TW201837083A - Polyimide film - Google Patents

Abstract

The subject of the present invention is to provide a highly colorless transparent polyimide film. The polyimide film shows excellent performance in heat resistance, transparency, and strength as same as that of convention film, as well as can be produced at a lower cost than conventional film, and has a higher resistance to methyl ethyl ketone than a conventional colorless transparent polyimide film. The colorless transparent polyimide film according to the present invention is made of a specific polyimide resin. The specific polyimide resin at least comprises a tetracarboxylic acid-based compound-derived moiety including a biphenyltetracarboxylic acid-based compound-derived moiety and an aromatic tetracarboxylic acid-based compound-derived moiety having an ether group; and at least comprises a diamine-derived moiety including an aromatic diamine-derived moiety having a fluorine group and an aromatic diamine-derived moiety having sulfo group. And also, the polyimide film has haze value within a range of from 0.1 or more to 2.0 or less.

Description

Polyimine film

The present invention relates to a polyimide film which is substantially colorless and transparent, and particularly relates to a polyimide film which is substantially colorless and transparent, which is suitable for an optical fiber, a substrate for a liquid crystal display surface, a substrate for light emission, a protective sheet, and the like.

Polyimine films generally have excellent thermal stability, electronic properties, and mechanical properties, and are suitable for use in a variety of products that can be used in harsh environments. On the other hand, the polyimide film is also mostly cloudy due to excessive heat which is formed until the film formation, or has a yellow or brown colored substance. When the white fluorinated polyimide film or the colored polyimide film is used as a film substrate of a liquid crystal display device, it is feared that the visual field is not only darkened, but also the original function of the liquid crystal display device is impaired. . Therefore, in order to solve such problems, a colorless and transparent polyimide film has been developed. In addition, the colorless and transparent polyimide film can be used as a film for a wide range of liquid crystal display devices, optical fiber cable coatings, waveguides, and solar cell protective coatings (for example, For example, JP-A-62-7733, JP-A-2000-313804, JP-A-2012-040836, and the like. "Prior Technical Literature" "Concession Literature"

Japanese Laid-Open Patent Publication No. 2000-313804.

However, the colorless and transparent polyimine film proposed in the past has become a high price due to the high raw material cost, so that it becomes a problem that is quite unacceptable on the market. Further, the conventional colorless and transparent polyimide film has poor resistance to methyl ethyl ketone used in the production of a flexible printed circuit board or the like, and may be broken or broken when tension is applied. situation.

An object of the present invention is to provide an excellent heat resistance, transparency, and strength which are the same as conventional ones, and which can be produced at a lower cost than conventionally, and which has a higher color than a conventional colorless and transparent polyimide film. A colorless transparent polyimide film for the resistance of methyl ethyl ketone. "Means to solve the problem"

The polyimine film according to one aspect of the present invention is composed of a specific polyimine resin. Further, in the present invention, the polyimide film also includes a film, a sheet, or a tubular body. The specific polyimine resin system includes at least a biphenyltetracarboxylic acid compound (BPDA)-derived site, a tetracarboxylic acid-based compound-derived site having an ether group-containing aromatic tetracarboxylic acid-based compound-derived site, and at least A diamine-derived moiety having a fluorine-based aromatic diamine-derived moiety and an aromatic diamine-derived moiety having a sulfo group. In the present invention, the tetracarboxylic acid-based compound-derived moiety means a tetracarboxylic acid-inducing body such as "tetracarboxylic acid" or "tetracarboxylic dianhydride or tetracarboxylic acid diester". The part; the so-called diamine-derived part means a part derived from "diamine". Further, the specific polyimine resin may be a tetracarboxylic acid-based compound-derived site derived from a biphenyltetracarboxylic acid-based compound (BPDA)-derived site and an aromatic tetracarboxylic acid-based compound-derived site having an ether group. And may be composed of a diamine-derived moiety derived from an aromatic diamine having a fluorine group and an aromatic diamine-derived moiety having a sulfo group. Further, it is preferable that all of the tetracarboxylic acid compound-derived sites are sites derived from the aromatic tetracarboxylic acid compound; and the diamine-derived sites are preferably all derived from the aromatic diamine. Further, the film thickness of the polyimide film according to the present invention is preferably in the range of 5 μm or more and 50 μm or less, preferably in the range of 7.5 μm or more and 40 μm or less, and more preferably in the range of 10 μm or more and 30 μm or less. Further, when the film thickness of the polyimide film is 25 μm, the haze of the polyimide film is in the range of 0.1 or more and 2.0 or less. A colorless transparent polyimide film having a haze of 2.0 or less can stably pass light when used in a liquid crystal display device or the like.

