TW201718724A - Polyimide film, organic electroluminescent element, transparent conductive laminate, touch panel, solar cell, and display device - Google Patents

Abstract

A polyimide film comprising a polyimide that includes, relative to the total amount of repeating units, at least 30 mol% of a repeating unit represented by general formula (1) (in formula (1), R1, R2, and R3 each independently represent a hydrogen atom, or the like, R10 represents a specific group, and n is an integer of 0-12). The polyimide film has a tensile strength of at least 125 MPa and a breaking elongation of at least 15%.

Description

Polyimine film, organic electroluminescent device, transparent conductive laminate, touch panel, solar cell and display device

The present invention relates to a polyimide film, an organic electroluminescence device, a transparent conductive laminate, a touch panel, a solar cell, and a display device.

In recent years, in the field of display devices such as displays using organic electroluminescence devices and liquid crystal displays, etc., materials used for substrates and the like are required to have a high light transmittance such as glass and have sufficient It has a high heat resistance and a lightweight and soft material. Therefore, as a material used for the purpose of replacing the glass, etc., attention has been paid to the study of a film formed of a polyetherimide having high heat resistance and being lightweight and soft.

For example, an aromatic polyimine (for example, the trade name "KAPTON" manufactured by DuPont) and the like are known. However, these aromatic polyimines are polyimines having sufficient flexibility and high heat resistance, but they are brown in color and cannot be used for glass replacement or optical which must have light transparency. Use, etc.

Therefore, in recent years, the development of alicyclic polyimine having sufficient light transmittance has been developed as a viewpoint of use in the alternative use of glass, for example, International Publication No. 2011/099518 (Patent Document 1) Among them, a polyimine having a repeating unit of a specific formula has been disclosed. The polyimine disclosed in Patent Document 1 is a product having sufficient light transmittance and high heat resistance. However, in Patent Document 1, there is no particular description of the mechanical strength (toughness) such as tensile strength or elongation at break of the polyimide.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/099518

The present invention has been made in view of the above problems of the prior art, and has been proposed to improve the toughness of a higher tensile strength and elongation at break with a higher level of tensile strength and stretch characteristics and a sufficient balance. A polyimide film and an organic electroluminescence device using the same. Further, the present invention provides a transparent conductive laminate using the above polyimide film, a touch panel using the transparent conductive laminate, a solar cell, and a display device.

The inventors of the present invention have conducted intensive studies on the above-mentioned objects and found that the polyimine film is a polyfluorene containing 30 mol% or more of the repeating unit represented by the following general formula (1) with respect to the total repeat unit. When the film formed of the imine is used, the tensile strength and the stretch property of the film (the characteristic of the sufficient stretchability until the breakage) can be made higher and have a good balance, and the stretch is higher. The toughness of the strength and the elongation at break basis, thus completing the present invention.

In other words, the polyimine film of the present invention is formed by a polyimine containing 30 mol% or more of a repeating unit represented by the following general formula (1) with respect to the total repeat unit. It is 125 MPa or more, and the elongation at break is 15% or more.

In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and R ¹⁰ represents the following Equations (101)~(102):

One of the selected bases, n represents an integer from 0 to 12].

In the polyimine film of the present invention, the polyimine is preferably a repeating unit represented by the above formula (1) and contains 40 mol% or more based on the total repeating unit.

The organic electroluminescence device of the present invention is a film comprising the above-described polyimine film of the present invention.

Moreover, the transparent conductive laminate of the present invention is a film comprising the above-mentioned polyimide film of the present invention and a conductive material laminated on the polyimide film.

Moreover, the touch panel, the solar cell, and the display device of the present invention each include the above-described transparent conductive laminate of the present invention.

According to the content of the present invention, it is possible to provide a polyimide film having a higher level of tensile strength and stretchability and having a higher balance of tensile strength and elongation at break. Its organic electroluminescent element. Moreover, according to the content of the invention, a use can be mentioned A transparent conductive laminate of the polyimide film, a touch panel using the transparent conductive laminate, a solar cell, and a display device.

1‧‧‧Organic EL components

11‧‧‧ Polyimine film

12‧‧‧ gas barrier

13‧‧‧Transparent electrode layer

14‧‧‧Organic layer

15‧‧‧Metal electrode layer

Fig. 1 is a schematic longitudinal cross-sectional view showing a preferred embodiment of an organic electroluminescence device of the present invention.

2] An infrared absorption spectrum (IR spectrum) of the polyimide film obtained in Example 1.

Hereinafter, the present invention will be described in detail based on the preferred embodiment.

[polyimine film]

The polyimine film of the present invention is formed by a polyimine containing 30 mol% or more of the repeating unit represented by the following general formula (1) with respect to the total repeat unit, and has a tensile strength of 125 MPa. The above, and the elongation at break is 15% or more.

In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and R ^{10 is} as follows: Equations (101)~(102):

One of the selected bases, n represents an integer from 0 to 12].

Among the above formula (1), the alkyl group selected as R ¹ , R ² and R ³ is an alkyl group having 1 to 10 carbon atoms. When the carbon number exceeds 10, the glass transition temperature is lowered, and high heat resistance cannot be sufficiently achieved. Moreover, the carbon number of the alkyl group selected as R ¹ , R ² and R ³ is more easily purified, preferably 1 to 6, preferably 1 to 5, and more preferably 1 to 4. , 1~3 is especially good. Further, the alkyl groups selected as R ¹ , R ² and R ³ may be linear or branched. Further, from the viewpoint that the alkyl groups are easy to be purified, a methyl group or an ethyl group is preferred.

In the above formula (1), R ¹ , R ² and R ³ are easy to obtain a viewpoint of higher heat resistance at the time of producing a polyimine, and each has a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Preferably, the hydrogen atom, the methyl group, the ethyl group, the n-propyl group or the isopropyl group is preferably a hydrogen atom, and the hydrogen atom, the methyl group, the ethyl group, the n-propyl group or the isopropyl group are preferably used in view of the ease of obtaining the raw material or the ease of purification. Or methyl is especially good. Further, the viewpoints such as the ease of purification of the plural R ¹ , R ² and R ³ in the above formulas are particularly preferable.

Further, the group selected as R ¹⁰ in the above formula (1) is a group represented by the above formulas (101) to (102). In the case of R ¹⁰ , from the viewpoints of tensile strength, elongation at break, and heat resistance, the group represented by the above formula (101) is preferred, and tensile strength, elongation at break, and thickness direction retardation (retardation) are preferred. The viewpoint of (Rth) is preferably a group represented by the above formula (102). Further, in the present invention, the repeating unit represented by the above formula (1) may contain a repeating unit of two or more different types of R ¹⁰ .

Further, n in the above formula (1) represents an integer of 0 to 12. When the value of n exceeds the above upper limit, purification will not be easy. Further, the upper limit of the numerical range of n in the general formula (1) is more preferably purified, and 5 is preferable, and 3 is particularly preferable. Moreover, the lower limit of the numerical range of n in the general formula (1), the viewpoint of the stability of the raw material compound used when forming the repeating unit represented by the general formula (1), That is, from the viewpoint of easier production of polyimine, 1 is preferred, and 2 is particularly preferred. In this way, n in the general formula (1) is particularly preferably an integer of 2 to 3.

Furthermore, in the present invention, the polyimine is a repeating unit represented by the above formula (1), and is contained in an amount of 30 mol% or more based on the total repeat unit. The content of the repeating unit represented by the above formula (1) (containing a repeating unit represented by the general formula (1) of a plurality of species (for example, a group selected as R ¹ , R ² , R ³ , R ¹⁰ or the like) When the type is a combination of two or more different types of repeating units represented by the formula (1), etc., and the total amount thereof is 30 mol% or more with respect to the total repeat unit, the obtained polyfluorene may be obtained. The imide has a more balanced value of high tensile strength and high elongation at break, so that a polyimide film having higher toughness (mechanical strength) can be obtained (high-toughness polyimide film) ). The content of the repeating unit represented by the general formula (1) (the total amount of the repeating unit represented by the general formula (1)) gives a higher tensile strength and a higher elongation at break. From the viewpoint of heat resistance, transparency, and thickness direction retardation (Rth), it is preferably 40 mol% or more, more preferably 50 mol% or more, relative to the total repeat unit in the polyimide. Good, 70% or more is especially good, and 90% or more is especially good.

In the present invention, the polyimine may be a repeating unit represented by the above formula (1), and may be contained in an amount of 30 mol% or more based on the total repeating unit, and may contain other impurities. Repeat the unit. The other repeating units are not particularly limited, and a known repeating unit which can constitute a polyimine can be suitably used. Further, other repeating units which can be used simultaneously with the repeating unit represented by the above formula (1) are particularly suitable for use in the viewpoint of heat resistance, transparency, and thickness direction retardation (Rth). ):

In the formula (2), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and R ^a represents a carbon number of 6~. 40 aryl groups (except for the groups represented by the above formulas (101) to (102)), and n represents an integer of 0 to 12].

The repeating unit represented. Further, the plurality of the general formula R (2) in the ^1, R ^2, R ³ and n, in the general formula R (1) in the ^1, R ^2, R ³ and n have the same meaning of (the plurality of preferred The content is the same as R ¹ , R ² , R ³ and n in the above formula (1).

In the above formula (2), R ^a is an aryl group having 6 to 40 carbon atoms other than the group represented by the above formula (101) to (102) (again, R ^a is the above formula (101) to ( 102) The base of the formula (1) is the same as the repeating unit represented by the above formula (1). Therefore, the above formula (101) to (102) are excluded from R ^a in the formula (2). Base).

The carbon number of the aryl group selected as R ^a in the above formula (2) is preferably 6 to 40 (more preferably 6 to 30, particularly preferably 12 to 20). When the carbon number exceeds the above upper limit, the heat resistance and the tensile strength tend to be lowered.

In addition, R ^a in the above-mentioned general formula (2) is preferably at least one of the groups represented by the following general formulae (201) to (204) from the viewpoint of heat resistance and tensile strength.

