KR20180016950A - Polyimide, polyamic acid, polyamic acid solution, and polyimide film - Google Patents

Abstract

The present invention relates to a polyimide film, comprising: a repeating unit (A) represented by a specific general formula; and a repeating unit (B) represented by a specific general formula, wherein a content of the repeating unit (A) with respect to a total amount of the repeating units (A) and (B) is 5-35 mol%. An object of the present invention is to provide a polyimide which is able to evenly achieve a sufficiently high total light transmittance, a sufficiently low yellow color, and a sufficiently low coefficient of linear expansion to a higher level, and the polyimide film having the polyimide.

Description

POLYAMIDE ACID, POLYAMIC ACID SOLUTION, AND POLYIMIDE FILM} BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide film,

The present invention relates to a polyimide, a polyamic acid, a polyamic acid solution and a polyimide film.

In the field of display devices using organic electroluminescence devices and display devices such as liquid crystal displays, the emergence of light and flexible materials having high light transmittance has been demanded as a material used for substrates thereof and the like. A film containing light and flexible polyimide has attracted attention as a material for such applications. With respect to such polyimide, recently, aliphatic polyimide having sufficient light transmittance has been developed. For example, in International Publication No. 2011/099518 (Patent Document 1), it is known that a repeating unit ≪ / RTI > is disclosed.

International Publication No. 2011/099518

The polyimide described in Patent Document 1 has a sufficiently high transparency. However, the polyimide described in Patent Document 1 is not always sufficient from the viewpoint of sufficiently exhibiting a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level. Thus, the conventional polyimide is not necessarily sufficient in that it sufficiently exhibits sufficiently high total light transmittance, sufficiently low yellow color and sufficiently low coefficient of linear expansion to a higher level.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a polyimide which can sufficiently attain a high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level, , A solution of the polyamic acid, and a polyimide film containing the polyimide.

The inventors of the present invention have conducted intensive studies to achieve the above object and as a result have found that the polyimide can be produced by mixing the polyimide with the repeating unit (A) represented by the following general formula (1) and the repeating unit (B) (A) relative to the total amount of the repeating units (A) and (B) is 5 to 35 mol%, the total light transmittance is sufficiently high, the sufficiently low yellow color and the sufficiently low The present invention has been accomplished on the basis of finding that the coefficient of linear expansion can be uniformly maintained at a higher level.

That is, the polyimide of the present invention has the following general formula (1):

R ¹ , R ² and R ³ in the formula (1) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,

(A) represented by the formula

(2): < EMI ID =

[In the formula (2), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]

, And the content of the repeating unit (A) in the total amount of the repeating units (A) and (B) is 5 to 35 mol%.

As the polyimide of the present invention, it is preferable that all of R ¹⁰ in the general formulas (1) and (2)

[In the formula (3), R ⁵ represents a fluoroalkyl group having 1 to 10 carbon atoms]

Is preferably a group represented by

As the polyimide of the present invention, it is preferable that the content of the repeating unit (A) relative to the total amount of the repeating units (A) and (B) is 5 to 25 mol%.

In addition, the polyamic acid of the present invention is represented by the following general formula (4):

Wherein R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,

(C) represented by the general formula

(5): < EMI ID =

[In the formula (5), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]

, And the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) is 5 to 35 mol%.

Further, the polyamic acid solution of the present invention comprises the polyamic acid of the present invention and an organic solvent.

In addition, the polyimide film of the present invention includes the polyimide of the present invention.

According to the present invention, there is provided a polyimide which makes it possible to uniformly maintain a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level, a polyamide acid , A solution of the polyamic acid and a polyimide film containing the polyimide.

1 is a graph showing the IR spectrum of the polyimide obtained in Example 1. Fig.

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

[Polyimide]

The polyimide of the present invention has the following general formula (1):

R ¹ , R ² and R ³ in the formula (1) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,

(A) represented by the formula

(2): < EMI ID =

[In the formula (2), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]

, And the content of the repeating unit (A) in the total amount of the repeating units (A) and (B) is 5 to 35 mol%.

Regarding the repeating unit (A), the alkyl group which may be selected as R ¹ , R ² and R ³ in the general formula (1) is an alkyl group having 1 to 10 carbon atoms. When the number of carbon atoms exceeds 10, the glass transition temperature is lowered and heat resistance at a sufficiently high level required for use in various substrate materials and the like can not be achieved. The number of carbon atoms of the alkyl group which can be selected as R ¹ , R ² and R ³ is preferably 1 to 6, more preferably 1 to 5, and most preferably 1 to 4, from the viewpoint of easier purification. , More preferably from 1 to 3 carbon atoms. The alkyl group which may be selected as R ¹ , R ² , and R ³ may be linear or branched. As the alkyl group, a methyl group and an ethyl group are more preferable from the viewpoint of easiness of purification.

R ¹ , R ² and R ³ in the above general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, More preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, independently from each other, from the viewpoints of easy availability of raw materials and easier purification, Or a methyl group. A plurality of R ¹ , R ² and R ³ in this formula are particularly preferably the same in terms of ease of purification and the like.

R ¹⁰ in the general formula (1) is an arylene group having 6 to 40 carbon atoms (fluorine-containing arylene group) having a fluorine-containing substituent. The fluorine-containing substituent referred to herein is not particularly limited as long as it contains fluorine, and examples thereof include a fluorine atom itself or an alkyl group (fluoroalkyl group) in which at least a part of the fluorine atom is substituted with a fluorine atom. Among such fluorine-containing substituents, from the viewpoint of obtaining a higher degree of heat resistance, fluoroalkyl groups having 1 to 10 carbon atoms (e.g., methyl, fluoromethyl, trifluoromethyl, trifluoroethyl, N-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, nonafluoro-sec-butyl group, nonafluoroisobutyl group, nonafluoro-t- A perfluorohexyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorononyl group, and a perfluorodecyl group) are preferable, and among them, More preferred is a fluoroalkyl group having 1 to 5 (more preferably 1 to 3) carbon atoms. The fluorine-containing substituent is more preferably a fluoroalkyl group having 1 to 5 carbon atoms (more preferably 1 to 3 carbon atoms) from the viewpoint of availability of the starting material. As to the R ¹⁰ , the fluorine-containing substituent of the arylene group is more preferably a fluoroalkyl group (particularly preferably a perfluoroalkyl group) having 1 to 3 (more preferably 1 to 2) carbon atoms Do. The term "fluoroalkyl group" as used herein means a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (the group may be such that at least a part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, Some hydrogen atoms may be further substituted with a substituent other than a fluorine atom (for example, a halogen atom other than a fluorine atom, a hydroxyl group, an alkoxy group, a phenoxy group, a deuterium, etc.), and a "perfluoroalkyl group" Means a group in which all of the atoms are substituted with fluorine atoms.

The present invention relates to an arylene group having a fluorine-containing substituent which can be selected as R ¹⁰ in the above-mentioned general formula (1), wherein the carbon number of the arylene group (the number of carbon atoms means the number of carbon atoms of the arylene group itself, The number of carbon atoms in the fluorine-containing substituent is excluded) is 6 to 40. [ The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 12 to 20. If the carbon number exceeds the upper limit, the heat resistance tends to decrease. Examples of the arylene group include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthracenylene group, a fluorenylene group, a phenanthrylene group, a chrysenylene group, an indenylene group, a pyrenylene group, A phenylene group and a naphthylene group are preferable, and a biphenylene group and a phenylene group are more preferable from the viewpoint of availability.

The arylene group having a fluorine-containing substituent which can be selected as R ¹⁰ in the general formula (1) is preferably an arylene group having a fluorine-containing substituent represented by the following general formula (3):

[In the formula (3), R ⁵ represents a fluoroalkyl group having 1 to 10 carbon atoms (more preferably a perfluoroalkyl group)

Is preferably a group represented by the following general formula (3-I)

Is particularly preferable.

In the polyimide of the present invention, plural kinds of repeating units (A) having different kinds of R ¹⁰ and the like may be used in combination as the repeating unit (A).

Regarding the repeating unit (B), R ¹⁰ in the general formula (2) is synonymous with R ^{10 in} the general formula (1) (the preferred examples thereof are the same as those of R ¹⁰ in the general formula (1) ). In the polyimide of the present invention, plural kinds of repeating units (B) having different kinds of R ¹⁰ and the like may be used in combination as the repeating unit (B).

From the viewpoint that the polyimide of the present invention has a sufficient level of heat resistance and exhibits sufficiently high total light transmittance, sufficiently low yellow color and sufficiently low coefficient of linear expansion to a higher level, the repeating unit It is preferable that all R ¹⁰ in A) and (B) are the same.

In the polyimide of the present invention, the content of the repeating unit (A) relative to the total amount of the repeating unit (A) represented by the general formula (1) and the repeating unit (B) The content is 5 to 35 mol% based on the molar amount. If the content of the repeating unit (A) represented by the general formula (1) is less than the lower limit described above, it tends to be difficult to have a sufficiently high total light transmittance (more preferably, 83.0% or more of the total light transmittance) (Preferably a coefficient of linear expansion of -20 ppm / K to 20 ppm / K), so that it is possible to achieve a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a high level It is not possible to have it evenly. On the other hand, when the content of the recurring unit (A) exceeds the upper limit, it is impossible to have a sufficiently low linear expansion coefficient (preferably, a coefficient of linear expansion of -20 ppm / K to 20 ppm / K) The yellow color and the sufficiently low coefficient of linear expansion can not be uniformly maintained at a high level.