Further, the colorless and transparent polyimine film according to the present invention is formed of a polyimide precursor solution prepared by using a specific monomer. The polyimine precursor solution is obtained by reacting a specific tetracarboxylic acid compound with a specific diamine in a polar organic solvent. Further, when the polyimine precursor solution is prepared, all known aromatic tetracarboxylic acid compounds or aromatic diamines can be added to the extent that the essence of the present invention is not impaired. In addition, the molar ratio of each of the tetracarboxylic acid compounds in the plurality of kinds of tetracarboxylic acid compounds can be appropriately adjusted in accordance with the purpose and use of the colorless transparent polyimide film.

It may be used as an organic solvent used for preparing the above-mentioned polyimine precursor solution, and may be, for example, N,N-dimethylacetamide (DMAc), N,N-dimethyl Carbenamide (DMF), N,N-diethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone (NMP), phenol, cresol, Xylenol, resorcinol, 3-chlorophenol, 4-chlorophenol, 3-bromophenol, 4-bromophenol, 2-chloro-5-hydroxytoluene, diethylene glycol dimethyl ether, triethylene glycol Dimethyl ether, cyclobutyl hydrazine, γ-butyrolactone, tetrahydrofuran, and dioxolane. Among these, N,N-dimethylacetamide (DMAc) is more suitable for the user. Further, these solvents may be used in combination of two or more kinds.

Further, a dispersing agent, a solid lubricant, an anti-settling agent, a leveling agent, a surface conditioner, and a moisture absorbent may be added to the above-mentioned polyimine precursor solution in a range not impairing the essence of the present invention. , gelling preventive agent, antioxidant, ultraviolet absorber, light stabilizer, plasticizer, anti-conjuncting agent, surfactant, antistatic agent, antifoaming agent, antibacterial agent, antifungal agent, preservative, tackifier Well known additives.

Further, the colorless and transparent polyimine film according to the present invention is obtained by forming a coating film from the above polyimide precursor solution, and performing ruthenium conversion on the coating film.

Further, in the specific polyimine resin of the above polyimine film, the molar fraction of the biphenyltetracarboxylic acid compound (BPDA)-derived portion relative to the entire tetracarboxylic acid-based compound-derived portion The ratio is preferably in the range of 70 mol% or more and 99 mol% or less; more preferably in the range of 80 mol% or more and 97.5 mol% or less; more preferably in the range of 90 mol% or more and 95 mol% or less. This is because the polyamidene film having a molar ratio of 50 mol% or more with respect to the biphenyltetracarboxylic acid compound (BPDA) derived from the tetracarboxylic acid compound-derived compound has a high glass transition temperature, and is used in the production of liquid crystal. When a display device, a flexible printed circuit board, or the like is used, sufficient heat resistance can be maintained when welding or the like is performed.

The biphenyltetracarboxylic acid compound (BPDA)-derived site, although formed of a biphenyltetracarboxylic acid-based compound (BPDA), may, for example, be a biphenyltetracarboxylic acid-based compound (BPDA), for example. "Biphenyltetracarboxylic acid" or "biphenyltetracarboxylic dianhydride, and a biphenyltetracarboxylic acid inducer such as a biphenyltetracarboxylic acid diester". Further, the biphenyltetracarboxylic acid can be obtained by hydrolyzing a biphenyltetracarboxylic dianhydride by a known method; the biphenyltetracarboxylic acid diester can be a biphenyltetracarboxylic acid by a known method. The acid dianhydride is obtained by diesterification.