[In the formula (203), R ^b represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, and a trifluoromethyl group, and in the formula (204), Q is a formula: -O -, -S-, -CO-, -CONH-, -COO-, -C ₆ H ₄ -, -C ₁₀ H ₆ -, -NHCO-C ₆ H ₄ -CONH-, -CONH-C ₆ H ₄ -NHCO-, -OCO-C ₆ H ₄ -COO-, -COO-C ₆ H ₄ -OCO-, -OC ₁₀ H ₆ -O-, -OCO-C ₁₀ H ₆ -COO-, -COO-C _{10 H 6 -OCO -, - CONH} -C 10 H 6 -NHCO -, - NHCO-C 10 H 6 -CONH -, - SO 2 -, - C (CF 3) 2 -, - C (CH 3) 2 -, -CH ₂ -, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, and, -C( CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ - is selected from the group formed by the group].

Further, in the above formula (203), R ^b is preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group from the viewpoint of heat resistance, and particularly preferably a hydrogen atom. Further, in the above formula (204), Q is preferably a group represented by the formula: -CONH-, -COO-, or -C ₆ H ₄ - from the viewpoint of heat resistance and tensile strength, and -CONH The group represented by -, -C ₆ H ₄ - is more preferably, and the group represented by -CONH- is particularly preferred.

Further, these are selected as the groups represented by the general formulae (201) to (204) of R ^a . For example, in terms of heat resistance and tensile strength, the base represented by the general formula (203) or (204) is Preferably, the group represented by the formula (204) is more preferable.

Further, among the repeating units represented by the above formula (2), the polyimine may be a group having a higher tensile strength, and R ^a is ^a group represented by the above formula (204). Further, in the above formula (204), Q is a repeating unit of a group represented by -CONH- or -C ₆ H ₄ -, and R ^a is ^a group represented by the above formula (204), and the above-mentioned The repeating unit in which the Q in the formula (204) is a group represented by -CONH- is particularly preferable.

Further, when the polyimine contains the repeating unit represented by the formula (2), the content of the repeating unit represented by the above formula (2) is preferably 10 to 70 mol% based on the total repeating unit. 20~60 m % is preferred. When the content of the repeating unit represented by the above formula (2) does not reach the above lower limit, the effect of containing the repeating unit represented by the formula (2) may not be sufficiently obtained (in particular, the tensile strength may be further improved). The tendency of the effect, etc.). On the other hand, when the content of the repeating unit represented by the above formula (2) exceeds the above upper limit, the value of the elongation at break decreases and the mechanical strength tends to decrease.

Further, the polyimide film of the present invention has a tensile strength of 125 MPa or more. When the tensile strengths are less than the above lower limit, a film having higher toughness cannot be obtained. Further, from the same viewpoint, the tensile strength of the polyimide film is preferably 130 MPa or more, more preferably 135 MPa or more. Further, the upper limit of the tensile strength of the polyimide film is not particularly limited, and is generally preferably 1000 MPa or less. When the values of the tensile strengths exceed the above upper limit, the processing tends to be difficult.

Further, the polyimine film of the present invention has a fracture elongation of 15% or more. When the elongation at break does not reach the aforementioned lower limit, a film having higher toughness cannot be obtained. Further, from the same viewpoint, the elongation at break of the polyimide film is preferably 20% or more, more preferably 25% or more. Further, the upper limit of the elongation at break of the polyimide film is not particularly limited, and is usually preferably 300% or less. When the value of the elongation at break exceeds the above upper limit, it tends to be difficult to process.

Further, the value of the tensile strength and the elongation at break of the polyimide film of the present invention is a value obtained by the following method. In the case of the above-mentioned measurement, the product name "Super Dumbbell Cutter (type: SDMK-1000-D, JIS K7139 (2009 issued) specification A22) is used in the "Duble Co., Ltd." An SD type lever type sample cutter (Dunber Co., Ltd. cutter (type SDL-200)) was used to prepare a measurement sample of a cut polyimide film (thickness: 13 μm). In addition, the measurement sample obtained in this manner is a dumbbell shape which is basically obtained according to the specification of the form A22 (scale test piece) described in JIS K7139 (issued in 2009) except for the thickness of 13 μm. Sheet), its size is: full length: 75mm, tab (between) distance: 57mm, parallel section length: 30mm, shoulder radius: ≧30mm, end width: 10mm, central parallel section width: 5mm Thickness: 13 μm. When used, the width between the grips is 57 mm, and the width of the grip portion is 10 mm (the same width as the full width of the end). Next, using a Tensilon-type universal testing machine (for example, the model "UCT-10T" manufactured by A & D Co., Ltd.), the width of the sample to be measured is 57 mm and the width of the grip portion. After being coordinated for 10 mm (the full width of the end portion of the test piece), the tensile test of the above-mentioned measurement sample was carried out according to the full weight of the load: 0.05 kN, test speed: 300 mm/min, and the tensile test was performed. Tensile strength (stress at break (unit: MPa)) and value of elongation at break (unit: %) (the tests are based on JIS K7162 (issued in 1994)). Further, the value (%) of the elongation at break is a sample in which the distance between the marking portions of the sample before the start of the tensile test (= the width between the grippers: 57 mm) is L ₀ and the sample is broken by the tensile test. When the distance between the marking portions (the width between the grips at the time of breaking: 57 mm + α) is L, it is calculated according to the following formula: [Elongation at break (%)] = {(LL ₀ ) / L ₀ } × 100 Seek.

Further, the polyimine is preferably 90% or more, more preferably 95% or more, and particularly preferably 96 to 100%. When the yield of the ruthenium iodide does not reach the above lower limit, heat resistance may be lowered, coloration may not occur, and pores may be generated or expanded during heating. These sulfhydrylation ratios can be calculated in the following manner. In other words, the polyimine to be measured is dissolved in a heavy solvent such as heavy chloroform (preferably heavy chloroform), and subjected to ¹ H-NMR measurement, and an NH of 10 ppm (10 ppm ± 1 ppm) is obtained from a chart of ¹ H-NMR. The H can be calculated as a method of integrating the H of COOH in the vicinity of 12 ppm (12 ppm ± 1 ppm). In this case, the integral ratio (the imidization ratio) is first, and the acid dianhydride and the diamine portion of the raw material compound are used, and the heavy solvent (DMSO-d ₆ etc.) in which these are soluble is produced. a sample of these ¹ H-NMR spectra, and in the ¹ H-NMR chart, the position (chemical shift) and integral value of the acid dianhydride H, and the H in the diamine were determined. Position (chemical shift) and integral value, using the position and integral value of H of the acid dianhydride, and the position and integral value of H of the diamine, ¹ H-NMR of the polyimine of the above-mentioned measurement target In the graph, the integral value of H in the vicinity of 10 ppm and the H in the vicinity of 12 ppm is calculated by relative comparison. Further, when the ruthenium iodide ratio is measured, the amount of the polyimine obtained by measuring the ¹ H-NMR spectrum is set to be 0.01 to 5.0 mass% based on the weight of the heavy solvent (preferably heavy chloroform). The amount of the acid dianhydride of the compound and the amount of the diamine are in an amount of 0.01 to 5.0 mass% for such a heavy solvent (DMSO-d ₆ or the like) which is soluble. Further, when the ruthenium iodide ratio was measured, the amount of the polyimine, the amount of the acid dianhydride of the raw material compound, and the amount of the diamine (the above concentration) were measured in the same concentration. In the ¹ H-NMR measurement, the measurement device was an NMR measuring machine (manufactured by VARIAN Co., Ltd., trade name: UNITY INOVA-600).

Further, among these polyimines, a temperature (Td 5%) which is reduced by 5% by weight is preferably 400 ° C or more, and preferably 450 ° C to 550 ° C. If the temperature of the 5% by weight is less than the lower limit, the heat resistance tends to be insufficient. On the other hand, when the temperature exceeds the upper limit, it is difficult to produce a polyimide having such characteristics. tendency. Further, the temperature is reduced by 5% by weight, and the heating can be carried out under the conditions of a nitrogen gas atmosphere and a nitrogen gas flow, the scanning temperature is set to 30 ° C to 550 ° C, and the temperature increase rate is 10 ° C / min. The temperature at which the weight of the sample is reduced by 5% can be obtained. In the measurement, for example, a thermogravimetric analyzer ("TG/DTA220" manufactured by SII‧Nippon Scientific Co., Ltd.) can be used as the measurement device.

Further, these polyimines preferably have a glass transition temperature (Tg) of 250 ° C or higher, and preferably 300 to 500 ° C. When the glass transition temperature (Tg) is less than the lower limit, the heat resistance tends to be insufficiently sufficient. On the other hand, when the glass transition temperature (Tg) exceeds the upper limit, it may be difficult to manufacture. The tendency of polybenzimine with these properties. In the glass transition temperature (Tg), the measurement device is a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku Corporation), and can be measured at the same time as the softening temperature measurement. Moreover, when measuring the glass transition temperature, it is preferable to carry out the measurement so that the temperature rise rate is 5 ° C / min, the nitrogen atmosphere, and the scanning range of 30 ° C to 550 ° C.

Further, among these polyimines, the softening temperature is preferably from 250 to 550 ° C, preferably from 350 to 550 ° C, and more preferably from 360 to 510 ° C. When the softening temperature is less than the lower limit, the heat resistance is lowered. For example, when a polyimide film is used as a substrate for a transparent electrode of a solar cell or a liquid crystal display device or an organic EL display device, In the heating step in the production process, it may be difficult to sufficiently suppress deterioration of the quality of the film (substrate) (cracks, etc.). On the other hand, when the polyvalent imine is produced, it may not be possible. The solid ring-phase condensation reaction with poly-proline is carried out simultaneously with a sufficient solid phase polymerization reaction, and when a film is formed, a tendency to embrittle the film is formed.

Further, the softening temperature of the polyimine can be measured in the following manner. In other words, a film made of polyimine, which is 5 mm in length, 5 mm in width, and 0.013 mm (13 μm) in thickness, was prepared as a measuring device using a thermomechanical analyzer (trade name "TMA8311"). Using a nitrogen atmosphere and a heating rate of 5 ° C / min, the transparent quartz probe (diameter of the front end: 0.5 mm) was drilled at a pressure of 500 mN in a temperature range of 30 ° C to 550 ° C. Membrane method, which can simultaneously measure glass transfer Temperature (Tg) (i.e., measured by the so-called Penetration method). Moreover, in performing these measurements, the softening temperature can be calculated based on the measurement data based on the method described in JIS K 7196 (1991).