From the viewpoint that the polyimide of the present invention has a sufficiently high total light transmittance and a sufficiently low yellow color and a sufficiently low linear expansion coefficient to a higher level, The content of the repeating unit (A) relative to the total amount of the repeating unit (A) and the repeating unit (B) represented by the general formula (2) is more preferably 5 to 25 mol%, more preferably 10 to 20 mol% , And particularly preferably 12.5 to 17.5 mol%. From the same viewpoint, the content of the repeating unit (B) relative to the total amount of the repeating unit (A) and the repeating unit (B) is 95 to 65 mol% based on the molar amount, and 95 , More preferably from 90 mol% to 75 mol%, still more preferably from 90 mol% to 80 mol%, particularly preferably from 87.5 mol% to 82.5 mol%.

In the polyimide of the present invention, other repeating units may be contained in such a range that the effect of the present invention is not impaired. Such another repeating unit is not particularly limited, and a known repeating unit capable of forming a polyimide can be appropriately used. When the polyimide of the present invention contains other repeating units, the total amount of the repeating unit (A) represented by the general formula (1) and the repeating unit (B) represented by the general formula (2) (A) and (B) so as to be at least 50 mol% (more preferably at least 70 mol%) based on the total repeating units in the polyimide. The content ratio of the total amount of the repeating unit (A) and the repeating unit (B) to the total repeating units in the polyimide is more preferably 80 to 100 mol%, further preferably 90 to 100 mol% desirable. If the content ratio of the total amount of the repeating units (A) and (B) to the total repeating units in the polyimide is less than the lower limit described above, it tends to be difficult to uniformly provide sufficiently low yellow color and sufficiently low linear expansion coefficient. From the viewpoint of forming the polyimide more efficiently, it is preferable that the polyimide of the present invention contains substantially the repeating units (A) and (B) (substantially no other repeating units, more preferably Is preferably at least 95 mol%, more preferably at least 98 mol%, particularly preferably at least 99 mol%, of the total amount of the repeating unit (A) and the repeating unit (B).

The polyimide preferably has a coefficient of linear expansion of from -20 ppm / K to 20 ppm / K, more preferably from -10 ppm / K to 10 ppm / K, even more preferably from -5 ppm / K to 5 ppm / K. When the coefficient of linear expansion exceeds the upper limit, there is a tendency that peeling easily occurs due to thermal hysteresis in the case of combining with a metal or an inorganic material having a coefficient of linear expansion in the range of 5 to 20 ppm / K and using it as a substrate for microelectronics It becomes difficult to manufacture final products of microelectronics (for example, organic EL displays, touch panels, protective films for semiconductors (buffer coatings), interlayer insulating films, photoresists, microlenses for image sensors, etc.) with high yield. On the other hand, when the coefficient of linear expansion is less than the lower limit described above, there is a tendency that peeling or curling tends to occur when inorganic materials are laminated. When the device is an inorganic compound in the case of producing a device in an upper layer or a lower layer of a film containing polyimide, from the viewpoint of suppressing curling of the film and deformation during production, It is preferable to use polyimide having a low linear expansion coefficient. From this point of view, the polyimide of the present invention preferably has a linear expansion coefficient within the above range.

In the present invention, the following values are adopted as the coefficient of linear expansion of the polyimide. That is, first, a film having a size of 20 mm in length, 5 mm in width, and 13 m in thickness containing the polyimide is formed with respect to the polyimide as an object to be measured. Thereafter, the film is vacuum dried (at 120 DEG C for 1 hour) and heat-treated at 200 DEG C for 1 hour in a nitrogen atmosphere to obtain a dried film. The film thus obtained was used as a sample, and a tensile mode (49 mN) and a temperature raising rate of 5 deg. C / min. Were carried out under a nitrogen atmosphere using a thermomechanical analyzer (trade name "TMA8310" , And the change in length in the longitudinal direction of the sample at 50 to 200 DEG C was measured to find an average value of the change in length per 1 DEG C (1K) in the temperature range of 50 DEG C to 200 DEG C I ask. The average value thus obtained is adopted as the value of the coefficient of linear expansion of the polyimide of the present invention (the value of the coefficient of linear expansion of the polyimide film when the thickness is 13 탆 is set to the value of the coefficient of linear expansion of the polyimide of the present invention Value).

The polyimide preferably has a weight reduction temperature of 5% (Td 5%) of 400 캜 or higher, more preferably 450 to 550 캜. If the 5% weight reduction temperature is less than the lower limit described above, it tends to be difficult to obtain sufficient heat resistance for use as a substrate for a product of microelectronics. On the other hand, if the upper limit is exceeded, It tends to be difficult to do. The 5% weight reduction temperature was obtained by heating under the conditions of a scanning temperature of 30 to 550 DEG C and a heating rate of 10 DEG C / min while flowing a nitrogen gas in a nitrogen gas atmosphere, Can be obtained by measuring the temperature at which the temperature is reduced by 5%. For this measurement, for example, a thermogravimetric analyzer (" TG / DTA220 " made by SII Nanotechnology Co., Ltd.) may be used as the measuring apparatus.

The polyimide preferably has a glass transition temperature (Tg) of 300 ° C or higher, more preferably 350 ° C to 500 ° C. When the glass transition temperature (Tg) is less than the lower limit described above, it is difficult to obtain sufficient heat resistance because it is used as a substrate for a product of microelectronics (for example, for solar cells, liquid crystal display devices, There is a tendency that in the case of using polyimide as the substrate, it is difficult to adequately suppress deterioration (such as cracking) of the quality of the polyimide (substrate) in the heating process in the production process of the product On the other hand, when the upper limit is exceeded, it tends to be difficult to produce polyimide having such properties. The glass transition temperature (Tg) can be measured at the same time by using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku Corporation) as a measuring apparatus and measuring the softening temperature. In order to measure the glass transition temperature, it is preferable to carry out the measurement by scanning in the range of 30 ° C to 550 ° C under the nitrogen atmosphere at the temperature raising rate of 5 ° C / min.

The polyimide preferably has a softening temperature (softening point) of 300 to 550 占 폚, more preferably 320 to 550 占 폚, and still more preferably 340 to 510 占 폚. When the softening temperature is lower than the lower limit, the heat resistance is lowered. For example, when a film containing such a polyimide is used as a substrate for a transparent electrode of a solar cell, a liquid crystal display device, or an organic EL display device, There is a tendency that it is difficult to sufficiently suppress the deterioration (such as cracking) of the quality of such a film (substrate) in the manufacturing process. On the other hand, when the upper limit is exceeded, when the polyimide is produced, Sufficient solid phase polymerization reaction does not proceed at the same time as the condensation reaction, and the film tends to become brittle when the film is formed. The softening temperature of such a polyimide can be measured in the following manner. That is, a film containing polyimide having a size of 5 mm in length, 5 mm in width and 0.013 mm (13 m) in thickness was prepared as a measurement sample, and a thermomechanical analyzer (trade name "TMA8311" A transparent quartz pin (diameter at the tip: 0.5 mm) was infiltrated into the film at a pressure of 500 mN under the condition of a temperature range of 30 ° C to 550 ° C by employing the conditions of a temperature raising rate of 5 ° C / (Tg) can be measured at the same time (can be measured by the so-called penetration method). In this measurement, the softening temperature is calculated based on the measurement data in accordance with the method described in JIS K 7196 (1991).

Further, it is difficult to dissolve such a polyimide in a solvent to measure the molecular weight. Therefore, the molecular weight (number average molecular weight or weight average molecular weight) and molecular weight distribution of polyamic acid (polyamic acid) . The number average molecular weight (Mn) of the polyamic acid (polyamic acid) which is a precursor of the polyimide is preferably 1000 to 1000000 in terms of polystyrene, and more preferably 10000 to 500000. If the number average molecular weight is less than the lower limit described above, not only sufficient heat resistance becomes difficult to achieve but also it is difficult to obtain polyimide efficiently. On the other hand, when the number average molecular weight is more than the upper limit, viscosity is increased, , A large amount of a diluting solvent for viscosity adjustment is required, which tends to make processing difficult.

The weight average molecular weight (Mw) of the polyamic acid (polyamic acid) which is a precursor of such a polyimide is preferably 1,000 to 5,000,000 in terms of polystyrene. The lower limit of the numerical value range of the weight average molecular weight (Mw) is more preferably 5000, further preferably 10000, particularly preferably 20,000. The upper limit value of the numerical value range of the weight average molecular weight (Mw) is more preferably 5,000,000, more preferably 500,000, and particularly preferably 100,000. When the weight average molecular weight is less than the lower limit, sufficient heat resistance tends to be difficult to achieve, and it tends to be difficult to obtain polyimide efficiently. On the other hand, if the weight average molecular weight is more than the upper limit, viscosity tends to increase, , A large amount of a diluting solvent for viscosity adjustment is required, which tends to make processing difficult.

The molecular weight distribution (Mw / Mn) of the polyamic acid (polyamic acid) which is a precursor of such a polyimide is preferably 1.1 to 5.0, more preferably 1.5 to 3.0. If the molecular weight distribution is less than the lower limit described above, it tends to be difficult to produce. On the other hand, when the upper limit is exceeded, it tends to be difficult to obtain a uniform film when the film is formed. The molecular weight (Mw or Mn) and the molecular weight distribution (Mw / Mn) of the polyimide were measured by a gel permeation chromatography (GPC) measuring device (EcoSEC HLC-8320GPC manufactured by TOSOH, column: (GPC column: TSKgel Super AW2500, 3000, 4000, column temperature: 40 DEG C, developing solvent: dimethylacetamide solvent (flow rate: 0.5 mL / min) containing 10 mM LiBr) was used to obtain polystyrene .

As such polyimide, it has been used for the use of a flexible transparent material such as a transparent display, a solar cell, a touch panel, a front film, and a transparent FPC in place of a suitable value (not more than 16) of the yellowness index It is more preferable that the total light transmittance is not less than 83% (more preferably not less than 85%, particularly preferably not less than 87%) from the viewpoint of ensuring a high visibility required at the time of use. If the total light transmittance is less than the lower limit described above, even if the yellowness is 16 or less, it becomes difficult to exhibit the transparency (visibility) required for various applications depending on the value of the yellowness.