Further, in the specific polyimine resin which forms the polyimine film described above, the moieties of the aromatic tetracarboxylic acid compound-derived moiety having an ether group with respect to all the tetracarboxylic acid compound-derived sites are The fraction is preferably in the range of 1 mol% or more and 30 mol% or less; more preferably in the range of 2.5 mol% or more and 20 mol% or less; more preferably in the range of 5 mol% or more and 10 mol% or less. This is because the polyimide film composed of a specific polyimine resin such as this is extremely low in degree of clouding and capable of maintaining high transparency.

The aromatic tetracarboxylic acid compound-derived moiety having an ether group is formed of an aromatic tetracarboxylic acid compound having an ether group. For example, the aromatic tetracarboxylic acid compound having an ether group may be, for example, "Aromatic tetracarboxylic acid having an ether group" or "aromatic tetracarboxylic dianhydride having an ether group" and an aromatic tetracarboxylic acid inducer having an ether group such as an aromatic tetracarboxylic acid diester having an ether group "." Further, in the present invention, the aromatic tetracarboxylic dianhydride having an ether group may, for example, be, for example, 2,2-bis[3,4-(dicarboxyphenoxy)phenyl]propane dianhydride (BPADA). ), 5,5'-oxybis(isobenzofuran-1,3-dione) (ODPA), 4,4'-oxybis(isobenzofuran-1,3-dione), 4,5 '-Oxygen bis(isobenzofuran-1,3-dione), 5,5-[1,4-phenylenebis(oxy)]bis(isobenzofuran-1,3-dione), 4,4'-[2,1-Extenophenylbis(oxy)]bis(isobenzofuran-1,3-dione), 3,3'-(p-phenylenedioxy)diphthalic anhydride , 5,5'-[1,2-phenylenebis(oxy)bis(isobenzofuran-1,3-dione), 5,5'-[1,3-phenylene bis(oxygen) Bis(isobenzofuran-1,3-dione), 4,4'-[m-phenylenebis(oxy)bis(isobenzofuran-1,3-dione), 4,5'- [1,4-phenylenebis(oxy)bis(isobenzofuran-1,3-dione), 1,4-bis(dicarboxyphenoxy)phthalic anhydride, and the like. Among these, 2,2-bis[3,4-(dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 5,5'-oxybis(isobenzofuran-1,3- Diketone) (ODPA) is more suitable for use. Further, the aromatic tetracarboxylic dianhydride having an ether group can be hydrolyzed by a known method to obtain an aromatic tetracarboxylic acid having an ether group; and the above-mentioned ether group can also be obtained by a known method. The aromatic tetracarboxylic dianhydride is subjected to diesterification to obtain an aromatic tetracarboxylic acid diester having an ether group.

Further, in the specific polyimine resin of the above polyimine film, the molar fraction of the aromatic diamine-derived moiety having a fluorine group with respect to all the diamine-derived sites is preferably 40. The range of mol% or more is 98 mol% or less; more preferably 50 mol% or more and 95 mol% or less; more preferably 60 mol% or more and 90 mol% or less. This is because a polyimide film composed of a specific polyimine resin such as this can exhibit excellent transparency.