Further, the polyamidene forming the films preferably has a thermal decomposition temperature (Td) of 450 ° C or higher, and preferably 480 to 600 ° C. When the thermal decomposition temperature (Td) is less than the lower limit, the heat resistance tends to be insufficiently sufficient. On the other hand, when the temperature exceeds the upper limit, the polyimine having such characteristics tends to be difficult to be produced. Further, the thermal decomposition temperature (Td) can be measured by using a TG/DTA220 thermogravimetric analyzer (manufactured by SII‧Nippon Scientific Co., Ltd.) under a nitrogen atmosphere at a temperature elevation rate of 10 ° C/min. The temperature of the intersection formed by the decomposition curve before and after the decomposition can be obtained.

Further, the number average molecular weight (Mn) of the polyimine is preferably from 1,000 to 1,000,000 in terms of polystyrene, and preferably from 10,000 to 500,000. When the number average molecular weight is less than the lower limit, not only is it difficult to achieve sufficient heat resistance, but also the polymerization solvent may not be sufficiently precipitated at the time of production, and the polyimine may not be efficiently produced. When the above upper limit is exceeded, the viscosity is increased, so it takes a longer time to dissolve, or a large amount of solvent must be used, which tends to increase the difficulty of processing.

Further, the weight average molecular weight (Mw) of the polyimine forming the films is preferably from 1,000 to 5,000,000 in terms of polystyrene. Further, the lower limit of the numerical range of the weight average molecular weight (Mw), Preferably, 5000 is preferred, 10,000 is preferred, and 20,000 is particularly preferred. Further, the upper limit of the numerical range of the weight average molecular weight (Mw) is preferably 5,000,000, more preferably 500,000, and particularly preferably 100,000. When the weight average molecular weight is less than the above lower limit, not only is it difficult to achieve sufficient heat resistance, but also the polymerization solvent may not be sufficiently precipitated at the time of production, and the polyimine may not be efficiently produced. When the above upper limit is exceeded, the viscosity is increased, so it takes a longer time to dissolve, or a large amount of solvent must be used, which tends to increase the difficulty of processing.

Further, the molecular weight distribution (Mw/Mn) of the polyimine is preferably from 1.1 to 5.0, more preferably from 1.5 to 3.0. When the molecular weight distribution does not reach the lower limit, the production tends to be difficult. On the other hand, when the molecular weight distribution exceeds the upper limit, a uniform film tends to be difficult to obtain. Further, the molecular weight (Mw or Mn) or the molecular weight distribution (Mw/Mn) of the polyimine can be measured by a gel permeation chromatography (GPC) measuring device of a measuring device (degasser: DG manufactured by JASCO) -2080-54, liquid supply pump: JA-20 company made of PU-2080, interface: JASCO company made LC-NetII/ADC, column: Shodex company GPC column KF-806M (×2), column oven: JASCO Corporation 860-CO, RI detector: JASCO company RI-2031, column temperature 40 ° C, chloroform solvent (flow rate 1mL / min.) measured by the polystyrene conversion method.

Further, in the polyimine, the linear expansion coefficient is preferably 0 to 100 ppm/K, and preferably 10 to 70 ppm/K. When the coefficient of linear expansion exceeds the upper limit, the linear expansion coefficient ranges from 5 to 20 ppm. When a metal or inorganic compound of /K is combined to form a composite, there is a tendency that peeling tends to occur during heat treatment. Further, when the linear expansion coefficient is less than the lower limit, the solubility may be lowered or the film properties may be lowered.

The linear expansion coefficient of the polyimine is measured by forming a polyimide film having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm, and then drying the film in vacuum (120 ° C, 1 hour). The dried film obtained by heat-treating at 200 ° C for 1 hour in a nitrogen atmosphere was used as a sample for measurement, and the measuring device was a thermomechanical analyzer (trade name "TMA8310"), which was used in a nitrogen atmosphere and in a tensile mode. (49 mN) and a temperature increase rate of 5 ° C / min, the change of the longitudinal length of the sample in the range of 50 ° C to 200 ° C was measured, and the length per 1 ° C was varied in the temperature range of 50 ° C to 200 ° C. The value obtained by the average.

Further, the polyimine in the films is preferably one which is soluble in a cast solution having a low boiling point. As long as it is a film formed of the polyimine, it can be more easily produced. In addition, the casting solvent referred to herein has a boiling point in terms of solubility, volatility, evapotranspiration, removability, film formability, productivity, industrial availability, reusability, presence or absence of existing equipment, and price. The solvent is preferably 200 ° C or less (preferably 20 to 150 ° C, more preferably 30 to 120 ° C, particularly preferably 40 to 100 ° C, most preferably 60 ° C to 100 ° C). Further, the solvent having a boiling point of 200 ° C or less is preferably a halogen solvent having a boiling point of 200 ° C or less, and dichloromethane (dichloromethane), chloroform (chloroform), carbon tetrachloride, and dichlorochloride. Ethane, trichloroethane, tetrachloroethane, tetrachloroethane, chlorobenzene, o-dichloro More preferably, benzene is preferably dichloromethane (dichloromethane) or chloroform (chloroform). Further, these casting solvents may be used alone or in combination of two or more.

Further, these polyimide films are preferably those having extremely high transparency, and preferably having a total light transmittance of 80% or more (more preferably 85% or more, particularly preferably 87% or more). Further, those polyimide films having a higher transparency are preferred, and HAZE (turbidity) is preferably 5 or less (more preferably 4 or less, particularly preferably 3 or less). Moreover, it is preferable that these polyimine films have a higher transparency, and the yellowness (YI) is preferably 10 or less (more preferably 8 or less, particularly preferably 6 or less). These total light transmittance, HAZE (haze), and yellowness (YI) can be easily achieved by appropriately selecting the type of polyimine or the like. Further, these samples for measurement of total light transmittance, HAZE (haze), and yellowness (YI) were used, and a polyimide film having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm was formed, and a measuring device was used. The value obtained by measuring the product name "turbidity meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.

The form of the polyimide film is not particularly limited as long as it is in the form of a film, and can be appropriately designed into various shapes (a disk shape, a cylindrical shape (a film processed into a cylindrical shape), etc.). Can be.

Further, the thickness of the polyimide film of the present invention is not particularly limited, and is preferably 1 to 500 μm, more preferably 10 to 200 μm. When the thickness does not reach the lower limit, the strength may be lowered and the handling may be difficult. On the other hand, when the thickness exceeds the upper limit, it may be produced. It is necessary to carry out a plurality of coatings, and there is a tendency to cause a complicated processing.

Further, when the polyimide film of the present invention is used in a display device, the retardation (Rth) in the thickness direction measured at a wavelength of 590 nm is converted to a thickness of 10 μm from the viewpoint of suppressing the decrease in contrast and improving the effect of the viewing angle. A film of -1000 to 1000 nm (more preferably -500 to 500 nm, more preferably -250 to 250 nm) is preferred. In addition, the "Rth" in the thickness direction of the polyimine film of the present invention is a polyimine film which is measured in the manner described below by using the product name "AxoScan" manufactured by AXOMETRICS Co., Ltd. using a measuring device. The value of the refractive index (589 nm) is implanted in the above-mentioned measuring device, and the retardation in the thickness direction of the polyimide film is measured using light having a wavelength of 590 nm at a temperature of 25 ° C and a humidity of 40%, and is based on The measured value of the obtained retardation in the thickness direction (measured value by automatic measurement (automatic calculation) of the measuring device) can be obtained by converting the retardation value of the film to 10 μm per thickness. Further, the size of the polyimide film of the measurement sample is not particularly limited as long as it is larger than the photometric portion (diameter: about 1 cm) of the measuring instrument platform, and generally has a length of 76 mm and a width of 52 mm. A thickness of 13 μm is preferred.

In addition, the value of "the refractive index (589 nm) of the polyimine film used" for measuring the retardation (Rth) in the thickness direction is the same as that of the polyimide which is a film to be measured which is delayed. After the unstretched film formed by the polyimide, the unstretched film is used as a measurement sample (again, the film to be measured is an unextended thin film) In the case of a film, the film can be used as a measurement sample, and the measuring device is a refractive index measuring device (trade name "NAR-1T SOLID" manufactured by ATAGO Co., Ltd.), and a light source of 589 nm is used at a temperature of 23 ° C. The measurement of the refractive index of the 589 nm light in the in-plane direction (direction perpendicular to the thickness direction) of the sample was measured. Further, since the measurement sample is not extended, the refractive index in the in-plane direction of the film is a fixed value in any of the in-plane directions, and the original of the polyimine can be measured by measuring the refractive index. In some cases, since the refractive index in the in-plane axis of the in-plane is Nx, the refractive index in the in-plane direction perpendicular to the axis of the axis is Ny, which is Nx=Ny). . In this manner, the original refractive index (589 nm) of the polyimide was measured by measuring the film which was not stretched, and the obtained measurement value was used as the retardation (Rth) for measuring the thickness direction. In addition, the size of the polyimine film of the measurement sample is not particularly limited as long as it can be used in the above-described refractive index measuring device, and may be 1 cm square (1 cm in length and width), and the thickness is The size of 13μm.

The polyimine film of the present invention has a high tensile strength and a high degree of elongation at break, and has excellent balance (higher toughness on the basis of the above). For example, a film for a flexible circuit board, a heat-resistant insulating tape, an enamel, a protective coating for a semiconductor, a liquid crystal alignment film, a transparent conductive film for organic EL, A substrate material for a display (a substrate for a display such as a TFT substrate, a transparent electrode substrate (for example, a transparent conductive film for organic EL)), or an organic EL illumination film, Flexible substrate film, flexible organic EL substrate film, flexible transparent conductive film, organic thin film transparent conductive film for solar cell, transparent sensitized film for dye-sensitized solar cell, flexible gas A barrier film, a substrate material for a touch panel (such as a film for a touch panel), an outer film for a flexible display, a back film for a flexible display, and the like. Further, the polyimine film of the present invention has a higher toughness and higher mechanical strength as described above, and is used for the above-mentioned use (in particular, a substrate material for a display (TFT substrate, transparent) When a substrate for a display such as an electrode substrate or a substrate material for a touch panel (such as a film for a touch panel) is used, the final product (for example, an organic EL device) which is produced by mechanical strength can be sufficiently improved. Yield).