It is more preferable that such a polyimide has a haze (turbidity) of 5 or less (more preferably 4 or less, particularly preferably 3 or less) from the viewpoint of obtaining a higher degree of transparency.

It is more preferable that such a polyimide has a yellowness degree (YI) of not more than 16.0 (more preferably not more than 11.0, particularly preferably not more than 10.5) from the viewpoint of obtaining a higher degree of transparency. If the yellowness exceeds the upper limit, it becomes difficult to secure a high color, brightness, saturation, brightness, tone, contrast, chromaticity and transparency (visibility) necessary for the application, Even if it is 83% or more, it is difficult to exhibit the performance required for use in various applications.

The total light transmittance, haze, and yellowness (YI) were measured using a haze meter NDH-5000 (trade name, manufactured by Nippon Denshoku Kogyo Kagaku Co., Ltd., The total light transmittance and haze were measured with a trade name " Spectral Color Spectrometer SD6000 " (trade name " Hazemeter NDH-5000 ", manufactured by Nippon Denshoku Kogyo K.K.) Color meter SD6000 ") and a film containing polyimide having a thickness of 10 to 15 mu m (preferably 13 mu m) as a sample for measurement. However, regarding the yellowness index (YI), a conversion value converted into a value of a film having a thickness of 13 mu m or a value of a film having a thickness of 13 mu m is adopted as described below. That is, the total light transmittance and the haze (turbidity) can be measured with the same polyimide from the same polyimide because the thickness is sufficiently thin and there is no influence on the measured value if the film contains polyimide having a thickness of 10 to 15 m can do. On the other hand, since the yellowness index (YI) tends to be influenced by the film thickness, in the present invention, in using the film having the thickness in the above range (10 to 15 mu m) as a sample for measurement, (YI) is converted into a value of a film having a thickness of 13 mu m (or a measured value thereof when the film is measured using a film having a thickness of 13 mu m). Thus, in the present invention, the value of the yellowness index (YI) is a value converted into a value of a film having a thickness of 13 mu m or a value of a film having a thickness of 13 mu m. For the measurement of the total light transmittance, the haze (turbidity) and the yellowness (YI) in this viewpoint (the yellowness value can be converted into the value of the film having a thickness of 13 mu m) (Further, when YI is measured using a film having a thickness other than 13 占 퐉 as a sample for measurement, a value of a thickness of 13 占 퐉 as described above It is preferable that a film containing polyimide having a thickness of 13 占 퐉 is prepared and used as a sample for measurement) from the viewpoint that such conversion becomes unnecessary. The length and width of the measurement specimen may be any size that can be disposed on the measurement site of the measurement apparatus, and the length and width may be appropriately changed. The total light transmittance was determined by measurement in accordance with JIS K7361-1 (published in 1997), and haze (turbidity) was measured by measurement in accordance with JIS K7136 (published in 2000) ) Is obtained by carrying out measurements in accordance with ASTM E313-05 (issued in 2005).

Methods which can be suitably used for producing such a polyimide will be described later.

[Polyamide acid]

The polyamic acid of the present invention is represented by the following general formula (4):

Wherein R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,

(C) represented by the general formula

(5): < EMI ID =

[In the formula (5), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]

, And the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) is 5 to 35 mol%.

Such a polyamic acid can be suitably used in the production of the polyimide of the present invention (it can be obtained as a reaction intermediate (precursor) in producing the polyimide of the present invention). This formula (4) in the R ^1, R ^2, R ^3, R ¹⁰ and n have the above general formula (1) of R ^1, R ^2, R ^3, R ¹⁰ and n and those of the same, even his right the Are the same as R ¹ , R ² , R ³ , R ¹⁰ and n in the general formula (1). Further, the general formula (5) in R ¹⁰ is the formula (2) in R ¹⁰ and those of the same (that is, the formula (1) in R ¹⁰ and those of the same), a group of the formula: also his right of the general ( 2) the same as those of R ^10.

In the polyamic acid of the present invention, the content of the repeating unit (C) relative to the total amount of the repeating unit (C) represented by the general formula (4) and the repeating unit (D) Is 5 to 35 mol% based on the molar amount. When the content of the repeating unit (C) represented by the general formula (4) is less than the lower limit described above, when the polyimide is produced using such a polyamic acid, the total light transmittance at a sufficiently high total light transmittance (preferably not less than 83.0% It is difficult to have a sufficiently high coefficient of linear expansion (preferably, a coefficient of linear expansion of -20 ppm / K to 20 ppm / K), and a sufficiently high total light transmittance And a polyimide having sufficiently low yellow color and sufficiently low coefficient of linear expansion to a high level can not be obtained. On the other hand, when the content of the recurring unit (C) exceeds the upper limit, in this case also, when the polyimide is produced by using such a polyamic acid, a sufficiently low linear expansion coefficient (preferably -20 ppm / K to 20 ppm / K The polyimide having a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion can not be produced at a high level even at a high level.

In the polyamic acid of the present invention, from the viewpoint of obtaining a polyimide having sufficiently low yellow color and sufficiently low linear expansion coefficient at a higher level by using such polyamic acid, the repeating units (C) and The content of the repeating unit (C) relative to the total amount of the repeating unit (D) is more preferably from 5 to 25 mol%, still more preferably from 10 to 20 mol%, even more preferably from 12.5 to 17.5 mol% desirable.

In the polyamic acid of the present invention, other repeating units may be contained in the range not impairing the effect of the present invention. Such another repeating unit is not particularly limited, and a known repeating unit capable of forming a polyamic acid can be appropriately used. In the polyamic acid of the present invention, in the case of containing other repeating units, the total amount of the repeating unit (C) represented by the general formula (4) and the repeating unit (D) represented by the general formula (C) and (D) so as to be at least 50 mol% (more preferably at least 70 mol%) based on the total repeating units in the polyamic acid. The content ratio of the total amount of the repeating unit (C) and the repeating unit (D) to the total repeating units in the polyamic acid is preferably 80 to 100 mol%, more preferably 90 to 100 mol% More preferable. When the content ratio of the total amount of the repeating units (C) and (D) is less than the above lower limit, it tends to be difficult to produce a polyimide having a sufficiently high total light transmittance, sufficiently low yellow color and sufficiently low linear expansion coefficient . From the standpoint of forming polyimide more efficiently by using such a polyamic acid, it is preferable that the polyamic acid of the present invention contains substantially repeating units (C) and (D) (C) and (D) is 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 99 mol% or more) is preferable Do.

The polyamic acid preferably has an intrinsic viscosity [?] Of 0.05 to 3.0 dL / g, more preferably 0.1 to 2.0 dL / g. When the intrinsic viscosity [?] Is less than 0.05 dL / g, the obtained film tends to become brittle when the polyimide on the film is produced using the same, while when it exceeds 3.0 dL / g, The processability is lowered, and it becomes difficult to obtain a uniform film, for example, when a film is produced. The inherent viscosity [?] Can be measured as follows. That is, first, the polyamidic acid is dissolved in the tetramethylurea (TMU) to a concentration of 0.5 g / dL using tetramethylurea (TMU) as a solvent to obtain a measurement sample (solution). Next, the viscosity of the sample to be measured is measured using a dynamic viscometer under the temperature condition of 30 占 폚 by using the sample to be measured, and the obtained value is adopted as intrinsic viscosity [?]. As this dynamic viscometer, an automatic viscosity measuring device (trade name: VMC-252) manufactured by LIGO Co., Ltd. is used.

Hereinafter, a method which can be suitably used for producing such a polyamic acid will be described.

(A method suitably usable for producing a polyamic acid)

A method that can be suitably used for producing such a polyamic acid is not particularly limited, and for example, the following general formula (10):

Wherein R ¹ , R ² and R ³ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is an integer of 0 to 12, Indicates]

(A) represented by the following general formula (11):

(I) having a content of the compound (A) of 5 to 35 mol% based on the total amount of the compounds (A) and (B) )and,

(12): < EMI ID =

[In the formula (12), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]

(Compound (II)) containing a compound represented by the general formula (II) in the presence of an organic solvent,

Wherein the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) is 5 to 35 mol%, and the content of the repeating unit (C) Can be suitably used. The repeating unit (C) is formed from the compound (A) and the compound represented by the general formula (12), and the repeating unit (D) Lt; / RTI >

R ¹ , R ² , R ³ and n in the compound (A) represented by the general formula (10) used in the process for producing the polyamic acid are represented by R ¹ , R ² , R ^3, and n (the corresponding ones are the same as R ¹ , R ² , R ³ and n in the general formula (1)). Further, R ¹⁰ in the compound represented by the above general formula 12 is R ¹⁰ and copper in the formula (1) and (2) (R ¹⁰ in the even his right above general formula (1) and (2), and The same).

The method for producing the compound (A) represented by the general formula (10) is not particularly limited and a known method (for example, a method described in International Publication No. 2011/099518) can be suitably used .

The method for producing the compound (B) represented by the general formula (11) is not particularly limited and a known method can be appropriately used. Such compound (B) is pyromellitic anhydride (1,2,4,5-benzenetetracarboxylic acid dianhydride, pyromellitic anhydride), and commercially available compounds may be suitably used.

The method for producing the compound represented by the above general formula (12) is not particularly limited and a known method can be suitably employed. As the compound represented by the general formula (12), a commercially available compound may be suitably used.

