 A

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

The present invention relates to the following matters.
1. A tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride 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 are reacted in a solvent. Colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. A polyamic acid solution composition obtained by adding a colloidal solution.
2. 2. The polyamic acid solution composition according to item 1, wherein the amount of silica 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. Item 3. The polyamic acid solution composition according to any one of Items 1 to 2, wherein the silica has a particle size of 1 to 60 nm.

4). The polyimide obtained by heat-treating the polyamic acid solution composition has a light transmittance at a wavelength of 400 nm of a film having a thickness of 10 μm of 70% or more, and a linear expansion coefficient of 300 to 400 ° C. is 350 ppm / ° C. or less. Item 4. The polyamic acid solution composition according to any one of Items 1 to 3, wherein the solution is a polyamic acid solution composition.
5. Item 5. The polyamic acid solution composition according to item 4, wherein the polyimide obtained by heat-treating the polyamic acid solution composition has a linear expansion coefficient of 300 to 400 ° C of 250 ppm / ° C or less.

6). The tetracarboxylic dianhydride containing the fluorine atom is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
The diamine containing a fluorine atom is 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl and / or 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoro. Item 6. The polyamic acid solution composition according to any one of Items 1 to 5, which is propane.

7). A method for producing the polyamic acid solution composition according to any one of Items 1 to 6,
A tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride 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 are reacted in a solvent. Producing a polyamic acid solution,
In the obtained polyamic acid solution, colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. A method for producing a polyamic acid solution composition comprising the steps of adding and mixing a colloidal solution.

8). The polyimide obtained by heat-processing the polyamic acid solution composition in any one of said claim | item 1 -6.
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 Item 8.

10. A method of manufacturing a flexible device which is a display device or a light receiving device,
The process of forming the solid polyimide resin film by applying the polyamic acid solution composition according to any one of Items 1 to 6 on a carrier substrate and heat-treating, and the process of forming a circuit on the polyimide resin film And the manufacturing method of the flexible device characterized by including the process of peeling the polyimide resin film in which the said circuit was formed in the surface from the said 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.

  According to the present invention, there is provided a polyamic acid solution composition capable of obtaining a polyimide having excellent transparency and a linear expansion coefficient, particularly a linear expansion coefficient at a high temperature (for example, a linear expansion coefficient of 300 to 400 ° C.) controlled to be relatively low. 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 highly transparent and has a comparatively high linear expansion coefficient, particularly a linear expansion coefficient at a high temperature (for example, a linear expansion coefficient of 300 to 400 ° C.). Is controlled low. 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 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% of tetracarboxylic dianhydride containing a fluorine atom. The tetracarboxylic acid component contained in an amount of at least mol% and the diamine containing a fluorine atom in an amount of at least 50 mol%, preferably at least 75 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%. It is obtained from the diamine component contained. The tetracarboxylic acid component includes tetracarboxylic acid and tetracarboxylic acid derivatives such as tetracarboxylic dianhydride.

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

  A in chemical formula (1) is a chemical structure derived from a tetracarboxylic acid component, which is a tetravalent group obtained by removing a carboxyl group from tetracarboxylic acid, and B is a chemical structure derived from a diamine component. , A divalent group obtained by removing an amino group from a diamine, provided that 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more of A is a fluorine atom. Is a tetravalent group obtained by removing a carboxyl group from tetracarboxylic acid containing B, and B is 50 mol% or more, preferably 75 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more. A divalent group obtained by removing an amino group from a diamine containing a fluorine atom.

  Examples of the tetracarboxylic dianhydride containing a fluorine atom used in the present invention include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) represented by the following formula (2). ), 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 -Pyromellitic anhydride], 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 4- (trifluoromethyl) pyromellitic dianhydride, 1,4-difluoropyromellitic dianhydride 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride and the like. Among these, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride can be preferably used.

  In addition, the tetracarboxylic dianhydride containing a fluorine atom may use 1 type, or may use 2 or more types.

  Examples of the diamine containing a fluorine atom used in the present invention include 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2′-TFMB) represented by the following formula (3). 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'-biphenyl) -4,4'-diamine, 4,4'-diaminooctafluorobiphenyl, , 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 trifluoride, 4,4-diamino-2- (trifluoro) And methyl) diphenyl ether. Among these, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane can be preferably used.