The method for producing the polyimide film is not particularly limited, and when a film formed of the polyimine containing the above repeating unit is produced, the following formula (3) can be used:

[In the formula ^{(3), R 1, R} 2, R 3, n and the general formula (1) in the ^{R 1, R 2, R 3} , n has the same meaning]

The tetracarboxylic dianhydride represented by the following formula (301) to (302):

In the aromatic diamine of at least one of the diamine compounds, the content of the repeating unit represented by the above formula (1) in the obtained polyimine is 30 mol% or more based on the total repeating unit. In a method of producing a polyimide film by a known method (for example, a method for producing a polyimine disclosed in International Publication No. 2011/099518 and International Publication No. 2014/034760) .

Moreover, the method of producing the polyimine film may be, for example, a tetracarboxylic dianhydride represented by the above formula (3) in the presence of a polymerization solvent, and the above formula ( The aromatic diamine of at least one of the diamine compounds represented by 301) to (302) (the design of the polyimine which can be blended with the target contains only the two represented by the above formula (301) to (302) At least one component of the amine compound may be used, or at least one of the diamine compounds represented by the above formulas (301) to (302) may be mixed with another diamine compound. Forming a repeat containing the following formula (4): The unit is 30 mol% or more with respect to the total repeat unit (more preferably 40 mol% or more, more preferably 50 mol% or more, particularly preferably 70 mol% or more, and most preferably 90 mol% or more). After the polyamine acid, a solution of the polyamic acid containing the polyamic acid is applied onto the surface of a substrate (for example, a glass substrate or the like), and then, the polyphosphonium amide is imidized. Laminated on the substrate to form a repeating unit represented by the above formula (1), which is 30 mol% or more (more preferably 40 mol% or more, more preferably 50 mol%) with respect to the total repeat unit. % or more, particularly preferably 70 mol% or more, and most preferably 90 mol% or more of a film formed of polyimine (hereinafter, referred to as "method (A)") .

[In the formula ^{(4), R 1, R} 2, R 3, n and the general formula (1) in the ^{R 1, R 2, R 3} , n is the same meaning (which are preferred, and also through the the formula R (1) in the ^{1, R 2, R 3,} n has the same meaning) and the R & lt formula ¹⁰ (R 1) are of the same meaning ¹⁰ (which are preferred, but also with the general formula ( 1) R ¹⁰ has the same meaning)].

With respect to the tetracarboxylic dianhydride moiety represented by the above formula (3), R ¹ , R ² and R ³ in the formula (3) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and fluorine. One of the selected groups of atoms, n is an integer from 0 to 12. In the above formula (3), R ¹ , R ² , R ³ and n are the same as those of R ¹ , R ² , R ³ and n in the above formula (1), and preferably, It is preferably the same as those of R ¹ , R ² , R ³ and n in the above formula (1). The method for producing the tetracarboxylic dianhydride represented by the above formula (3) is not particularly limited, and a known method can be suitably employed. For example, the method described in International Publication No. 2011/099517 can be used. Or the method described in International Publication No. 2011/099518.

Further, the tetracarboxylic dianhydride represented by the above formula (3) contains a compound represented by the following formula (5) from the viewpoint of adjusting film properties, thermal properties, mechanical properties, optical properties, and electrical properties. (A) and at least one of the compounds (B) represented by the following formula (6), and the total amount of the above compounds (A) and (B) is preferably 90 mol% or more.

[In the formula ^{(5), R 1, R} 2, R 3, n, and the general formula (3) in the ^{R 1, R 2, R 3} , n has the same meaning]

[In the formula ^{(6), R 1, R} 2, R 3, n and the general formula (3) in the ^{R 1, R 2, R 3} , n has the same meaning]

The compound (A) represented by the above formula (5) is such that two norbornyl groups are trans-coordinated, and the two norbornyl groups are respectively internal with respect to the carbonyl group of the cycloalkanone An isomer of the tetracarboxylic dianhydride represented by the above formula (3) which is stereo-coordinated to the endo. Further, the compound (B) represented by the above formula (6) is such that the two norbornyl groups are cis-coordinated, and the two norbornyl groups are respectively separated from the carbonyl group of the cycloalkanone The isomer of the tetracarboxylic dianhydride represented by the above formula (3) which is stereo-coordinated to the endo. Further, the method for producing the tetracarboxylic dianhydride containing the above-mentioned ratios of the above-mentioned isomers is not particularly limited, and a known method can be suitably employed, for example, the international publication No. 2014/034760 can be appropriately employed. The method of recording, etc.

Further, the aromatic diamine which is reacted with the tetracarboxylic dianhydride represented by the formula (3) contains 30 mol% or more with respect to the total repeat unit in the polyimine which is obtained by mixing ( More preferably 40 mol% or more, more preferably 50 mol% or more, especially preferably 70 mol% or more, the best In the manner of 90 mol% or more of the repeating unit represented by the above formula (1), a diamine compound represented by the formula (301) (1,4-bis(4-aminobenzene) is used in an appropriate ratio. At least one of oxy)benzene) and a diamine compound (4,4'-bis(4-aminophenoxy)biphenyl) represented by the formula (302). Based on these viewpoints, the content of at least one of the diamine compounds represented by the general formulae (301) to (302) is 30 mol% or more (more preferably 40 mol% or more, more preferably 50 mol%). More than %, particularly preferably 70 mol% or more, and most preferably 90 mol% or more). Further, for the diamine compounds represented by the above formulas (301) to (302), for example, commercially available articles may be used.

Further, in the method for producing the polyimine film, when the repeating unit represented by the above formula (2) is used as another repeating unit, the reaction is carried out with the tetracarboxylic dianhydride represented by the formula (3). The aromatic diamine is preferably a mixture of at least one of the diamine compounds represented by the above formulas (301) to (302) and a mixture of other diamine compounds.

The other diamine compound is not particularly limited, and for example, a known aromatic diamine compound used in the production of polyimine can be suitably used. Among these other diamine compounds, from the viewpoint of heat resistance and transparency, the formula: H ₂ NR ^a -NH ₂ (wherein, R ^a is an aryl group having 6 to 40 carbon atoms (however, the above The diamine compound represented by the group represented by the formula (101) to (102) is preferably a diamine compound. Further, R ^{a in} the formula of the other diamine compounds has the same meaning as R ^a in the above formula (2) (which is preferably the same). Further, these other diamine compounds are, for example, 4,4'-diaminobenzimidamide, 4,4"-diamino-p-biphenyl, from the viewpoint of heat resistance and transparency. 4-amino benzoic acid 4-aminobenzene is more preferred, and 4,4'-diaminobenzimidamide is particularly preferred. These other diamine compounds may be used alone or in combination of two or more. Any other aromatic diamine may be suitably used as a commercially available article.

Further, the polymerization solvent used in the above method (A) is capable of dissolving the tetracarboxylic dianhydride represented by the above formula (3) and the aromatic diamine (containing the above formula (301) to (302). At least one of the diamine compounds (a mixture of at least one of the diamine compounds represented by the above formulas (301) to (302) and another diamine compound) may be used. Organic solvents are preferred.

The organic solvents, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ-butane Aprotic polar solvent such as ester, propylene carbonate, tetramethyl urea, 1,3-dimethyl-2-tetrahydroimidazolidone, hexamethylphosphonium triamide, pyridine, etc.; m-cresol, dimethyl a phenolic solvent such as a phenol, a phenol or a halogenated phenol; an ether solvent such as tetrahydrofuran, dioxane, cellosolve, glycol diether or diethylene glycol dimethyl ether; benzene; An aromatic solvent such as toluene or xylene; a ketone solvent such as cyclopentanone or cyclohexanone; a nitrile solvent such as acetonitrile or benzonitrile; and the like. These polymerization solvents (organic solvents) may be used alone or in combination of two or more.

Further, in the above method (A), the ratio of the tetracarboxylic dianhydride represented by the above formula (3) to the aromatic diamine is The amount of the amine group having the aromatic diamine is preferably from 0.2 to 2 equivalents, and from 0.8 to 1.2 equivalents, based on the use of the tetracarboxylic dianhydride represented by the above formula (3). good. When the ratio of use is less than the lower limit, the polymerization reaction may not proceed efficiently, and the polyglycine having a high molecular weight may not be obtained. On the other hand, when the ratio is more than the above upper limit, There is a tendency to obtain a high molecular weight polylysine.

In the method (A), the amount of the polymerization solvent (organic solvent) used is the total amount of the tetracarboxylic dianhydride and the aromatic diamine represented by the above formula (3) with respect to the total amount of the reaction solution. It is preferably in an amount of 0.1 to 50% by mass (more preferably 10 to 30% by mass). When the amount of the organic solvent used is less than the lower limit, the polyamine may not be efficiently produced. On the other hand, when the amount exceeds the upper limit, the viscosity tends to be less likely to be agitated due to the high viscosity.

In the method (A), the method of reacting the tetracarboxylic dianhydride represented by the above formula (3) with the aromatic diamine is not particularly limited, and a tetracarboxylic acid can be suitably used. A known method which may be used for the reaction of the dianhydride with the aromatic diamine, for example, may be carried out by dissolving the aromatic diamine in a solvent under an inert atmosphere of nitrogen, helium or argon at atmospheric pressure. Further, the tetracarboxylic dianhydride represented by the above formula (3) is further added, followed by a further reaction for 10 to 48 hours. Further, in carrying out these reactions, the temperature conditions are preferably about -20 to 100 °C. When the reaction time or the reaction temperature does not reach the lower limit, there is a tendency that the reaction does not easily proceed sufficiently. On the other hand, when the reaction temperature exceeds the upper limit, This increases the probability of mixing of substances (oxygen, etc.) which cause deterioration of the polymer, and tends to lower the molecular weight.

Further, in the above method (A), the polyamic acid formed as an intermediate, wherein R ¹ , R ² , R ³ and n in the above formula (4) are in the above formula (1) ^{R 1, R 2, R 3} , n has the same meaning, which are preferred, but also with the general formula R (1) in the ^{1, R 2, R 3,} n has the same meaning. And, the general formula (4) and R ¹⁰ in the general formula (1) R ¹⁰ in the meaning of the same, which are preferred, it also has the same meaning. Thus, R ¹⁰ in the above formula (4) may be one selected from the group represented by the above formulas (101) to (102).

Further, in the above method (A), the polyamic acid formed as an intermediate has an intrinsic viscosity [η] of preferably 0.05 to 3.0 dL/g, more preferably 0.1 to 2.0 dL/g. When the intrinsic viscosity [η] is less than 0.05 dL/g, when the film-form polyimide is produced, the obtained film tends to be embrittled. On the other hand, when it exceeds 3.0 dL/g, the viscosity is high. If it is too high, workability is deteriorated. For example, when a film is produced, it is difficult to obtain a uniform film.