The tetracarboxylic dianhydride (compound (I)) is preferably a compound represented by the formula (I) in which the content of the compound (A) relative to the total amount of the compounds (A) and (B) . When the content of the compound (A) is lower than the lower limit and exceeds the upper limit, the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) Mol%) can not be formed. In the compound (I), from the same viewpoint, the content ratio of the compound (A) to the total amount of the compounds (A) and (B) is more preferably 5 to 25 mol% More preferably 20 mol%, and particularly preferably 12.5 to 17.5 mol%.

As the compound (I), tetracarboxylic dianhydrides other than the compounds (A) and (B) may be mixed and used in order to contain other repeating units in the polyamic acid of the present invention. As other tetracarboxylic acid dianhydrides other than the compounds (A) and (B), known tetracarboxylic dianhydrides which can be used for the production of polyimides can be suitably used. In this case, the amount of the tetracarboxylic dianhydride other than the compounds (A) and (B) to be used is such that the content of the repeating units (C) and (D) in the polyamic acid to be obtained falls within a desired range The range of the amount of the content, and the like). Further, the tetracarboxylic dianhydride (compound (I)) is required to have a sufficiently high level of heat resistance and to exhibit a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level The compound (I) contains substantially the above-mentioned compounds (A) and (B) (the compound (I) contains substantially the tetracarboxylic dianhydride other than the compounds (A) and (B) (A) and (B) in the compound (I) is 95 mol% or more, more preferably 98 mol% or more, particularly preferably 99 mol% or more , Most preferably 100 mol%) is preferable.

As the compound (II), other diamine compounds (such as other aromatic diamines and alicyclic diamines) other than the compound represented by the general formula (12) may be added to the polyamide acid of the present invention in order to contain other repeating units. It can be appropriately contained. As these other diamine compounds, other known diamine compounds that can be used for the production of polyimide can be suitably used. As such other diamine compounds, for example, both terminal amino-modified siloxanes and the like can be suitably used. Specific examples of such a two-terminal amino-modified siloxane include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, amino-modified silicone oil from Shin-Etsu Chemical Co., Ltd. (for example, PAM- X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 and X-22-9409), dimethylsiloxane diamines from Gelest DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32, DMS-A32R and DMS-A35). The amount of the diamine compound other than the compound represented by the general formula (12) in the compound (II) is such that the content of the repeating units (C) and (D) in the polyamide acid to be obtained falls within a desired range (The range of the above-mentioned appropriate content, etc.). From the viewpoint of sufficiently exhibiting a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level, the diamine compound (compound (II)) has a sufficient level of heat resistance, (II) substantially does not contain a diamine compound substantially different from the compound represented by the general formula (12), and the compound (II) is more preferably a compound represented by the general formula (12) is 95 mol% or more, more preferably 98 mol% or more, particularly preferably 99 mol% or more, and most preferably 100 mol%).

The organic solvent is preferably an organic solvent capable of dissolving both the tetracarboxylic dianhydride (compound (I)) and the diamine compound (compound (II)). Examples of such organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide,? -Butyrolactone, A non-protonic polar solvent such as a carbonate, tetramethyl urea (tetramethyl urea (TMU)), 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide and pyridine; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol; Ether solvents such as tetrahydrofuran, dioxane, cellosolve and glyme; Ketone solvents such as cyclopentanone, cyclohexanone and cycloheptanone; Aromatic solvents such as benzene, toluene and xylene; And the like. These organic solvents may be used singly or in a mixture of two or more kinds.

The ratio of the tetracarboxylic dianhydride (compound (I)) to the diamine compound (compound (II)) is such that the amount of the tetracarboxylic dianhydride (compound (II) The acid anhydride group in the compound (I) is preferably 0.2 to 2 equivalents, more preferably 0.8 to 1.2 equivalents. If the use ratio is less than the lower limit described above, the polymerization reaction does not progress efficiently and a high molecular weight polyamic acid tends not to be obtained. On the other hand, when the upper limit is exceeded, a tendency of not obtaining a high molecular weight polyamic acid .

The amount of the organic solvent to be used is preferably from 1 to 50% by weight (more preferably from 1 to 50% by weight, based on the total amount of the reaction solution) of the tetracarboxylic dianhydride (compound (I)) and the diamine compound (compound By mass to 10% by mass to 30% by mass). If the amount of the organic solvent used is less than the lower limit, the polyamic acid can not be efficiently obtained. On the other hand, if the amount exceeds the upper limit, stirring tends to be difficult due to high viscosity.

From the viewpoint of obtaining a polyamic acid having an improved reaction rate and a high degree of polymerization when the tetracarboxylic dianhydride (compound (I)) is reacted with the diamine compound (compound (II)), A basic compound may be further added. Examples of such basic compounds include, but are not limited to, triethylamine, tetrabutylamine, tetrahexylamine, 1,8-diazabicyclo [5.4.0] undecene-7, pyridine, isoquinoline, Choline and the like. The amount of the basic compound to be used is preferably 0.001 to 10 equivalents, more preferably 0.01 to 0.1 equivalents based on 1 equivalent of the tetracarboxylic acid dianhydride (compound (I)). If the amount of the base compound used is less than the lower limit described above, the effect of addition tends to be lowered. On the other hand, if the amount exceeds the upper limit, the base compound tends to cause coloration or the like.

The reaction temperature for the reaction of the tetracarboxylic dianhydride (compound (I)) with the diamine compound (compound (II)) may be suitably adjusted to a temperature at which these compounds can be reacted, But it is preferably -20 캜 to 200 캜. As a method for reacting the tetracarboxylic dianhydride (compound (I)) with the diamine compound (compound (II)), a known method capable of carrying out a polymerization reaction of a tetracarboxylic dianhydride and a diamine compound And the diamine compound is dissolved in a solvent in an inert atmosphere such as nitrogen, helium, or argon at atmospheric pressure, and then the tetracarboxylic acid dianhydride ( The compound (I)) is added, and then the reaction is carried out for 10 to 48 hours. If the reaction temperature or the reaction time is less than the lower limit, it tends to be difficult to sufficiently react. On the other hand, if the reaction temperature or the reaction time exceeds the upper limit, the probability of incorporation of a substance (oxygen or the like) deteriorating the polymer is increased and the molecular weight tends to decrease.

Thus, the polyamic acid of the present invention can be obtained by reacting the tetracarboxylic acid dianhydride (compound (I)) with the diamine compound (compound (II)) in the presence of an organic solvent. When the polyamic acid of the present invention is isolated from the organic solvent after the production of the polyamic acid in such a manner, the method for isolating the polyamic acid of the present invention is not particularly limited, and a known method capable of isolating polyamic acid is suitably used For example, a method of isolation as a re-precipitate may be adopted.

[Polyamic acid solution]

The polyamic acid solution of the present invention comprises the above polyamic acid of the present invention and an organic solvent. As the organic solvent to be used in such a polyamic acid solution, the same organic solvents as those used in a method suitably usable for producing the aforementioned polyamic acid can be suitably used. Therefore, the polyamic acid solution of the present invention may be produced by a method suitably usable for producing the above-mentioned polyamic acid, and the reaction solution obtained after the reaction is directly converted into a polyamic acid solution. That is, the polyamic acid solution of the present invention can be prepared by reacting the tetracarboxylic dianhydride (compound (I)) with the diamine compound (compound (II)) in the presence of the organic solvent, , And then obtaining a solution containing the polyamic acid and the organic solvent.

The content of the polyamic acid in the polyamic acid solution is not particularly limited, but is preferably 1 to 50% by mass, and more preferably 10 to 30% by mass. When the content is less than the above lower limit, the molecular weight of the polyamic acid tends to decrease. On the other hand, when the content exceeds the upper limit, the production of polyimide tends to be difficult. Such a polyamic acid solution can be suitably used for producing the polyimide of the present invention.

When such a polyamic acid solution is used in the production of polyimide, various kinds of additives (high molecular weight or imidization accelerators, deterioration inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, modifiers A surface modifier, a hardening agent, a leveling agent, a surfactant, a filler (a glass fiber, a filler, a talc, a mica, a silica, a filler, Etc.) may be suitably added and used. With respect to the case of using such an additive, the content of the additive in the polyamic acid solution is not particularly limited, but it is preferably about 0.0001 to 80 mass% (more preferably 0.1 to 50 mass%).

(A method suitably available for producing polyimide)

A method that can be suitably used for producing the polyimide of the present invention is not particularly limited, but by imidizing the polyamic acid of the present invention,

A polyimide containing the repeating unit (A) and the repeating unit (B) and containing the repeating unit (A) in an amount of 5 to 35 mol% based on the total amount of the repeating units (A) and (B) It is possible to suitably use the method of obtaining the same. The repeating unit (A) is formed from the repeating unit (C), and the repeating unit (B) is formed from the repeating unit (D).

Such a method for imidizing a polyamic acid can be any method capable of imidizing a polyamic acid, and there is no particular limitation, and a known method can be suitably employed. For example, when the polyamic acid of the present invention is used in an amount of 60 To a temperature of from 450 to 450 DEG C (more preferably from 80 to 400 DEG C), or a method of imidizing by using a so-called " imidizing agent " is preferably employed.