  In addition, 1 type may be used for the diamine containing a fluorine atom, or 2 or more types may be used for it.

  The polyamic acid of the present invention may be obtained using other tetracarboxylic acid components and / or other diamine components as long as the properties of the present invention are not impaired. For example, in 100 mol% of all tetracarboxylic acid components, 50 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less is one or more other tetracarboxylic acid components. Further, in 100 mol% of the diamine component, 50 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less, particularly preferably 10 mol% or less is one or more other diamines. It may be a component.

  Examples of other tetracarboxylic acid components that can be used include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and dicyclohexyl. −3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride, 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3; 5,6-tetracarboxylic dianhydride, 4,8-ethano-1H, 3H-benzo [ 1,2-c: 4,5-c ′] difuran 1,3,5,7-tetron and the like alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, 9,9-bis ( 3,4-dicarboxyphenyl) fluorene Tetracarboxylic dianhydrides containing a fluorene skeleton such as anhydride (BPAF), tetracarboxylic dianhydrides containing sulfur atoms such as 4,4′-thiodiphthalic dianhydride, 4,4 ′-(dimethylsila Diyl) diphthalic dianhydride and other tetracarboxylic dianhydrides containing silicon atoms, 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 Products, diphenylsulfonetetracarboxylic dianhydride, p-terphenyltetracarboxylic dianhydride, m-terphenyltetracarboxylic dianhydride, etc. .

  Examples of other diamine components that can be used include trans-1,4-cyclohexanediamine (CHDA), cis-1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( Aminomethyl) cyclohexane, 1.3-adamantanediamine, 1,3-bis (4-aminophenyl) adamantane, alicyclic diamines such as 1,3-cyclohexanediamine, 1,6-hexamethylenediamine, 1,10- Aliphatic diamines such as decamethylenediamine, diamines containing a fluorene skeleton such as 9,9-bis (4-aminophenyl) fluorene (BAFL), 9.9-bis [(4-aminophenoxy) phenyl] fluorene, 4, 4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide Diamines containing sulfur atoms such as diamines, diamines containing silicon atoms such as 4,4- (dimethylsiladiyl) diaminobenzene, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3 , 4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,4-toluenediamine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, bis (4-amino-3-carboxyphenyl) methane, 2,4-diaminotoluene and the like can be mentioned.

  The polyamic acid of the present invention can be obtained as a polyamic acid solution (or 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.

  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 examples thereof include the same solvents as those used for preparing the polyamic acid. The solvent may be a mixture of two or more.

  In the polyamic acid solution composition of the present invention, the silica is further added in an amount of 1 to 100 parts by weight, preferably 5 to 90 parts by weight, more preferably 10 to 10 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic acid component and the diamine component. Included in an amount of 90 parts by weight. In a certain embodiment, it is preferable that a polyamic acid solution composition further contains a silica in the quantity of 5-70 mass parts with respect to 100 mass parts of total amounts of a tetracarboxylic-acid component and a diamine component. By adding silica in an amount in this range, the linear expansion coefficient at a high temperature (for example, a linear expansion coefficient at 300 to 400 ° C.) is reduced while maintaining high transparency of the polyimide obtained from the polyamic acid solution composition. be able to. Moreover, it is possible to control the linear expansion coefficient of the obtained polyimide at a particularly high temperature, depending on the amount of silica added.

  The silica used in the present invention has a particle size measured by a dynamic light scattering method of 200 nm or less, more preferably 1 to 60 nm, particularly preferably 1 to 50 nm, from the viewpoint of transparency of the resulting polyimide and dispersibility of silica. More preferably, it is 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 then silica is added thereto. It can manufacture by adding so that it may become the quantity of 1-100 mass parts with respect to 100 mass parts of total amounts of a tetracarboxylic-acid component and a diamine component.

  In the present invention, from the viewpoint of the molecular weight of the resulting 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. And it is preferable to produce a polyamic acid solution composition by mixing.