Moreover, the intrinsic viscosity [η] of these polylysines can be measured in the following manner. That is, first, using the N,N-dimethylacetamide as a solvent, the polylysine is dissolved in the N,N-dimethylacetamide to a concentration of 0.5 g/dL. The sample (solution) was measured. Subsequently, using the above-mentioned measurement sample, the viscosity of the above-mentioned measurement sample was measured by a dynamic viscosity meter under the temperature condition of 30 ° C, and the obtained value was made into the intrinsic viscosity [η]. Moreover, the dynamic viscometers are used for automatic viscosity measurement by the clutch company. Fixing device (product name "VMC-252").

Further, the substrate to be used in the above method (A) is not particularly limited, and it may be blended with a shape of a film formed of a target polyimine, etc., and may be suitably formed of a known material which may be used to form a film. a substrate (for example, a glass plate or a metal plate).

Further, in the above method (A), the method of applying the polyamic acid solution to the substrate is not particularly limited, and for example, a spin coating method, a spray coating method, or a dip coating method can be suitably employed. A well-known method such as a dropping method, a gravure printing method, a screen printing method, a letterpress printing method, a mold coating method, a curtain coating method, and an inkjet method.

In the above method (A), the method for imidating the polyphosphonium hydrazide is not particularly limited as long as the method for imidating the polyphosphonium amide is not particularly limited. A well-known method (method of ruthenium imidation described in International Publication No. 2011/099518, International Publication No. 2014/034760, etc.) can be suitably used. A method for imidating the polyphosphonium hydrazide, for example, by using a polylysine containing a repeating unit represented by the above formula (4) at 60 to 400 ° C (more preferably 60 to 370 ° C, More preferably, the temperature is 150 to 360 ° C), and a method of heat-treating the oxime iodide or a so-called hydrazine imidization method is preferred.

Moreover, in the method (A), it is also possible to use the polyamido acid containing the repeating single crystal represented by the above formula (4) before the imidization of the polyphosphonium amide. In the polymerization solvent (organic solvent), the tetracarboxylic dianhydride represented by the above formula (3) and the aforementioned aromatic The reaction of the obtained diamine is carried out, and the obtained reaction liquid (reaction liquid containing poly-proline containing the repeating unit represented by the above formula (4)) is applied to the substrate, and then dried. The treatment is carried out to remove the solvent, followed by a method of imidating the hydrazine by the aforementioned heat treatment. The temperature conditions in the drying treatment methods are preferably from 0 to 180 ° C, more preferably from 60 to 150 ° C. Further, the polyphosphonic acid containing the repeating unit represented by the above formula (4) may be isolated from the reaction liquid. In this case, the method for separating the polyglycolic acid is not particularly limited, and A well-known method of separating the polyamic acid can be used as appropriate, and for example, a method of forming a reprecipitate by means of forming a reprecipitate can be used.

The polyimine film of the present invention can be obtained by laminating on the substrate via the methods (A). Further, when the polyimide film obtained in this manner is peeled off from the substrate and recovered, the peeling method is not particularly limited, and a known method can be suitably employed. For example, the substrate may be laminated. A method in which a laminate obtained by using a polyimide film is immersed in a high-temperature water (for example, water having a temperature of 80 ° C or higher), and a polyimide film is peeled off from a substrate.

[Organic Electroluminescent Element]

The organic electroluminescence device of the present invention is a film comprising the above-described polyimine film of the present invention.

For example, when the polyimide film of the present invention is provided, the other constituent contents are not particularly limited, and a known constitution can be appropriately used. Also, these organic The electroluminescent device is not particularly limited. For example, in view of improving the yield at the time of production, it is preferred that the polyimine film of the present invention described above is used as a substrate for transparent electrode lamination.

In the following, an embodiment of an organic EL device used as the organic electroluminescent device (organic EL device) of the present invention will be briefly described with reference to the drawings. In the following description and the drawings, the same or equivalent elements will be denoted by the same reference numerals, and the repeated description will be omitted.

Fig. 1 is a schematic longitudinal cross-sectional view showing a preferred embodiment of an organic electroluminescence device (organic EL device) of the present invention. The organic EL element 1 of the embodiment shown in Fig. 1 is provided with a polyimide film 11, a gas barrier layer 12, a transparent electrode layer 13, an organic layer 14, and a metal electrode layer 15.

The polyimide film 11 of the organic EL device is formed of the above-described polyimide film of the present invention. In the present embodiment, the polyimide film 11 is used as a substrate of an organic EL device (a substrate for transparent electrode layer bonding).

Further, the gas barrier layer 12 is a member having higher resistance to gas (including water vapor), and is suitably used as a layer which can suppress gas from penetrating into the inside of the element. The gas barrier layer 12 is not particularly limited. For example, it is suitable as a layer formed of an inorganic substance such as SiN, SiO ₂ , SiC, SiO _x N _y , TiO ₂ or Al ₂ O ₃ or an ultrathin plate glass. Wait. These gas barrier layers 12 can be appropriately disposed (formed) on the polyimide film 11 by laminating a well-known gas barrier layer.

Further, the thickness of the gas barrier layer 12 is not particularly limited, and is preferably in the range of 0.01 to 5000 μm, preferably in the range of 0.1 to 100 μm. When the thickness is less than the lower limit, there is a tendency that sufficient gas barrier properties are not obtained. On the other hand, when the thickness exceeds the upper limit, the thickness is increased and the flexibility or flexibility is obtained. The tendency to disappear.

The transparent electrode layer 13 is a layer that is utilized as a transparent electrode of an organic EL element. The material of the transparent electrode layer 13 is not particularly limited as long as it can be used as a transparent electrode of the organic EL element, and for example, indium oxide, zinc oxide, tin oxide, and a composite thereof can be used. Indium, tin, oxide (ITO), gold, platinum, silver, copper. Among these, ITO is preferable from the viewpoint of transparency and conductivity.

Further, the thickness of the transparent electrode layer 13 is preferably in the range of 20 to 500 nm. When the thickness is less than the lower limit, the conductivity tends to be insufficient. On the other hand, when the thickness exceeds the upper limit, the transparency is not good, and the EL light that emits light tends to be insufficiently directed to the outside.

Further, a so-called thin film transistor (TFT) layer can be formed between the gas barrier layer 12 and the transparent electrode layer 13. When the TFT layer is provided in this manner, a device (TFT element) having a transparent electrode to which a TFT is connected can also be formed. The material of the TFT layer (oxide semiconductor, amorphous germanium, polyfluorene, organic transistor, etc.) or the composition is not particularly limited, and it can be appropriately designed based on the constitution of a known TFT. Further, when a TFT layer is provided on the laminate of the polyimide film 11 and the gas barrier layer 12, the laminates may be used as a TFT substrate. Also, the TFT layers The production method is not particularly limited, and a known method can be suitably employed. For example, a production method such as a low temperature multi-twist method, a high temperature multi-twist method, an amorphous germanium method, or an oxide semiconductor method can be used.

The organic layer 14 is not particularly limited as long as it is a component for forming an organic EL device, and a component used in an organic layer of a known organic EL device can be suitably used. Further, the constitution of the organic layer 14 is not particularly limited, and a known constitution can be employed. For example, a laminate formed of a hole transport layer, a light-emitting layer, and an electron transport layer can also be used as an organic layer. .

As the material of the hole transport layer, a well-known material which can form a hole transport layer can be suitably used, for example, naphthyldiamine (α-NPD), triphenylamine, triphenyldiamine derivative ( Derivatives such as TPD), benzidine, pyrazoline, styrylamine, hydrazone, triphenylmethane, carbazole, and the like.

Further, the light-emitting layer is a layer in which electrons injected from an electrode layer or the like are bonded to a hole to generate light, and the material of the light-emitting layer is not particularly limited, and a light-emitting layer of an organic EL element can be suitably used. Known materials, for example, 4,4'-N, N'-dicarbazole-biphenyl (CBP), doped with pyridylto ruthenium (III) complex (Ir(ppy) ₃ The resulting material, or 8-hydroxyquinoline aluminum (Alq ₃ , green, low molecular), bis-(8-hydroxy)quinaldine aluminum phenoxide (Alq) ' ₂ OPh, blue, low molecular weight), 5,10,15,20-tetraphenyl-21H, 23H-porphine (5,10,15,20-tetraphenyl-21H, 23H- porphine) (TPP, red, Low molecular weight, poly(9,9-dioctylfluorene-2,7-diyl) (PFO, blue, macromolecular), poly[2 -Methoxy-5-(2'-ethylhexyloxy)-1,4-(1-cyanoethylene)benzene (poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4 - (1-cyanovinylene) phenylene] (MEH-CN-PPV, red, polymer), a material formed of a fluorescent organic solid such as ruthenium, etc., a known material which generates light by application of a voltage

Further, the material of the electron transport layer is not particularly limited, and a known material used for forming the electron transport layer can be suitably used. For example, an aluminum quinolol complex (Alq), a phenanthroline derivative, or the like can be used. An oxadiazole derivative, a triazole derivative, a quinoxaline derivative, a siloles derivative, and the like.

Further, when the organic layer 14 is a laminate formed of a hole transport layer, a light-emitting layer, and an electron transport layer, the thickness of each layer of the hole transport layer, the light-emitting layer, and the electron transport layer is not particularly limited, and The range of 1 to 50 nm (hole transport layer), the range of 5 to 200 nm (light emitting layer), and the range of 5 to 200 nm (electron transport layer) are preferred. Further, the entire thickness of the organic layer 14 is preferably in the range of 20 to 600 nm.

The metal electrode layer 15 is an electrode formed of a metal. The material of the metal electrodes is not particularly limited as long as it is a substance having a small power factor, and is not particularly limited, for example, aluminum, MgAg, MgIn, AlLi, or the like. Further, the thickness of the metal electrode layer 15 is preferably in the range of 50 to 500 nm. When the thickness does not reach the aforementioned lower limit, the conductivity tends to decrease, and the other On the other hand, when the above upper limit is exceeded, peeling or cracking tends to occur.

Further, the method for producing the organic EL device is not particularly limited. For example, after the polyimine film of the present invention described above is prepared, the foregoing layer may be laminated on the surface of the polyimide film. A method of manufacturing a gas barrier layer, the transparent electrode, the organic layer, and the metal electrode.