In the case of employing the imidization process by applying such a heat treatment, the progress of the reaction tends to be retarded when the heating temperature is lower than 60 DEG C, while if the heating temperature exceeds the upper limit, the molecular weight And the like tend to occur. The reaction time (heating time) in the case of adopting the imidization method by conducting the heat treatment is preferably 0.5 to 5 hours. If the reaction time is less than the lower limit described above, it tends to be difficult to imidize sufficiently. On the other hand, when the upper limit is exceeded, there is a tendency that coloration occurs or molecular weight decreases due to thermal decomposition. Since the polyamic acid of the present invention can produce polyimide having sufficiently low yellow color and sufficiently low coefficient of linear expansion even when imidized by heating under oxygen containing conditions such as in the atmosphere, Is not particularly limited, and may be in an inert gas atmosphere or in an atmospheric condition. In addition, in the case of producing by heating in the air, polyimide can be produced in a simpler facility or the like, and polyimide can be produced without controlling atmospheric gas, Can be improved. Further, in the case of imidization by heating, a so-called accelerator (additive) may be used in order to promote high molecular weight or imidization. As such accelerators, known reaction accelerators (for example, imidazole compounds, pyridine compounds, tertiary amine compounds such as triethylamine, amino acid compounds, etc.) may be suitably used. The amount of such promoter to be used is not particularly limited and is, for example, 1 to 60 parts by mass, and preferably 5 to 50 parts by mass, based on 100 parts by mass of the solid content (polyamic acid) in the polyamic acid solution.

In the case of employing a method of imidizing a polyamic acid using a so-called " imidizing agent ", it is preferable to imidize the polyamic acid of the present invention in a solvent in the presence of an imidizing agent. As such a solvent, those similar to the organic solvent used in the process for producing a polyimide acid of the present invention may be suitably used.

As the imidization agent, a known imidization agent can be appropriately used. Examples thereof include acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, pyridine, collidine, lutidine, triethylamine, N- And tertiary amines such as methylpiperidine. Further, in the case of imidization by adding an imidization agent, the reaction temperature at imidization is preferably 0 to 200 캜, more preferably 30 to 150 캜. The reaction time is preferably 0.1 to 48 hours. If the reaction temperature or time is less than the lower limit described above, it tends to be difficult to imidize sufficiently. On the other hand, if the reaction temperature or time exceeds the upper limit, the probability of incorporation of a substance (oxygen or the like) deteriorating the polymerized material tends to increase, . The amount of the imidization agent to be used is not particularly limited and may be in the range of from several millimoles to several moles (preferably about 0.01 to 4.0 moles) relative to 1 mole of the repeating unit represented by the formula (5) in the polyamic acid .

As a method which can be suitably used for producing the polyimide of the present invention, the tetracarboxylic acid dianhydride (compound (I)) and the diamine compound (compound (II)) are reacted in the presence of an organic solvent , The repeating unit (C) and the repeating unit (D), and the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) is 5 to 35 mol% (I) of obtaining an acid (the polyamic acid of the present invention);

Wherein the content of the repeating unit (A) relative to the total amount of the repeating units (A) and (B) is at least one kind selected from the group consisting of the repeating units (A) (II) of obtaining a polyimide having 5 to 35 mol% (the polyimide of the present invention);

And the like. As described above, when the method including the step (I) and the step (II) is adopted as the method for producing the polyimide of the present invention, it is possible to produce the polyimide in a series of steps.

In the case of employing the method including the steps (I) and (II), and adopting the imidization by performing the heat treatment at the time of imidization, after the step (I) The reaction solution obtained by reacting the tetracarboxylic dianhydride (compound (I)) with the diamine compound (compound (II)) in an organic solvent without isolating the polyamic acid of the present invention (Reaction liquid containing a polyamic acid) is used as it is or the above-mentioned promoter is added to the reaction solution, and the reaction solution is subjected to a treatment for removing the solvent by evaporation (solvent removal treatment) to remove the solvent, A method of imidization may be employed. By subjecting the solvent to evaporation removal treatment, the polyamide acid of the present invention can be isolated in the form of a film or the like, and then heat treatment can be performed. In the process of evaporating and removing the solvent, the temperature is preferably 0 to 180 ° C, more preferably 30 to 150 ° C. If the temperature is lower than the lower limit in the process of evaporating and removing such a solvent, there is a tendency that it is difficult to sufficiently evaporate the solvent to remove the solvent. On the other hand, when the upper limit is exceeded, a film containing bubbles or voids . In this case, for example, in the case of producing a film-like polyimide, the reaction solution obtained is directly applied on a substrate (for example, a glass plate), and the process of evaporating and removing the solvent and the heat treatment are carried out, It is possible to prepare a film-like polyimide. The method of applying such a reaction liquid is not particularly limited, and a known method (casting method, etc.) can be suitably employed. When the polyamic acid of the present invention is isolated from the reaction solution and used, isolation is not particularly limited and a known method capable of isolating polyamic acid can be suitably employed. For example, And a method of isolating it as a precipitate may be employed.

Further, in the case of using the method including the steps (I) and (II), in the case of employing the imidization method using the " imidization agent ", from the viewpoint of forming the polyimide on the film more efficiently, The reaction liquid obtained by reacting the tetracarboxylic acid dianhydride (compound (I)) with the diamine compound (compound (II)) in an organic solvent is used as it is (step (I) The polyamide acid of the present invention is not isolated and the above reaction solution is used as it is), an imidizing agent is added to the reaction solution, and the reaction solution is applied to a substrate such as glass while the imidization does not sufficiently proceed , A method of imidizing on the substrate can be suitably employed.

[Polyimide film]

The polyimide film of the present invention comprises the polyimide of the present invention.

The shape of such a polyimide film is not particularly limited and may be appropriately designed in various shapes (such as a disc shape, a cylindrical shape (a film is processed normally), etc.).

The thickness of the polyimide film of the present invention is not particularly limited, but is preferably 1 to 500 占 퐉, more preferably 10 to 200 占 퐉. If the thickness is less than the lower limit described above, the strength tends to be lowered and handling becomes difficult. On the other hand, when the thickness exceeds the upper limit, there is a tendency that a plurality of coatings are required or processing is complicated.

Such a polyimide film is produced by suitably adjusting the coating method or the like so that the shape of the obtained polyimide is in a desired shape (film form) while employing the method described as a method that can be suitably used for producing the above-mentioned polyimide It is possible.

Although the polyimide, polyamic acid, polyamic acid solution and polyimide film of the present invention have been described above, the polyimide and polyimide films of the present invention are sufficiently high in overall light transmittance, sufficiently low in yellow, It is possible to sufficiently suppress the occurrence of film peeling or the like due to heat even when the film is laminated on a metal substrate or the like and to have sufficient visibility, For example, a film for a flexible wiring board, a heat-resistant insulating tape, a wire enamel, a protective coating for a semiconductor, a liquid crystal alignment film, a transparent conductive film for an organic EL, A transparent electrode substrate, a transparent electrode substrate of an electronic paper, etc.), a solar cell Flexible substrate films for flexible organic EL, flexible transparent conductive films, transparent conductive films for organic thin film solar cells, transparent conductive films for dye-sensitized solar cells, flexible gas barrier films, touch panels (A so-called transfer belt), an interlayer insulating film, a sensor substrate, and the like, for a substrate material for a touch panel, a front film for a flexible display, a back film for a flexible display, In addition, the polyimide of the present invention originates from its linear expansion coefficient and can be used as a substrate material for a display (a substrate for a display such as a TFT substrate or a transparent electrode substrate) or a substrate material for a touch panel Film, etc.), it is possible to further improve the yield of a final product (for example, an organic EL device).

From the polyimide characteristics of the present invention, it is possible to use a polyimide film for a semiconductor device such as a microelectronic (an organic EL display, a liquid crystal display, a touch panel, a flexible display panel, a high brightness LED wafer, a thin silicon wafer, a three- In the case of using the polyimide of the present invention as a material of a substrate used for a product of a semiconductor device, an interlayer insulating film, a photoresist, a microlens for an image sensor, etc., it is possible not only to cope with the enlargement of the device, It is possible to sufficiently prevent the cracks and curls in the heating step of the product, thereby achieving a high yield of the final product, and contributing to the improvement of the production efficiency and the improvement of the processing ability.

[Example]

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

First, a method for evaluating properties of the polyimide film and the like obtained in each of the examples and comparative examples will be described.

<Identification of Molecular Structure>

The molecular structures of the compounds obtained by the respective Examples and Comparative Examples were identified by IR measurement using an IR measuring device (trade name: FT / IR-4100, manufactured by Nihon Bunko KK).

&Lt; Measurement of intrinsic viscosity [?]

The value (unit: dL / g) of the intrinsic viscosity [?] Of the polyamic acid obtained as an intermediate in each of the Examples and Comparative Examples was measured using an automatic viscosity meter (trade name "VMC-252" , And tetramethylurea (TMU) as a solvent at a concentration of 0.5 g / dL under a temperature condition of 30 캜.

&Lt; Measurement of Glass Transition Temperature (Tg) and Softening Temperature >

The values of the glass transition temperature (Tg) and the softening temperature (unit: ° C) of the polyimide obtained in each of the Examples and Comparative Examples were measured using a film containing the polyimide prepared in each of the Examples and Comparative Examples, A measurement sample having a size of 5 mm in length, 5 mm in width and 0.013 mm in thickness (13 탆) was prepared. Using a thermomechanical analyzer (trade name "TMA8311" manufactured by Rigaku Corporation) (Diameter of tip: 0.5 mm) at 500 mN pressure onto the film under the conditions of a temperature of from room temperature (캜) / 캜 to a temperature of 30 캜 to 550 캜 (scanning temperature) The softening temperature (softening point) was calculated on the basis of measurement data in accordance with the method described in JIS K7196 (1991), except that the measurement sample was used for measuring the softening temperature.

<Measurement of 5% weight reduction temperature (Td 5%)>

The values (unit: 占 폚) of the 5% weight reduction temperature (Td 5%) of the polyimide obtained in each of the Examples and Comparative Examples were obtained by using the polyimide films prepared in each of the Examples and Comparative Examples, (TG / DTA220, manufactured by SII, Nanotechnology Co., Ltd.) was used, and the scanning temperature was set to 30 to 550 DEG C, and nitrogen gas was flown under a nitrogen atmosphere at a rate of 10 DEG C / min And measuring the temperature at which the weight of the used sample was reduced by 5%.