  Although it does not specifically limit as a solvent of colloidal silica, For example, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), propylene glycol monomethyl ether acetate (PMA), ethylene glycol mono-n-propyl Examples include ether (NPC), ethylene glycol (EG), isopropanol (IPA), methanol, methyl ethyl ketone, methyl isobutyl ketone, xylene, n-butanol, and propylene glycol monomethyl ether. The solvent of colloidal silica is preferably selected according to the solvent of the polyamic acid solution so that desired physical properties can be obtained, and is usually preferably a solvent having high compatibility with the polyamic acid solution. Depending on the choice of solvent, the transparency and / or linear expansion coefficient of the resulting polyimide may change.

  In addition, the organic solvent to be used may be one type or two or more types.

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

  The polyamic acid solution composition of the present invention can also contain other additive components, for example, fillers other than silica, if 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. 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 in an N-methyl-2-pyrrolidone 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. 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 resulting polyimide are excellent.

  In the polyamic acid solution composition of the present invention, the solid content concentration resulting from the polyamic acid is not particularly limited, but is preferably 5% by mass to 45% by mass with respect to the total amount of the polyimide precursor and the solvent. %, More preferably 7% by mass to 40% by mass, and still more preferably 9% by mass to 30% by 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.

  As described above, the polyamic acid solution composition of the present invention is excellent in transparency, and can obtain a polyimide whose linear expansion coefficient, in particular, the linear expansion coefficient at a high temperature is controlled to be relatively low.

  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 imidation reaction can also be performed by chemically reacting a polyamic acid, which is a polyimide precursor, 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.

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

  According to the present invention, the light transmittance at a wavelength of 400 nm in a film having a thickness of 10 μm is 70% or more, and the linear expansion coefficient at 300 to 400 ° C. is 350 ppm / ° C. or less, and further 250 ppm / ° C. or less. A polyimide can be obtained. There has never been a polyamic acid solution composition that is excellent in transparency and at the same time can obtain a polyimide whose linear expansion coefficient at a high temperature is controlled to be low.

  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 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 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 polyimide precursor 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 the polyamic acid solution composition is formed on the carrier substrate, and the solvent is removed by heat treatment at a relatively low temperature to remove the self-supporting film (the state in which the film does not flow, polymerization and The substrate for flexible devices is formed by the method of dehydration and imidization by heat treatment in the state where the self-supporting film is left as it is or after being peeled off from the base material if necessary. Can be suitably obtained. As used herein, “solvent removal” or “dehydration / imidization” does not mean that only solvent removal or only dehydration / imidation proceeds in the step. A considerable degree of dehydration and imidization also proceeds in the solvent removal step, and removal of the residual solvent proceeds 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.
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

  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 W ₁ before drying and the weight W ₂ after drying by the following formula.

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 content concentration. This diluted solution was added to Cannon Fenceke No. The flow-down time (T ₁ ) was measured using 100. The logarithmic viscosity was calculated from the following equation using the flow time (T ₀ ) of blank water.

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

(Linear expansion coefficient (CTE))
A polyimide film having a thickness of 10 μm is cut into a strip shape having a width of 4 mm to obtain a test piece, and a TMA / SS6100 (manufactured by SII Technology Co., Ltd.) is used, the length between chucks is 15 mm, the load is 2 g, and the heating rate is 20 ° C./min. The temperature was raised to ° C. From the obtained TMA curve, linear expansion coefficients from 50 ° C. to 200 ° C. and from 300 ° C. to 400 ° C. were 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-Tech). Then, the transmittance at a film thickness of 10 μm was calculated using a Lambert-Beer Law.

[Reference Example 1]
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 tube, and 25.12 g (0.0785 mol) of 2,2′-TFMB was added as a solvent. ) And 34.88 g (0.0785 mol) of 6FDA were added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content concentration of 11.43% and a logarithmic viscosity of 0.60.

[Comparative Example 1]
The polyamic acid solution obtained in Reference Example 1 was applied onto a glass plate as a substrate 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 30 minutes. Then, heat treatment was performed at 400 ° C. for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.

[Example 1]
Colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST; silica particle solid content concentration: 20 wt%; silica Particle diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 2 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.

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

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.

Example 3
To the polyamic acid solution obtained in Reference Example 1, 60 g of a colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST) is added and stirred, and the polyamic acid is stirred. A solution composition was obtained. The addition amount of silica is 20 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.

Example 4
To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution in which colloidal silica is dispersed in N, N-dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd., DMAc-ST) is added and stirred, and the polyamic acid is stirred. A solution composition was obtained. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 1.