The method of laminating the gas barrier layer 12 on the surface of the polyimide film 11 is not particularly limited, and a known method such as a vapor deposition method or a sputtering method can be suitably used, in which a fine film is formed. The point of view is to use sputtering. Further, in the method of laminating the transparent electrode layer 13 on the surface of the gas barrier layer 12, a known method such as a vapor deposition method or a sputtering method can be suitably used, and a fine film is formed from the viewpoint of sputtering. It is better.

Further, the method of laminating the organic layer 14 on the surface of the transparent electrode layer 13 is not particularly limited. For example, the organic layer is formed of a hole transport layer, a light-emitting layer, and an electron transport layer as described above. In the case of a laminate, the layers may be laminated on the transparent electrode layer 13 in order. Further, the method of laminating each of the organic layers 14 is not particularly limited, and it can be suitably carried out by a known method, and for example, a vapor deposition method, a sputtering method, a coating method, or the like can be employed. Among these methods, from the viewpoint of sufficiently preventing decomposition, deterioration, and denaturation of the organic layer, it is preferred to use a vapor deposition method.

Further, the method of laminating the metal electrode layer 15 on the organic layer 14 is not particularly limited, and it can be suitably carried out by a known method. For example, a vapor deposition method, a sputtering method, or the like can be employed. Among these methods, in view of preventing decomposition, deterioration, and denaturation of the previously formed organic layer 14, it is preferable to use a vapor deposition method.

Further, when the organic EL device is manufactured in this manner, the polyimine film 11 can be used as a substrate supporting the so-called element portion to form an organic EL device, so that a high yield due to its mechanical strength can be formed. It also has a high degree of flexibility.

In the above, in order to explain the preferred embodiment of the organic EL device of the present invention, the organic EL device of the present invention is not limited to the above embodiment. For example, in the above embodiment, the organic layer 14 is formed of a laminate of a hole transport layer, a light-emitting layer, and an electron transport layer. However, the form of the organic layer is not particularly limited, and a known organic may be appropriately employed. The composition of the layer, for example, an organic layer formed by a laminate of a hole injection layer and a light-emitting layer; an organic layer formed by a laminate of the light-emitting layer and the electron injection layer; and a hole injection layer and a light-emitting layer and electrons An organic layer formed by laminating the injection layer; or an organic layer formed by a buffer layer and a laminate of the hole transport layer and the electron transport layer. Further, the material of each of the other forms of the organic layers is not particularly limited, and a known material can be suitably used. For example, a material of the electron injecting layer may be an anthracene derivative or the like, a material of the hole injecting layer, a triphenylamine derivative or the like may be used, and a material of the anode buffer layer may be copper indigo or PEDOT. Further, even if the layer is not disposed in the above-described embodiment, any layer that can be used by the organic EL element can be appropriately disposed. For example, it is easy to perform charge injection or hole injection into the organic layer 14. On the transparent electrode layer 13 or on the organic layer 14, a metal fluoride such as lithium fluoride (LiF) or Li ₂ O ₃ , a highly active alkaline earth metal such as Ca, Ba or Cs, or an organic insulating material is provided. Floor.

[Transparent Conductive Laminate]

The transparent conductive laminate of the present invention is a film comprising the above-mentioned polyimide film of the present invention and a conductive material laminated on the polyimide film.

In this manner, the transparent electroconductive laminate of the present invention is obtained by laminating a film formed of the above-mentioned conductive material on the polyimine film of the present invention. In the transparent conductive laminate, the total light transmittance is preferably 78% or more (more preferably 80% or more, and still more preferably 82% or more) from the viewpoint of transparency. These total light transmittances can be easily achieved by appropriately selecting the type of the polyimide film of the present invention described above, the type of the conductive material, and the like. In addition, the total light transmittance can be measured by a measuring device manufactured by Nippon Denshoku Industries Co., Ltd. under the trade name "turbidity meter NDH-5000".

In addition, the conductive material is not particularly limited as long as it is a conductive material, and any known conductive material used for a solar cell, an organic EL device, or a transparent electrode of a liquid crystal display device is used. Suitable metals such as gold, silver, chromium, copper, tungsten, etc.; metal oxides such as tin, indium, zinc, cadmium, titanium, etc., doped with other elements (for example, tin, antimony, cadmium, a composite obtained from molybdenum, tungsten, fluorine, zinc, antimony, aluminum, etc. (for example, indium tin oxide (ITO (In ₂ O ₃ :Sn)), fluorine-doped tin oxide (FTO (SnO ₂ :F)), Aluminum-doped zinc oxide (AZO (ZnO: Al)), indium-doped zinc oxide (IZO (ZnO: I)), antimony-doped zinc oxide (GZO (ZnO: Ge)), etc.; Further, among these conductive materials, transparency and conductivity can be sufficiently exhibited at a higher level and in a balanced manner, and ITO (excellently, ITO containing 3 to 15% by mass of tin) is used. good.

The film thickness of the film (conductive film) formed of the conductive materials is appropriately changed depending on the application, and is not particularly limited, and is preferably 1 to 2000 nm, and 10 nm. 1000 nm is preferred, preferably 20 to 500 nm, and particularly preferably 20 to 200 nm. When the thickness of the conductive film is less than the lower limit, the surface resistance value cannot be lowered to an extremely low point, and when used in a solar cell, there is a tendency that the photoelectric conversion efficiency is backward, and on the other hand, the upper limit is exceeded. At the time, the transmittance is lowered and the film formation time is too long, which tends to lower the production efficiency.

The method of laminating the film formed of the conductive materials on the polyimine film of the present invention is not particularly limited, and may be suitably carried out by a known method, for example, for the above-mentioned polymerization. On the quinone imine film, a film of the conductive material is formed by a vapor deposition method such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method, and the film is laminated on the foregoing. A method on a polyimide film. Further, in this manner, when the film is laminated on the polyimide film, a gas barrier film is formed on the polyimide film in advance, and the gas is blocked by the gas on the polyimide film. The film may be laminated to the aforementioned film. Moreover, the gas barrier films are not particularly limited, and may be appropriately A known film used for a solar cell, an organic EL device, a transparent electrode of a liquid crystal display device, or the like can be used, and the formation method can be suitably carried out by a known method.

In the transparent conductive laminate of the present invention, since the polyimide film is a film having higher toughness, it is, for example, a transparent electrode for a solar cell, a display device (organic EL display device, liquid crystal display device, etc.). Transparent electrodes and the like are particularly useful, which can substantially improve the yield of such final articles.

[Touch panel, solar cell, display device]

The touch panel, the solar cell, and the display device of the present invention each have the above-described transparent conductive laminate of the present invention.

The "display device" as used herein is not particularly limited as long as it is a transparent conductive laminate, and examples thereof include a liquid crystal display device and an organic EL display device. In addition, the touch panel, the solar cell, and the display device are not particularly limited as long as they have the above-described transparent conductive laminate of the present invention, and may be appropriately designed in accordance with the design purpose. Constitute content. The configuration includes, for example, a touch panel including another transparent electrode disposed so as to sandwich the transparent electrode and the gap, and the solar cell includes a transparent electrode, a semiconductor layer, and a conductive layer for the counter electrode. The organic EL display device includes a transparent electrode, an organic layer, and a conductive layer for a counter electrode, and includes a transparent electrode, a liquid crystal layer, and a conductive layer for a counter electrode as a liquid crystal display device. Also, the organic layer or the liquid crystal layer or the semiconductor The material of each layer of the layer or the like is not particularly limited, and a known material can be suitably used. Further, in the touch panel, the solar cell, and the display device of the present invention, it is preferable to use the transparent conductive laminate of the present invention as the transparent electrode user. In this manner, when the transparent conductive laminate of the present invention is used as the electrode, the temperature is often used in the manufacturing process of a touch panel, a solar cell, a display device (liquid crystal display device, or an organic EL display device). Under the circumstance, the transparent electrode layer (film formed of a conductive material) can be sufficiently suppressed from being scratched, and the touch panel, the solar cell, and the display device having extremely high quality can be manufactured in an excellent yield.

[Examples]

Hereinafter, the present invention will be more specifically described based on the examples and comparative examples, but the present invention is not limited by the following examples.

First, the chemical formula of the aromatic diamine used in each of the examples and the comparative examples and the abbreviation of the compound are as follows.

Next, methods for evaluating characteristics such as the polyimide film obtained in each of the examples and the comparative examples will be described.

<Determination of molecular structure>

The molecular structure of the compound obtained in each of the examples and the comparative examples was determined by IR measurement using an IR measuring machine (manufactured by JASCO Corporation, trade name: FT/IR-4100).

<Measurement of intrinsic viscosity [η]

In each of the examples and the comparative examples, the value of the intrinsic viscosity [η] of the obtained polyamic acid (unit: dL/g) of the obtained intermediate was measured by using the automatic viscosity of the company as described above. The apparatus (trade name "VMC-252") was measured at a temperature of 30 ° C for a measurement sample having a concentration of 0.5 g/dL using N,N-dimethylacetamide as a solvent.

<Measurement of tensile strength and elongation at break>

In each of the examples and the comparative examples, the tensile strength (unit: MPa) and the elongation at break (unit: %) of the polyimide film (thickness: 13 μm) were measured as follows. In other words, first, the SD type lever type sample cutter (Dunber Co., Ltd.'s cutter (type SDL-200)) is equipped with the product name "Super Dumbbell Cutter" manufactured by Dunbar Co., Ltd. Type: SDMK-1000-D, JIS K7139 (released in 2009) A22 is the standard), and the polyimine film is cut into a total length: 75 mm, the distance between the marking portions: 57 mm, and the length of the parallel portion: 30 mm The radius of the shoulder: 30 mm, the width of the end portion: 10 mm, the width of the central parallel portion: 5 mm, and the thickness: 13 μm. The test piece of the dumbbell shape of the sample was prepared (except for the thickness of 13 μm, all other according to JIS) K7139 Form A22 (scaled test piece) made by the specification). Next, using a Tensilon-type universal testing machine (for example, the model "UCT-10T" manufactured by A & D Co., Ltd.), the above-mentioned measurement sample is configured such that the width between the grips is 57 mm, and the width of the grip portion is 10 mm. After the method of the full width of the end portion, the tensile test is performed on the above-mentioned measurement sample according to the full weight of the load: 0.05 kN, test speed: 300 mm/min, and tensile strength and elongation at break are determined. value. Moreover, these tests are based on the test conducted in accordance with JIS K7162 (issued in 1994). Further, the value (%) of the elongation at break is a sample in which the distance between the marking portions of the sample before the start of the tensile test (= the width between the grippers: 57 mm) is L ₀ and the sample is broken by the tensile test. The distance between the marking portions (the width between the grips at break: 57 mm + α) is L, and is calculated by the following formula: [Elongation at break (%)] = {(LL ₀ ) / L ₀ } ×100.