&Lt; Measurement of total light transmittance, haze (turbidity) and yellowness (YI)

The values (unit:%), haze (turbidity: HAZE) and yellowness (YI) of the total light transmittance of the polyimide obtained in each of the Examples and Comparative Examples were measured as the samples for measurement , And the measurement was carried out using a measuring device "Hazemeter NDH-5000" manufactured by Nippon Denshoku Kogyo Co., Ltd. or "spectrophotometer SD6000" available from Nippon Denshoku Kogyo Co., Ltd. . Further, the total light transmittance and haze were measured with a trade name &quot; Hazemeter NDH-5000 &quot;, manufactured by Nippon Denshoku Kogyo Co., Ltd., and the degree of yellowness was measured with a trade name &quot; Spectral Color Spectrometer SD6000 &quot;, manufactured by Nippon Denshoku Kogyo Co., did. The total light transmittance was determined by performing measurement in accordance with JIS K7361-1 (published in 1997), and the haze (turbidity) was obtained by performing measurement in accordance with JIS K7136 (published in 2000) ) Was obtained by carrying out measurements in accordance with ASTM E313-05 (published in 2005).

&Lt; Measurement of coefficient of linear expansion (CTE) >

The coefficient of linear expansion was obtained by forming films having a size of 20 mm in length, 5 mm in width, and 13 m in thickness from the polyimide (film-shaped polyimide) obtained in each example and each comparative example, (Dry film) obtained by drying (120 ° C, 1 hour (Hr)) and heat treatment at 200 ° C for 1 hour (Hr) in a nitrogen atmosphere were respectively used. A thermomechanical analyzer Under the conditions of a tensile mode (49 mN) and a temperature raising rate of 5 deg. C / min under the nitrogen atmosphere and measuring the change in length of the sample at 50 deg. C to 200 deg. C, And the average value of the change in length per 1 DEG C in the temperature range of 200 DEG C was determined.

(Example 1)

&Lt; Preparation process of CpODA &

According to the method described in Synthesis Example 1, Example 1 and Example 2 of International Patent Publication No. 2011/099518, a compound represented by the following general formula (13):

Spiro-? -Cyclopentanone-? '- spiro-2 "-norbornane-5,5", 6,6 "-tetracarboxylic acid dianhydride: CpODA) .

&Lt; Production process of polyamic acid >

First, a 30 ml three-necked flask was sufficiently dried by heating with a heat gun. Subsequently, the atmosphere gas in the sufficiently dried three-necked flask was replaced with nitrogen, and the atmosphere in the three-way flask was changed to nitrogen atmosphere. Subsequently, as the aromatic diamine (diamine compound), the following general formula (14):

(15.00 mmol, manufactured by Seika Chemical Co., Ltd.) represented by the following formula (1) was added, and then 33.8 g of tetramethylurea (TMU) (poly (Amount of the amide acid was 20 mass% (mass%)) was further added and stirred to obtain a dissolution liquid by dissolving aromatic diamine (TFMB) in the tetramethylurea.

Then, 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (13) and the compound represented by the general formula (11) as the tetracarboxylic acid dianhydride were mixed in a three- (2.75 g, 12.75 mmol) of pyromellitic anhydride (anhydrous pyromellitic acid: PMDA: manufactured by TOKYO KASEI KOGYO CO., LTD.) Was added to the mixture, and the mixture was stirred at room temperature (25 ° C) for 12 hours under a nitrogen atmosphere, Solution. Thus, a polyamic acid was formed in the reaction solution.

A part of the reaction solution (tetramethylurea solution of polyamic acid: polyamic acid solution) was used to prepare a tetramethylurea solution having a polyamic acid concentration of 0.5 g / dL. As described above, The intrinsic viscosity [?] Of the polyamic acid as the reaction intermediate was measured, and the intrinsic viscosity [?] Of the polyamic acid was 0.76 dL / g.

&Lt; Process for producing polyimide-containing film: Processes (i) to (iii)

(Process (i): solvent removal treatment)

Alkali glass (trade name: Eagle XG, length: 100 mm, width: 100 mm, thickness: 0.7 mm, made by Corning Inc.) was prepared as a glass substrate and the reaction solution (polyamic acid solution) On the surface of the glass substrate, a coating film was formed on the glass substrate by spin coating so that the thickness of the coated film after heat curing became 13 占 퐉. Thereafter, the glass substrate on which the coating film was formed was placed on a hot plate at 60 DEG C and allowed to stand for 2 hours, and the solvent was removed by evaporation (solvent removal treatment).

(Step (ii): heating step after solvent removal treatment)

After the solvent removal treatment as described above, the glass substrate on which the coating film was formed was placed in an inert gas oven in which nitrogen flowed at a flow rate of 3 L / min. In an inert gas oven, Heated for 0.5 hour at a temperature condition of 135 占 폚 and finally heated for one hour at a temperature condition of 350 占 폚 (hereinafter referred to as &quot; final heating temperature condition &quot; according to circumstances) And cured to obtain a polyimide-coated glass on which a thin film (polyimide film) containing polyimide was coated on the glass substrate.

(Process (iii): process for recovering the film)

The thus obtained polyimide-coated glass was immersed in boiled water at 90 DEG C and the polyimide film was peeled off from the glass substrate to obtain a polyimide film (length: 100 mm, width 100 mm, thickness 13 mu m ) Was recovered to obtain a film containing polyimide.

Further, in order to identify the molecular structure of the compound forming the thus obtained film, IR spectrum was measured using an IR measuring device (trade name: FT / IR-4100, manufactured by Nihon Bunko K.K.). The IR spectrum as a result of this measurement is shown in Fig. As apparent from the results shown in Fig. 1, in the compound constituting the film formed in Example 1, C = O stretching vibration of imidocarbonyl was observed at 1715.3 cm ^-1 . From the molecular structure identified based on these results and the like, it was confirmed that the obtained film contained polyimide.

The polyimide obtained in this way is a polymer obtained by polymerizing a repeating unit (repeating unit corresponding to the repeating unit (A)) corresponding to the repeating unit represented by the general formula (1) and a repeating unit (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is such that the molar ratio Repeating unit]: [repeating unit corresponding to repeating unit (B)]) is 15:85. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Example 2)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, Instead of using a mixture of 1.1534 g (3.00 mmol) of the compound (CpODA) represented by the above general formula (13) and 2.6172 g (12.00 mmol) of the pyromellitic anhydride (PMDA) Mixture, and also

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 34.30 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

The obtained polyimide can be obtained by using the kind of the monomers used or the ratio thereof and the number of repeating units (repeating units corresponding to the repeating units (A)) corresponding to the repeating units represented by the general formula (1) (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is a mole ratio Unit]: [repeating unit corresponding to repeating unit (B)]) is 20:80.

(Example 3)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (1.50 mmol) of the compound (CpODA) represented by the general formula (13) and 2.9446 g (13.50 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) Mixture, and also

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 33.30 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

The obtained polyimide can be obtained by using the kind of the monomers used or the ratio thereof and the number of repeating units (repeating units corresponding to the repeating units (A)) corresponding to the repeating units represented by the general formula (1) (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is a mole ratio Unit]: [repeating unit corresponding to repeating unit (B)]) is 10:90.

(Example 4)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (4.50 mmol) of the compound (CpODA) represented by the general formula (13) and 2.2903 g (10.50 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) (Polyimide film) containing polyimide was obtained in the same manner as in Example 1, except that TMU in an amount such that the concentration of polyamic acid in the reaction liquid became 20 mass% was used. Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

The obtained polyimide can be obtained by using the kind of the monomers used or the ratio thereof and the number of repeating units (repeating units corresponding to the repeating units (A)) corresponding to the repeating units represented by the general formula (1) (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is a mole ratio Unit]: [repeating unit corresponding to repeating unit (B)]) is 30:70.

(Example 5)

Except that the final heating temperature condition adopted in the step (ii) of the production process of the film containing polyimide was changed from 350 占 폚 to 300 占 폚, a thin film containing polyimide (polyimide Film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Example 6)

(Polyamic acid solution) used in the step (i) of the production process of the polyimide-containing film was mixed with 42.25 g (20 mass% solution of polyamic acid) of the reaction solution obtained by performing the production process of polyamic acid (15): &lt; EMI ID =

0.8 parts by weight of an accelerator (manufactured by Tokyo Ohka Kogyo K.K.) containing an imidazole-based compound represented by the following formula (1) in an amount of 10 parts by weight based on 100 parts by weight of a solid component (polyamic acid) in a polyamic acid solution) (Reaction solution (polyamic acid solution) to which the above promoter was added)

Further, in the same manner as in Example 1 except that the final heating temperature condition employed in the step (ii) of the production process of the film containing polyimide was changed from 350 캜 to 300 캜, a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Example 7)

(Polyamic acid solution) used in the step (i) of the production process of the polyimide-containing film was mixed with 42.25 g (20 mass% solution of polyamic acid) of the reaction solution obtained by performing the production process of polyamic acid 0.8450 g of an accelerator (manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing an imidazole-based compound represented by the above general formula (15) (10 parts by mass to 100 parts by mass of a solid component (polyamic acid) in a polyamic acid solution (Polyamic acid solution) added with the above-mentioned accelerator,

The final heating temperature condition employed in the step (ii) of the production process of the film containing polyimide was changed from 350 캜 to 300 캜,

Further, in the step (ii) of the production process of a film containing polyimide, the atmosphere gas used is changed from nitrogen to air (the gas flowing in the inner oven is changed from nitrogen to air, , A thin film (polyimide film) containing polyimide was obtained in the same manner as in Example 1. Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Example 8)

Instead of using 4.8035 g (15.00 mmol: manufactured by Seika Kagaku Co., Ltd.) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) represented by the above general formula (14) as an aromatic diamine alone, 4.7074 g (14.7 mmol) of the compound (TFMB) represented by the formula (14) and 0.4020 g (corresponding to 0.3 mmol) of an amino-modified silicone oil (trade name "X-22-9409" available from Shin-Etsu Chemical Co., The mixture was used,

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 35.02 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

The obtained polyimide can be obtained by using the kind of the monomers used or the ratio thereof and the number of repeating units (repeating units corresponding to the repeating units (A)) corresponding to the repeating units represented by the general formula (1) (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is a mole ratio Unit]: [repeating unit corresponding to repeating unit (B)]) is 15:85.