The aromatic diamine having a fluorine group may, for example, be, for example, diaminotrifluorotoluene, bis(trifluoromethyl)phenylenediamine, diaminotetrakis(trifluoromethyl)benzene, diamine. (pentafluoroethyl)benzene, 2,2'-bis(trifluoromethyl)benzidine (TFMB), 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis (three Fluoromethyl)-4,4'-diaminodiphenyl ether, 3,3'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 3,3',5 , 5'-fluorene (trifluoromethyl)-4,4'-diaminodiphenyl ether, 3,3'-bis(trifluoromethyl)-4,4'-diaminobenzophenone , bis(aminophenoxy)bis(trifluoromethyl)benzene, bis(aminophenoxy)indole (trifluoromethyl)benzene, bis[(trifluoromethyl)aminophenoxy]benzene , bis[(trifluoromethyl))aminophenoxy]biphenyl, bis{[(trifluoromethyl))aminophenoxy]phenyl}hexafluoropropane, 2,2-dual {4 -(p-aminophenoxy)phenyl}hexafluoropropane, 2,2-bis{4-(m-aminophenoxy)phenyl}hexafluoropropane, 2,2-dual {4-( O-amino group Oxy)phenyl}hexafluoropropane, 2-{4-(p-aminophenoxy)phenyl}-2-{4-(m-aminophenoxy)phenyl}hexafluoropropane, 2 -{4-(m-Aminophenoxy)phenyl}-2-{4-(o-aminophenoxy)phenyl}hexafluoropropane, 2-{4-(o-aminophenoxyl) Phenyl}-2-{4-(p-aminophenoxy)phenyl}hexafluoropropane or the like.

Further, in the specific polyimine resin forming the above polyimine film, the molar fraction of the aromatic diamine-derived moiety having a sulfo group with respect to all the diamine-derived sites is preferably 2 mol % or more and 60 mol % or less; more preferably 5 mol % or more and 50 mol % or less; more preferably 10 mol % or more and 40 mol % or less. This is because the raw material cost of the polyimide film composed of a specific polyimine resin such as this is low.

The diamine having a sulfo group may, for example, be, for example, 3,3'-diaminodiphenylphosphonium (3,3'-DDS) or 4,4'-diaminodiphenylphosphonium (4, 4'-DDS), 4-aminophenyl sulfide, bis(2-aminophenyl) sulfide, bis(3-amino-4-hydroxyphenyl)fluorene, bis[4-(4-amine) Phenoxy)phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole (BAPS-M), 2,5-diamino-1,4-phenyldithio Hydrogen chloride, 1,3-phenylenediamine-4-decanoic acid, 1,4-phenylenediamine-2-decanoic acid, and the like.

Further, in the specific polyimine resin forming the above polyimine film, the aromatic tetracarboxylic acid compound-derived moiety having an ether group is preferably 2,2-bis[3,4-(dicarboxyl). At least one selected from the group consisting of a phenoxy)phenyl]propane compound (BPADA)-derived site and a 4,4'-oxodioic acid compound (ODPA)-derived moiety.

Further, in the specific polyimine resin forming the above polyimine film, the aromatic diamine-derived moiety having a fluorine group is preferably 2,2'-bis(trifluoromethyl)benzidine (TFMB). ) Derived parts.

Further, in the specific polyimine resin forming the above polyimine film, the aromatic diamine-derived moiety having a sulfo group is preferably 3,3'-diaminodiphenylanthracene (3,3). '-DDS) derivatized moiety, 4,4'-diaminodiphenylphosphonium (4,4'-DDS)-derived moiety, and bis[4-(3-aminophenoxy)phenyl]anthracene ( The BAPS-M) derivative site constitutes at least one selected portion of the group.

Further, it is preferable that the above polyimide film has a tensile strength of from 100 MPa to 500 MPa.

Further, it is preferable that the specific polyimide resin of the above polyimine film has a glass transition temperature of from 260 ° C to 350 ° C. This is because the glass transition temperature of the polyimide film is 260 ° C or higher, that is, when the polyimide film is incorporated in a flexible printed circuit board or the like, the flexible printed circuit board or the like can be used. When the semiconductor component is soldered, the polyimide film has sufficient heat resistance, and it is possible to prevent physical properties such as a flexible printed circuit board from being lowered.

Further, the above-mentioned polyimide film has a tensile elongation of 3.5% or more and 35% or less, more preferably 5.0% or more, when the surface is wetted with methyl ethyl ketone (MEK). Within the range of 25% or less. This is because the polyimide film has such physical properties that the polyimide film does not break when the polyimide film is attached to the copper foil at the time of producing a flexible printed circuit board or the like. Caused.