<Measurement of glass transition temperature (Tg)>

The value of the glass transition temperature (Tg) of the compound (the compound forming the film) of each of the examples and the comparative examples (unit: ° C) was used for the polyimide film obtained by using each of the examples and the comparative examples. The thermomechanical analyzer (product name "TMA8311" manufactured by Rigaku Corporation) of the measuring device was measured in the same manner as the method for measuring the softening temperature described below (same conditions), and the softening temperature was simultaneously measured.

<Measurement of softening temperature>

The value (unit: ° C) of the softening temperature (softening point) of the compound (the compound forming the film) obtained in each of the examples and the comparative examples is a polyimide film obtained by using each of the examples and the comparative examples, and used. The thermomechanical analyzer (trade name "TMA8311", manufactured by Rigaku Corporation) is used as a measuring device in a nitrogen atmosphere at a temperature rise rate of 5 ° C / min and a temperature range of 30 ° C to 550 ° C (scanning temperature). The probe (diameter of the tip end: 0.5 mm) was measured by inserting the film at a pressure of 500 mN (that is, measured by a so-called Penetration method). In the measurement, the softening temperature was calculated based on the measurement data based on the method described in JIS K7196 (1991).

<Measurement of Temperature (Td5%) at 5% Weight Reduction>

The value (unit: ° C) of the temperature (Td 5%) at which the compound obtained in each of the examples and the like was reduced by 5% by weight, and the polyimine film obtained by using each of the examples and the comparative examples was a heat weight. Analytical device ("TG/DTA220" manufactured by SII‧Near Technology Co., Ltd.), set the scanning temperature to 30 °C to 550 °C, and heat under nitrogen atmosphere and nitrogen flow at 10 °C/min. The temperature at which the weight of the sample used was reduced by 5% was determined.

<Measurement of total light transmittance, HAZE (yellowness) and yellowness (YI)>

The total light transmittance values (unit: %), turbidity (HAZE), and yellowness (YI) are the aggregations obtained by using the respective examples and comparative examples. The imide film was obtained by using a product name "turbidity meter NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd. as a measuring device, and measuring according to JIS K7361-1 (issued in 1997).

<Measurement of refractive index>

The refractive index (refractive index of 589 nm light) of the polyimide film obtained in each of the examples and the comparative examples was obtained by the same method as that used in each of the examples and the comparative examples. A polyimide film (unstretched film) was cut into a 1 cm square (1 cm vertical and horizontal 1 cm) film having a thickness of 13 μm as a measurement sample, and the measurement device was a refractive index measuring device (trade name "NAR-1T SOLID" manufactured by ATAGO Co., Ltd. ”, using a light source of 589 nm, the refractive index (the original refractive index of the polyimine) of the light in the in-plane direction (the direction perpendicular to the thickness direction) with respect to the light of 589 nm is measured at a temperature of 23 ° C. Ways to get it.

<retardation (Rth) in the thickness direction>

The value of the retardation (Rth) in the thickness direction (unit: nm) was used as a measurement sample by using the polyimide film (vertical: 76 mm, width: 52 mm, thickness: 13 μm) obtained in each of the examples and the comparative examples. The measurement device is a product name "AxoScan" manufactured by AXOMETRICS Co., Ltd., and the refractive index of each polyimide film (the refractive index of the film obtained by the above refractive index measurement to the light of 589 nm) is input, and then the temperature is measured. : 25 ° C, humidity: 40%, using a wavelength of 590 nm light After measuring the retardation in the thickness direction, the obtained retardation value in the thickness direction (measured value obtained by automatic measurement of the measuring apparatus) was used to obtain a retardation value when the film thickness was 10 μm.

(Example 1)

<Preparation step of tetracarboxylic dianhydride>

The following general formula (7) is prepared based on the methods described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518:

Tetracarboxylic dianhydride (norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride ).

<Production Step of Polylysine>

First, a 30 ml three-necked flask was heated using a heat gun to make it sufficiently dry. Subsequently, the ambient gas in the three-necked flask which was sufficiently dried was replaced with nitrogen gas to form a nitrogen atmosphere in the three-necked flask. Next, in the above three-necked flask, 1,4-double as an aromatic diamine was added. (4-Aminophenoxy)benzene 0.2631 g (0.90 mmol: 4,4-BAB manufactured by Wakayama Seiki Co., Ltd.), and then 2.7 g of N,N-dimethylacetamide was added thereto, followed by stirring. A solution in which an aromatic diamine (4,4-BAB) is dissolved in the aforementioned N,N-dimethylacetamide is prepared.

Then, 0.3459 g (0.90 mmol) of the compound represented by the above formula (7) was added to a three-necked flask containing the above-mentioned solution, and the mixture was stirred under a nitrogen atmosphere at room temperature (25 ° C) for 12 hours. The reaction solution was prepared. Polylysine is formed in the reaction solution in this manner.

Further, using a portion of the reaction solution (N,N-dimethylacetamide solution of polylysine: polylysine solution), N, N having a polyglycine concentration of 0.5 g/dL was produced. The intrinsic viscosity [η] of the polyamine acid of the reaction intermediate was measured in the above manner, and the intrinsic viscosity [η] of the polyglycolic acid was found to be 0.98 dL/g.

<Manufacturing procedure of film formed by polyimine]

Prepare a large-sized glass slide (trade name "S9213" manufactured by Matsunaga Glass Industry Co., Ltd., vertical: 76 mm, width 52 mm, thickness: 1.3 mm), and prepare the reaction liquid (polylysine) obtained in the above manner. The solution was spin-coated on the surface of the glass substrate so that the thickness of the coating film after heat curing was 13 μm, and a coating film was formed on the glass substrate. Subsequently, the glass substrate on which the coating film was formed was placed on a hot plate at 60 ° C, left to stand for 2 hours, and the solvent was evaporated from the coating film (solvent removal treatment).

After performing the solvent removal treatment, the glass substrate on which the coating film was formed was placed in an oxygen-free oven at a flow rate of 3 L/min in a non-oxidizing oven under a nitrogen atmosphere at a temperature of 25 ° C. After standing for 0.5 hour, it was heated at 135 ° C for 0.5 hour, and then heated at 340 ° C (last heating temperature) for 1 hour to harden the coating film to obtain a coating on the aforementioned glass substrate. A polyimide film formed of an amine (polyimine film) is coated with a polyimide.

Subsequently, the polyimide-coated glass obtained in this manner is immersed in hot water at 90 ° C, and the polyimide film is peeled off from the glass substrate to obtain a polyimide film (length 76 mm, width 52 mm, Film having a thickness of 13 μm).

In addition, the IR spectrum of the compound of the polyimine film obtained in this manner was determined by using an IR measuring machine (manufactured by JASCO Corporation, trade name: FT/IR-4100). . The IR pattern obtained by performing these measurements is shown in Fig. 2. As is clear from the results shown in Fig. 2, in the compound constituting the film formed in Example 1, the C=O stretching vibration of the quinone imine carbonyl group was 1701 cm ^-1 . Based on the molecular structure determined by these results and the like, it was confirmed that the obtained film was formed of polyimine.

Further, the obtained polyimine is known from the type of the monomer to be used, and is a repeating unit represented by the above formula (1) (any one of R ¹ , R ² and R ^{3 in} the formula) All of them are hydrogen atoms, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (101), and the polyarylene imine is 100 mol% based on the total repeat unit. Further, the results of evaluation of the properties of the obtained polyimide film (the Tg or the softening temperature obtained by the evaluation method of the above characteristics) are shown in Table 1.

(Example 2)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine, using 4,4'-bis(4-aminophenoxy)biphenyl 0.3316g (0.90mmol: manufactured by Nippon Pure Pharmaceutical Co., Ltd.: APBP). In the manufacturing process of the film formed by polyimine, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 320 ° C. A polyimide film was obtained in the same manner as in Example 1. Further, when it was determined that the molecular structure of the compound which formed the film in the same manner as in Example 1 was confirmed, it was confirmed to be a polyimine. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (102), and the content of the polyimine is 100 mol% based on the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg obtained by the evaluation method of the above characteristics, the softening temperature, etc.) are shown in Table 1.