(Comparative Example 1)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (6.00 mmol) of the compound (CpODA) represented by the general formula (13) and 1.9631 g (9.00 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) Mixture, and also

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 36.3 g (the amount of the polyamic acid in the reaction liquid was 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

The obtained polyimide can be obtained by using the kind of the monomers used or the ratio thereof and the number of repeating units (repeating units corresponding to the repeating units (A)) corresponding to the repeating units represented by the general formula (1) (The repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the formula (2), and the content ratio of these repeating units is a mole ratio Unit]: [repeating unit corresponding to repeating unit (B)]) is 40:60.

(Comparative Example 2)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, , 3.2718 g (15.00 mmol) of pyromellitic anhydride (PMDA) represented by the above-mentioned general formula (11) was used alone,

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 32.3 g (the amount of the polyamic acid in the reaction liquid was 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1. The content of the repeating unit (repeating unit corresponding to the repeating unit (B)) corresponding to the repeating unit represented by the above-mentioned general formula (2) is 100 moles %.

(Comparative Example 3)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, Instead of using a mixture of the following general formula (16):

4.4133 g (15.00 mmol) of a compound (4,4'-biphthalic anhydride: BPDA: manufactured by Tokyo Kasei Kogyo Co., Ltd.) represented by the following formula

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 36.9 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 4)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, , 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (13) and 4,4'-biphthalic anhydride (BPDA: (CpODA: BPDA = 15:85) of 3.7513 g (12.75 mmol) of CpODA and BPDA (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 37.7 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 5)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, , 3.2718 g (15.00 mmol) of pyromellitic anhydride (PMDA) represented by the above-mentioned general formula (11) was used alone and the aromatic diamine represented by the general formula (14) Instead of using 4.8035 g (15.00 mmol: manufactured by Seika Chemical Co., Ltd.) of 2'-bis (trifluoromethyl) benzidine (TFMB)

, 3.1844 g (15.00 mmol) of a compound represented by the following formula (m-tolidine: m-Tol: manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 25.8 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 6)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, , 4.4133 g (15.00 mmol) of the compound represented by the above general formula (16) (4,4'-biphthalic anhydride: BPDA: manufactured by TOKYO KASEI KOGYO CO., LTD.) Was used alone,

Instead of using 4.8035 g (15.00 mmol: manufactured by Seika Chemical Co., Ltd.) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) represented by the above general formula (14) as an aromatic diamine, 3.1844 g (15.00 mmol) of the compound (m-Tol) represented by the formula (17)

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 30.4 g (the amount of the polyamic acid in the reaction liquid became 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 7)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (18): &lt; EMI ID =

(2.25 mmol) of a compound (1,2,4,5-cyclohexanetetracarboxylic dianhydride: CHDA) represented by the general formula (11) and 2.7810 g of pyromellitic anhydride (PMDA) 12.75 mmol), and

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 32.4 g (the amount of the polyamic acid in the reaction liquid was 20% by mass), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 8)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (19): &lt; EMI ID =

, 0.4728 g (2.25 mmol) of a compound (1,2,3,4-cyclopentanetetracarboxylic acid dianhydride: CPDA) represented by the general formula (11) and 2.7810 g of pyromellitic anhydride (PMDA) 12.75 mmol), and

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 32.2 g (the amount of the polyamic acid in the reaction liquid was 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 9)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, (20): &lt; EMI ID =

(2.25 mmol) of a compound (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride: CBDA) represented by the general formula (11) and 2.7810 g of pyromellitic anhydride (PMDA) represented by the general formula (11) 12.75 mmol), and

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 32.1 g (the amount of the polyamic acid in the reaction liquid was 20% by mass), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 10)

Instead of using 4.8035 g (15.00 mmol: manufactured by Seika Chemical Co., Ltd.) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) represented by the above general formula (14) as an aromatic diamine, 3.1844 g (15.00 mmol) of the compound (m-Tol) represented by the formula (17)

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 27.3 g (the amount of the polyamic acid in the reaction liquid was 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

(Comparative Example 11)

(2.75 mmol) of the compound (CpODA) represented by the general formula (13) and 2.7810 g (12.75 mmol) of the pyromellitic anhydride (PMDA) represented by the general formula (11) as the tetracarboxylic dianhydride, , 0.8650 g (2.25 mmol) of the compound (CpODA) represented by the general formula (13) and 4,4'-biphthalic anhydride (BPDA: (CpODA: BPDA = 15:85) of 3.7513 g (12.75 mmol) of CpODA and BPDA (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

Instead of using 4.8035 g (15.00 mmol: manufactured by Seika Chemical Co., Ltd.) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) represented by the above general formula (14) as an aromatic diamine, 3.1844 g (15.00 mmol) of the compound (m-Tol) represented by the formula (17)

Except that the amount of tetramethylurea (TMU) used was changed from 33.8 g to 31.2 g (the amount of the polyamic acid in the reaction liquid was 20 mass%), a thin film containing polyimide Polyimide film). Further, the IR spectrum of the obtained film was measured, and it was confirmed that such a film contains polyimide. The evaluation results of properties (Tg and softening temperature obtained by the above evaluation method of properties, etc.) are shown in Table 1.

As is evident from the results shown in Table 1, all of the films comprising the polyimide of the present invention (Examples 1 to 8) have a total light transmittance of 85% or more, indicating that the transparency is sufficiently high. The films including the polyimides of the present invention (Examples 1 to 8) were all films having a yellowness index (YI) of 16 or less (Examples 1 to 6 and 8 obtained by heating in a nitrogen atmosphere) 11 or less), and the CTE was -20 ppm / K to 20 ppm / K. As described above, the films including the polyimides of the present invention (Examples 1 to 8) all have a sufficiently high total light transmittance and a sufficiently low yellowing degree to such an extent that they can be used for applications requiring visibility, It has been confirmed that it has the same coefficient of linear expansion as that of the inorganic material of. That is, it has been confirmed that the films comprising the polyimides of the present invention (Examples 1 to 8) all have a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level. As apparent from the results shown in Table 1, the polyimide of the present invention (Examples 1 to 8) has Tg of 300 DEG C or higher, softening temperature of 300 DEG C or higher (softening point), 400 DEG C or higher Or more) and has a sufficiently high level of heat resistance. It is also seen that the polyimides of the present invention (Examples 1 to 8) have a haze (turbidity: HAZE) of 5 or less (a value of 1.1 or less) and a sufficiently low haze.

On the other hand, the polyimides obtained in Comparative Examples 1 and 2 had a high coefficient of linear expansion exceeding 20 ppm / K, and did not have a sufficiently low linear expansion coefficient. The polyimide obtained in Comparative Example 2 has a total light transmittance of less than 83.0, and has a very high level of light transmittance (the total light transmittance is preferably not less than 83.0, Permeability of not less than 85.0, preferably not less than 85.0).

These results and the structure of the polyimide obtained in Examples 1 to 8 and Comparative Examples 1 and 2 (in which the polyimide obtained in Comparative Example 1 contains the repeating unit (A) relative to the total amount of the repeating units (A) and (B) And the content of the repeating unit (B) is 100 mol% (the content of the repeating unit (A) is 0 mol%)), and the polyimide obtained in Comparative Example 2, The polyimide containing the repeating units (A) and (B) and having the proportion of the repeating unit (A) relative to the total amount of the repeating units (A) and (B) is 5 to 35 mol% (Preferably, a total light transmittance of not less than 83.0, more preferably not less than 85.0) and a sufficiently low yellowness (preferably YI of not more than 16) and a sufficiently low coefficient of linear expansion (preferably -20 ppm / CTE in the range of 20 ppm / K) to a higher level It can be seen that as having base.

Further, as compared with Example 1, in the case of using BPDA (aromatic tetracarboxylic acid dianhydride) instead of PMDA (aromatic tetracarboxylic acid dianhydride) in the mixture of tetracarboxylic dianhydride (Comparative Example 4) , The total light transmittance could not be made sufficiently high, and the value of YI was 18.2, so that the yellowness could not be made sufficiently low. In addition, in the case of using BPDA (aromatic tetracarboxylic acid dianhydride) (Comparative Example 4), the linear expansion coefficient was 60.7 ppm / K, and the coefficient of linear expansion could not be made sufficiently low. Thus, in the case of using BPDA (aromatic tetracarboxylic acid dianhydride) instead of PMDA (aromatic tetracarboxylic dianhydride) in the mixture of tetracarboxylic dianhydride (Comparative Example 4), the sufficiently low yellow color It can be understood that a sufficiently low coefficient of linear expansion can not be achieved. In contrast to the case where the tetracarboxylic acid dianhydride was solely composed of BPDA (Comparative Example 3), when the tetracarboxylic dianhydride was a mixture of BPDA and CpODA (Comparative Example 4), the value of the yellowness index (YI) When the kind of the aromatic tetracarboxylic dianhydride to be combined with CpODA is other than PMDA, it is necessary to sufficiently increase the total light transmittance, the sufficiently low yellow color and the sufficiently low linear expansion coefficient to a higher level It can be understood that it can not be equally distributed.