Example 5
Colloidal solution obtained by dispersing colloidal silica in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; silica particle solid content concentration: 30 wt%; silica 40 g (particle diameter: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 20 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 6
To the polyamic acid solution obtained in Reference Example 1, 80 g of a colloidal solution in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate (manufactured by Nissan Chemical Industries, Ltd., PMA-ST) is added and stirred, and the polyamic acid solution is stirred. A composition was obtained. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 7
To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution (PMA-ST, manufactured by Nissan Chemical Industries, Ltd.) in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate was added and stirred, and the polyamic acid solution was stirred. A composition was obtained. The addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 8
Colloidal solution in which colloidal silica is dispersed in ethylene glycol mono-n-propyl ether in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., NPC-ST-30; solid content concentration of silica particles: 30 wt%; silica particle size: 10 to 20 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 9
To the polyamic acid solution obtained in Reference Example 1, 120 g of a colloidal solution in which colloidal silica is dispersed in ethylene glycol mono-n-propyl ether (NPC-ST-30, manufactured by Nissan Chemical Industries, Ltd.) is added and stirred. Thus, a polyamic acid solution composition was obtained. The addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

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

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 11
To the polyamic acid solution obtained in Reference Example 1, 180 g of a colloidal solution in which colloidal silica is dispersed in ethylene glycol (manufactured by Nissan Chemical Industries, Ltd., EG-ST) is added and stirred to obtain a polyamic acid solution composition. Obtained. The addition amount of silica is 60 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

Example 12
Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 1 (Nissan Chemical Industries, Ltd., IPA-ST; silica particle solid content concentration: 30 wt%; silica particle size: 10 80 g) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 2,2′-TFMB).

This polyamic acid solution composition was applied to a glass plate of a substrate by a bar coater, and the coating film was heated to 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. For 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate.
And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 2.

[Reference Example 2]
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 27.11 g (0.0740 mol) of 6FAP and 6FDA were added. 32.89 g (0.0740 mol) was added and stirred at 50 ° C. to obtain a polyamic acid solution having a solid content of 11.47% and a logarithmic viscosity of 0.19.

[Comparative Example 2]
The polyamic acid solution obtained in Reference Example 2 was applied onto a base 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 30 minutes. Then, heat treatment was performed at 400 ° C. for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 13
Colloidal solution in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; silica particle solid content concentration: 30 wt%; silica particles) 80 g (diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 14
Colloidal solution in which colloidal silica is dispersed in propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA-ST; silica particle solid content concentration: 30 wt%; silica particles) 160 g (diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 15
Colloidal solution prepared by dispersing colloidal silica in methyl ethyl ketone in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., MEK-ST-40; silica particle solid content concentration: 40 wt%; silica particle diameter 10 ˜15 nm (no surface modification) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 16
Colloidal solution in which colloidal silica is dispersed in methyl ethyl ketone in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., MEK-AC-2101; solid content concentration of silica particles: 30 wt%; silica particle diameter of 10 ˜15 nm (with surface modification) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 17
Colloidal solution in which colloidal silica is dispersed in ethylene glycol mono-n-propyl ether in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., NPC-ST-30; solid content concentration of silica particles: 30 wt%; silica particle diameter 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 3.

Example 18
Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (Nissan Chemical Industries, Ltd., IPA-ST-30; silica particle solid content concentration: 30 wt%; silica particle diameter 10 ˜15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.

Example 19
Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (IPA-ST-S, manufactured by Nissan Chemical Industries, Ltd .; silica particle solid content concentration: 25 wt%; silica particle diameter 8 -10 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.

Example 20
Colloidal solution in which colloidal silica is dispersed in isopropanol in the polyamic acid solution obtained in Reference Example 2 (IPA-ST-S, manufactured by Nissan Chemical Industries, Ltd .; silica particle solid content concentration: 15 wt%; silica particle diameter 9 ˜15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.

Example 21
Colloidal solution in which colloidal silica is dispersed in ethylene glycol in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., EG-ST; silica particle solid content concentration: 20 wt%; silica particle diameter of 10 15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 4.