(Comparative Example 1)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 4,4'-diaminobenzimidil 0.2045 g. A polyimine film was obtained in the same manner as in Example 1 except that (0.90 mmol: manufactured by Nippon Pure Pharmaceutical Co., Ltd.: DABAN). Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 2)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 4,4'-diamino-2,2'-bis (three) Cyclomethyl)biphenyl 0.2882g (0.90mmol: manufactured by Tokyo Chemical Industry Co., Ltd.: 6FDA) was replaced, and in the production step of polyproline, the reaction solution was prepared under a nitrogen atmosphere at room temperature (25 ° C). Under the conditions of 12 hours of stirring, the temperature was changed, and the mixture was stirred under a nitrogen atmosphere at 60 ° C for 12 hours. Further, in the manufacturing process of the film formed by the polyimide, the final heating in the oxidation-free oven was not performed. The polyimine film was obtained in the same manner as in Example 1 except that the temperature was changed from 340 ° C to 360 ° C. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 3)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 1,3-bis(4-aminophenoxy)benzene 0.2631 g (0.90 mmol: manufactured by Wakayama Seiki Co., Ltd.: TPE-R), in addition, in the manufacturing process of the film formed by polyimine, the above-mentioned final heating temperature in the non-oxidizing oven was changed from 340 ° C to A polyimine film was obtained in the same manner as in Example 1 except for 300 ° C. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 4)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 2,2-bis[4-(4-aminophenoxy). Phenyl]propane 0.3695 g (0.90 mmol: manufactured by Wakayama Seiki Co., Ltd.: BAPP) was replaced, and in the manufacturing process of the film formed by polyimine, the aforementioned final heating temperature in the non-oxidizing oven was 340 ° C. A polyimine film was obtained in the same manner as in Example 1 except that the temperature was changed to 300 °C. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 5)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene except aromatic diamine is bis[4-(4-aminophenoxy)phenyl]fluorene. 0.3892g (0.90mmol: made by Wakayama Seiki Co., Ltd.: BAPS), in addition, in the manufacturing process of the film formed by polyimine, the above-mentioned final heating temperature in the non-oxidizing oven is changed from 340 ° C to 300 ° C A polyimide film was obtained in the same manner as in Example 1 except that the polyimide film was obtained. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 6)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene except aromatic diamine is 0.1802 g (0.90 mmol: 4,4'-diaminodiphenyl ether). Tokyo Chemical Co., Ltd.: 4,4'-DDE), in addition, in the manufacturing process of the film formed by polyimine, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 300 ° C, and the like. A polyimide film was obtained in the same manner as in Example 1. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 7)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is bis[4-(3-aminophenoxy)phenyl]fluorene In place of 0.3892 g (0.90 mmol: manufactured by Wakayama Seiki Co., Ltd.: BAPS-M), in the manufacturing process of the film formed by polyimine, the above-mentioned final heating temperature in the non-oxidizing oven was changed from 340 ° C to A polyimine film was obtained in the same manner as in Example 1 except for 300 ° C. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 8)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 2,2-bis[4-(4-aminophenoxy). Phenyl]hexafluoropropane 0.4666g (0.90mmol: Tokyo Chemical Industry Co., Ltd. A polyimide film was prepared in the same manner as in Example 1 except for the substitution of Bis-AF. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 9)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine is 1,3-bis(3-aminophenoxy)benzene 0.2631 g (0.90 mmol: manufactured by Mitsui Precision Chemical Co., Ltd.: 3,3-BAB), in addition, in the manufacturing process of the film formed by polyimine, the aforementioned final heating temperature in the non-oxidizing oven was changed from 340 ° C to 300 A polyimine film was obtained in the same manner as in Example 1 except for °C. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Comparative Example 10)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene in addition to the aromatic diamine, 0.1911 g (0.90 mmol) using m-toluidine: Wakayama Jinghua Industrial Co., Ltd. In the manufacturing step of the film formed by the polyimide, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the others are the same as in the first embodiment. In the method, a polyimide film is obtained. Further, the evaluation results of the properties of the poly-proline and polyimine films are shown in Table 1.

(Example 3)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene except aromatic diamine is 1,4-bis(4-aminophenoxy)benzene 0.2105g Mixture of (0.72 mol: 4,4-BAB) with 4,4'-diaminobenzimidil 0.0409 g (0.18 mol: DABAN) (4,4-BAB and DABAN molar ratio ([4,4 -BAB]: [DABAN]) is replaced by 80:20), and in the manufacturing step of the film formed by the polyimide, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the others are A polyimide film was obtained in the same manner as in Example 1. Further, when it was determined that the molecular structure of the compound which formed the film in the same manner as in Example 1 was confirmed, it was confirmed to be a polyimine. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (101). The content of the polyimine is 80 mol% based on the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg obtained by the evaluation method of the above characteristics, the softening temperature, etc.) are shown in Table 2.

(Example 4)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine, using 4,4'-bis(4-aminophenoxy)biphenyl a mixture of 0.2653 g (0.72 mol: APBP) and 4,4'-diaminobenzimidamide 0.0409 g (0.18 mol: DABAN) (the molar ratio of APBP to DABAN ([APBP]: [DABAN]) is 80:20) Alternatively, in the manufacturing step of the film formed by the polyimide, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the same method as in Embodiment 1 is employed. A polyimide film was obtained. Further, when it was determined that the molecular structure of the compound which formed the film in the same manner as in Example 1 was confirmed, it was confirmed to be a polyimine. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, and n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (102). The content of the polyimine is 80 mol% based on the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg obtained by the evaluation method of the above characteristics, the softening temperature, etc.) are shown in Table 2.

(Example 5)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine, using 4,4'-bis(4-aminophenoxy)biphenyl a mixture of 0.1990 g (0.54 mol: APBP) and 4,4'-diaminobenzimidamide 0.0818 g (0.36 mol: DABAN) (the molar ratio of APBP to DABAN ([APBP]: [DABAN]) is 60:40) Alternatively, in the manufacturing step of the film formed by the polyimide, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the same method as in Embodiment 1 is employed. A polyimide film was obtained. Further, when it was determined that the molecular structure of the compound which formed the film in the same manner as in Example 1 was confirmed, it was confirmed to be a polyimine. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (102), and the content of the polyimine is 60 mol% based on the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg obtained by the evaluation method of the above characteristics, the softening temperature, etc.) are shown in Table 2.

(Example 6)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine, using 4,4'-bis(4-aminophenoxy)biphenyl a mixture of 0.1326 g (0.36 mol: APBP) and 4,4'-diaminobenzimidamide 0.1227 g (0.54 mol: DABAN) (the molar ratio of APBP to DABAN ([APBP]: [DABAN]) is 40:60) Alternatively, in the manufacturing step of the film formed by the polyimide, the above-mentioned final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the same method as in Embodiment 1 is employed. A polyimide film was obtained. Further, when it was determined that the molecular structure of the compound which formed the film in the same manner as in Example 1 was confirmed, it was confirmed to be a polyimine. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (102). The content of the polyimine is 40 mol% with respect to the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg obtained by the evaluation method of the above characteristics, the softening temperature, etc.) are shown in Table 2.

(Comparative Example 11)

In the production step of polylysine, 1,4-bis(4-aminophenoxy)benzene other than aromatic diamine, using 4,4'-bis(4-aminophenoxy)biphenyl a mixture of 0.0663 g (0.18 mol: APBP) and 4,4'-diaminobenzimidamide 0.1636 g (0.72 mol: DABAN) (the molar ratio of APBP to DABAN ([APBP]: [DABAN]) is 20:80) Alternatively, in the manufacturing step of the film formed by the polyimide, the final heating temperature in the non-oxidizing oven is changed from 340 ° C to 350 ° C, and the same method as in Embodiment 1 is employed. A polyimide film was obtained. Further, the polyimine obtained in this manner is known from the type of the monomer used, and is a repeating unit represented by the above formula (1) (in the formula, R ¹ , R ² , R ³ Any of them is a hydrogen atom, n is 2, and R ¹⁰ is a repeating unit of the group represented by the above formula (102), and the content of the polyimine is 20 mol% based on the total repeat unit. Further, the evaluation results of the intrinsic viscosity [η] of the polyaminic acid or the properties of the polyimide film (the Tg or the softening temperature obtained by the evaluation method of the above characteristics) are shown in Table 2 (again, Table 2) For the purpose of comparison, the results of Examples 1 and 2 are also described together).

As is clear from the results shown in Tables 1 and 2, it was confirmed that any of the polyimine films of the present invention (Examples 1 to 6) had a tensile strength of 125 MPa or more, and the elongation at break was 15% or more, the tensile strength and the stretching property (the stretching property until the fracture) are higher and have a higher balance, and are highly tough. Further, the polyimine film of the present invention (Examples 1 to 8) has a Tg of 295 ° C or higher, a softening temperature of 470 ° C or more, and a temperature of 494 ° C or more when the weight is reduced by 5%. It is confirmed to be a person having a very high heat resistance. Further, in any of the polyimide films of the present invention (Examples 1 to 8), the total light transmittance was 87% or more, and it was confirmed that the film had extremely high transparency. From these results, the polyimine film (the polyimide film of the present invention) obtained in each of the examples has a high heat resistance and sufficient transparency, and is also highly tough (height). Toughness: Higher mechanical strength). Further, as is clear from the results shown in Table 2, when the repeating unit represented by the above formula (1) contains 40 mol% or more, the tensile strength and the stretching property can be made to have a higher level of balance. For those with high toughness (higher mechanical strength).

On the other hand, the polyimide film prepared in Comparative Examples 1 to 11 has a tensile strength of less than 125 MPa, or a tensile elongation of less than 15%, and therefore, it does not allow tensile strength and stretchability. Fully play a high level of balance. From these results, it was found that the polyimine film obtained in each of the comparative examples was not sufficiently tough in comparison with the polyimide film of the present invention (Examples 1 to 6), and the mechanical strength was not Extremely adequate.

[Industrial use]

As described above, according to the present invention, it is possible to provide a polyimine having a higher level of tensile strength and stretch characteristics and having a higher balance of tensile strength and elongation at break. A film, and an organic electroluminescence element using the same. Further, according to the present invention, a transparent conductive laminate using the polyimide film, a touch panel using the transparent conductive laminate, a solar cell, and a display device can be provided.

Further, since the polyimide film of the present invention has higher toughness and excellent mechanical strength, it can be used as a substrate material such as an organic EL display or a liquid crystal display or a touch panel. The yield of the final product resulting from the excellent mechanical strength is improved. Based on these viewpoints, the polyimide film of the present invention is particularly suitable for, for example, a film for a flexible circuit substrate, a heat-resistant insulating tape, a wire enamel, an enamel, a protective coating for a semiconductor, a liquid crystal alignment film, and an organic Transparent conductive film for EL (organic electroluminescence), film for organic EL illumination, flexible substrate film, substrate film for flexible organic EL, flexible transparent conductive film, and transparent conductive film for organic thin film solar cells A thin film, a transparent conductive film for a dye-sensitized solar cell, a flexible gas barrier film, a film for a touch panel, an outer film for a flexible display, and a back film for a flexible display.

Claims (7)

A polyimine film characterized in that the tensile strength is formed by a polyimine containing 30 mol% or more of a repeating unit represented by the following general formula (1) with respect to a total repeat unit. 125MPa or more, and the elongation at break is 15% or more; In the formula (1), R ¹ , R ² and R ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and R ¹⁰ represents the following Equations (101)~(102): One of the selected bases, n represents an integer from 0 to 12]. The polyimine film according to claim 1, wherein the polyimine is a repeating unit represented by the above formula (1) with respect to a complete repeat The position is 40% or more. An organic electroluminescence device comprising the polyimine film of claim 1 or 2. A transparent conductive laminate comprising a film of the polyimide film of claim 1 or 2 and a conductive material laminated on the polyimide film. A touch panel characterized by comprising the transparent conductive laminate of claim 4. A solar cell characterized by comprising the transparent conductive laminate of claim 4. A display device comprising the transparent conductive laminate of claim 4.