Further, in contrast to Example 1, in the mixture of the tetracarboxylic dianhydride, CHDA, CPDA or CBDA (aliphatic tetracarboxylic dianhydride) was used instead of CpODA (aliphatic tetracarboxylic dianhydride) , The total light transmittance was less than 83% and the total light transmittance at a sufficiently high level of 83% or more could not be obtained in the case of using (CHDA: Comparative Example 7, CPDA: Comparative Example 8, CBDA: Comparative Example 9) Able to know.

Further, as compared with Example 1, in the case of using m-Tol having no fluorine-based substituent (Comparative Example 10) instead of using TFMB having a fluorine-based substituent as an aromatic diamine, the value of YI was 44.6 And the yellowness degree could not be made sufficiently low (YI of 16 or less). And the value of the total light transmittance is 75.4%, which means that the total light transmittance at a sufficiently high level of 83% or more can not be obtained. Likewise, in the case of using m-Tol having no fluorine-based substituent (Comparative Example 11) instead of using TFA in which BPDA was used instead of PMDA as an aromatic dianhydride and TFMB having a fluorine-based substituent was used as an aromatic diamine, , The value of YI was 23.2, and the yellowness value could not be made sufficiently low (YI of 16 or less). And the total light transmittance is 79.6%, which means that the total light transmittance at a sufficiently high level of 83% or more can not be obtained.

In contrast to Comparative Example 2 and Comparative Example 5, the types of aromatic diamines used in the production of the polyimide are different. From the kind of the aromatic diamine, an arylene group having a fluorine-containing substituent (tetrafluoromethyl group) It was confirmed that the value of yellowness (YI) of the polyimide was lower than that of the polyimide when it was introduced into the repeating unit (Comparative Example 2). Likewise, in comparison with Comparative Example 3 and Comparative Example 6, the types of aromatic diamines used in the production of the polyimide are different. From the kind of the aromatic diamine, it is possible to use arylene having a fluorine-containing substituent (tetrafluoromethyl group) It was confirmed that the value of yellowness (YI) of the polyimide was lower in the case where the group was introduced into the repeating unit (Comparative Example 3). In contrast to Comparative Example 4 and Comparative Example 11, the type of aromatic diamine used in the production of the polyimide is different. From the kind of the aromatic diamine, an arylene group having a fluorine-containing substituent (tetrafluoromethyl group) It was confirmed that the value of yellowness (YI) of the polyimide was lower than that of the polyimide when it was introduced into the repeating unit (Comparative Example 4).

Considering the difference (tendency) of the effect due to the kind of aromatic diamine and the results of Examples 1 to 4, it is preferable that the composition contains the repeating units (A) and (B) ) And the proportion of the repeating unit (A) relative to the total amount of the repeating unit (A) and the repeating unit (B) is 5 to 35 mol%, a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion As shown in FIG.

The polyimide obtained in Example 7 was obtained in the same manner as in Example 6 except that air was used as the atmosphere gas in the heating step (obtained by using the polyamic acid of the present invention). Here, in general, when polyimide is produced using an aliphatic acid dianhydride and heating (firing) at a high temperature of about 300 DEG C is required, it is preferable to use a polyimide having a weight of at least 500 ppm or more When a polyimide is produced by firing a polyamic acid in an atmosphere containing an oxygen, the polyimide tends to be discolored by oxygen oxidation or be brittle due to a decrease in molecular weight accompanied by the main chain cleavage of the polymer by oxygen oxidation Is known. Therefore, in the case of producing a polyimide having high transparency by using an aliphatic acid dianhydride, in order to ensure higher visibility and the like, an inert gas (for example, an inert gas containing an inert gas and having an oxygen concentration of In an atmosphere of 100 ppm or less), polyamide acid is generally fired to obtain polyimide. On the contrary, although the polyimide of the present invention obtained in Example 7 was obtained by heating (firing) the polyamic acid in the air, the total light transmittance was 86% or more and not only had a very high transparency, It can be seen that the yellowness index (YI) of the polyimide is 16 or less. From these results, it is found that the polyamic acid of the present invention (Examples 1 to 8) has a high oxygen concentration condition (for example, an oxygen concentration of 500 ppm or more In the case of producing a polyimide for use in a product such as a field in which it is necessary to adopt a condition in which oxygen is generated, and the like, it is possible to make the polyimide sufficiently visible even after the production or use, It has become clear that it is particularly useful for the production of polyimides for use in products in the same fields as the above. In addition, the polyimide of the present invention obtained in Example 7 has a coefficient of linear expansion equal to that of Example 6 or Example 1 in which firing is performed in nitrogen (CTE: 1.2 ppm / K) It can be seen that it has a sufficiently low coefficient of linear expansion. It is understood from the results shown in Table 1 that although the polyimide of the present invention obtained in Example 7 was obtained by heating (firing) the polyamic acid in the air, as described above, the Tg of 300 deg. It has a softening point (softening point) of 400 ° C or higher (preferably 450 ° C or higher) and a Td of 5%, and it has a sufficiently high level of heat resistance.

From these results, it was found that the polyamic acid of the present invention (Examples 1 to 8) can be used even in the case of firing in a nitrogen atmosphere (Examples 1 to 6 and 8), regardless of the atmosphere during heating (firing) It is possible to sufficiently suppress the coloration of the obtained polyimide even when the polyimide is fired in air (Example 7), to obtain a polyimide having a high transparency and a sufficiently low coefficient of linear expansion while sufficiently suppressing an increase in yellowness Able to know.

<Laser peelability of the polyimide films obtained in Examples 1 to 8>

In the process for producing a polyimide-containing film, the step (iii) (the recovery step of the film: the polyimide-coated glass is immersed in boiling water at 90 캜 and the polyimide film is peeled off from the glass substrate, Except that the step of obtaining a film was carried out in the same manner as in Examples 1 to 8, respectively. Then, each of the polyimide-coated glasses was irradiated with a laser, and measurements regarding the peeling and the like of the peeling were made. That is, the irradiation energy density of the laser was set to 50 to 320 mJ / cm 2 (low energy density (50 mJ / cm 2)) using a product "pm848 (excimer laser XeCl, 308 nm, maximum pulse energy 320 mJ / / Cm &lt; 2 &gt;), the energy density was gradually raised every 10 mJ / cm &lt; 2 &gt; until peeling was confirmed and the irradiation energy density at which the peeling was confirmed was used), the pulse width was set to 20 to 30 ns, Of the surface of the polyimide-coated glass was set to 50%, the laser repetition frequency (repetition rate) was set to 30 Hz, and the irradiation surface shape of the laser beam was set to be a rectangle of 14 mm long and 30 mm wide, (Judged to be peelable when Newton rings were seen), presence or absence of coloration, and presence or absence of shot unevenness were visually determined.

As a result, all of the polyimide-coated glasses obtained by employing the steps similar to those of Examples 1 to 8 were found to have an overlapping ratio (overlapping ratio) of 50% at an irradiation energy density of 140 mJ / It can be peeled off without shots (Newton ring can be confirmed). From these results, it was found that the film comprising the polyimide of the present invention was peeled while sufficiently suppressing the change in quality by irradiating a laser beam when the film was laminated on glass (in the case of a laminate on a glass substrate) It is also possible to know. From these results, it can be seen that a film including the polyimide of the present invention is laminated on a glass substrate (so-called carrier substrate or the like), and then a thin film transistor or the like is directly mounted on the film, It is also apparent that the film containing the polyimide of the present invention can be suitably applied to a method of manufacturing a display or the like on which a thin film transistor or the like is mounted.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to efficiently form a polyimide and a polyimide thereof, which makes it possible to uniformly obtain a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level , A solution of the polyamic acid, and a polyimide film containing the polyimide.

The polyimide of the present invention has a sufficiently high total light transmittance, a sufficiently low yellow color and a sufficiently low coefficient of linear expansion to a higher level, so that it can be used as a film for a flexible wiring substrate, A transparent conductive film for organic electroluminescence (EL), an organic EL lighting film, a flexible substrate film, a flexible substrate film for flexible organic EL, a flexible transparent conductive film, an organic thin film solar cell transparent A conductive film, a transparent conductive film for a dye-sensitized solar cell, a flexible gas barrier film, a film for a touch panel, a front film for a flexible display, a back film for a flexible display, a TFT substrate for a flexible display, , A photoresist, an image sensor It is particularly useful as a material such as a micro lens.

Claims (6)

(1): &lt; EMI ID =

R ¹ , R ² and R ³ in the formula (1) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,
(A) represented by the formula
(2): &lt; EMI ID =

[In the formula (2), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]
, And the content of the repeating unit (A) relative to the total amount of the repeating units (A) and (B) is 5 to 35 mol%. The compound according to claim 1, wherein R ¹⁰ in the general formulas (1) and (2)

[In the formula (3), R ⁵ represents a fluoroalkyl group having 1 to 10 carbon atoms]
Is polyimide. The polyimide according to claim 1 or 2, wherein the content of the repeating unit (A) relative to the total amount of the repeating units (A) and (B) is 5 to 25 mol%. (4): &lt; EMI ID =

Wherein R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorine atom, and R ¹⁰ is a group having a fluorine-containing substituent An arylene group having 6 to 40 carbon atoms, and n represents an integer of 0 to 12,
(C) represented by the general formula
(5): &lt; EMI ID =

[In the formula (5), R ¹⁰ represents an arylene group having 6 to 40 carbon atoms and having a fluorine-containing substituent]
, And the content of the repeating unit (C) relative to the total amount of the repeating units (C) and (D) is 5 to 35 mol%. A polyamic acid solution comprising the polyamic acid according to claim 4 and an organic solvent. A polyimide film comprising the polyimide according to any one of claims 1 to 12.

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