[Comparative Example 3]
To the polyamic acid solution obtained in Reference Example 1, 214 g of the polyamic acid solution obtained in Reference Example 2 was added and stirred to obtain a polyamic acid solution composition. This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

[Example 22]
Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST; Silica particle solid content concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

Example 23
Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid content concentration: 30 wt%; silica particle diameter of 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

Example 24
Colloidal solution obtained by dispersing colloidal silica in 500 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid concentration: 30 wt%; silica particle diameter of 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

Example 25
Colloidal solution obtained by dispersing colloidal silica in 500 g of the polyamic acid solution obtained in Reference Example 2 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 1 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST: Silica particle solid concentration: 30 wt%; silica particle diameter of 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 80 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

Example 26
Colloidal solution obtained by dispersing colloidal silica in 214 g of the polyamic acid solution obtained in Reference Example 1 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (PMA-, manufactured by Nissan Chemical Industries, Ltd.) ST; Silica particle solid content concentration: 30 wt%; silica particle diameter of 10 to 15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this polyimide film were measured. The results are shown in Table 5.

Example 27
Colloidal solution obtained by dispersing colloidal silica in 56 g of the polyamic acid solution obtained in Reference Example 1 and propylene glycol monomethyl ether acetate in the polyamic acid solution obtained in Reference Example 2 (manufactured by Nissan Chemical Industries, Ltd., PMA- ST; Silica particle solid content concentration: 30 wt%; silica particle diameter of 10-15 nm) was added and stirred to obtain a polyamic acid solution composition. The addition amount of silica is 40 parts by mass with respect to 100 parts by mass of the monomer component (6FDA + 6FAP + 2,2′-TFMB).

  This polyamic acid solution composition was applied onto a glass plate as a substrate by a bar coater, and the coating film was applied at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 400 ° C. A heat treatment was performed for 1 minute to form a polyimide film having a thickness of 10 μm on the glass plate. And the polyimide film was peeled from the glass plate, and the linear expansion coefficient and light transmittance of this 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 capable of obtaining a polyimide having excellent transparency and a linear expansion coefficient, particularly a linear expansion coefficient controlled at a relatively high temperature.

The polyimide obtained by heat-treating the polyamic acid solution composition of the present invention has high transparency and has a relatively low linear expansion coefficient, particularly a linear expansion coefficient at high temperatures, so that it can be used in electrical, electronic and optical devices. For example, it can be suitably used as a display device such as a liquid crystal display, 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.

Claims (11)

  A tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride 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 are reacted in a solvent. Colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. A polyamic acid solution composition obtained by adding a colloidal solution.   The polyamic acid solution composition according to claim 1, wherein the amount of silica 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 claim 1, wherein the silica has a particle diameter of 1 to 60 nm.   The polyimide obtained by heat-treating the polyamic acid solution composition has a light transmittance at a wavelength of 400 nm of a film having a thickness of 10 μm of 70% or more, and a linear expansion coefficient of 300 to 400 ° C. is 350 ppm / ° C. or less. The polyamic acid solution composition according to claim 1, wherein the composition is a polyamic acid solution composition.   The polyamic acid solution composition according to claim 4, wherein the polyimide obtained by heat-treating the polyamic acid solution composition has a linear expansion coefficient of 300 to 400 ° C. of 250 ppm / ° C. or less. The tetracarboxylic dianhydride containing the fluorine atom is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
The diamine containing a fluorine atom is 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl and / or 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoro. It is a propane, The polyamic acid solution composition in any one of Claims 1-5 characterized by the above-mentioned. A method for producing the polyamic acid solution composition according to any one of claims 1 to 6,
A tetracarboxylic acid component containing a fluorine atom-containing tetracarboxylic dianhydride 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 are reacted in a solvent. Producing a polyamic acid solution,
In the obtained polyamic acid solution, colloidal silica is dispersed in an organic solvent so that the amount of silica is 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component. A method for producing a polyamic acid solution composition comprising the steps of adding and mixing a colloidal solution.   The polyimide obtained by heat-processing the polyamic acid solution composition in any one of Claims 1-6.   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 claim 8. 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 any one of claims 1 to 6 on a carrier substrate and heat-treating it to form a solid polyimide resin film, a step of forming a circuit on the polyimide resin film And the manufacturing method of the flexible device characterized by including the process of peeling the polyimide resin film in which the said circuit was formed in the surface from the said 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 10.