Further, when the film thickness of the polyimide film is 25 μm, the total light transmittance of the above polyimide film is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

Further, when the film thickness of the polyimide film is 25 μm, the yellowness of the above polyimide film is preferably 8.0 or less, more preferably 6.0 or less, still more preferably 4.0 or less.

Hereinafter, the polyimine film of the present invention will be described in detail using examples. "Embodiment 1"

1. Preparation of a polybendimimine precursor solution 18.86 g of biphenyltetracarboxylic dianhydride (BPDA), 0.34 g of 2,2-bis[3,4-(dicarboxyphenoxy)phenyl] Propane dianhydride (BPADA), 20.32 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 0.32 g of 4,4'-diaminodiphenyl fluorene (4,4'-DDS) The reaction was carried out in 110.17 g of N,N-dimethylacetamide (DMAc) to prepare a solid solution of 20 wt% of a polyimide precursor solution. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 99 mol% and 1 mol%, respectively; TFMB and 4,4 relative to all diamines. The molar fraction of '-DDS was 98 mol % and 2 mol %, respectively.

2. Preparation of Polyimine Film After applying the above polyimide precursor solution onto a glass substrate to form a coating film, the coating film was placed in an oven at 70 ° C, and after 20 minutes, the film was allowed to pass. The oven is heated to 120 °C. In addition, at this time, it takes a total of 20 minutes for the temperature of the oven to reach 120 ° C from 70 ° C. After the temperature of the oven reached 120 ° C, it was maintained at this temperature for 20 minutes, after which the oven was allowed to warm to 300 ° C. In addition, at this time, it takes a total of 39 minutes for the temperature of the oven to reach 300 ° C from 120 ° C. After the temperature of the oven reached 300 ° C, it was maintained at this temperature for 5 minutes. As a result, a polyimide film having a film thickness of 25 μm was formed on the glass substrate. Next, the polyimide film on the glass substrate was peeled off from the glass substrate to obtain a target polyimide film.

3. Measurement of physical properties of polyimine film The haze of the obtained polyimide film, the total light transmittance, the tensile strength (during drying), and methyl ethyl ketone were determined as follows. The amount of tensile elongation in the wet state and the glass transition temperature.

(1) Haze and total light transmittance of polyimine film Using a Suga test mechanism haze meter (HGM-2DP), the haze and total light penetration of the polyimide film were determined based on the old JIS K7105. At the time rate, the haze was 0.4%; the total light transmittance was 90.5%. In addition, b*値 and yellowness index were simultaneously measured at this time. The b*値 is 2.4; the yellowness is 4.0.

(2) Tensile strength of polyimine film The tensile strength of the polyimide film of tensile strength of 50 mm/min was measured using an automatic drawing AGS-10kNG manufactured by Shimadzu Corporation, and the tensile strength was 200 MPa. Further, at this time, the tensile modulus and the tensile elongation were also measured simultaneously. The tensile modulus was 4.4 GPa; and the tensile elongation was 21.3%.

(3) Tensile elongation of polyimine film in a state where methyl ethyl ketone is wet, the polyimine film is set on a jig of automatic drawing AGS-10kNG manufactured by Shimadzu Corporation, and methylethyl group is used. After the ketone oxime wets the entire surface of the polyimide film, the polyimide film is stretched at a tensile speed of 50 mm/min, and the tensile elongation (breaking elongation) at this time is measured. The tensile elongation was 17.8%.

(4) The glass transition temperature of the polyimide film was measured using a dynamic viscoelastic device (DM6100) manufactured by Seiko Instruments Co., Ltd., and the glass transition temperature was 347 ° C when the glass transition temperature of the polyimide film was measured based on the conditions shown below. . - Measurement conditions - Measurement environment: Under atmospheric atmosphere Film size: vertical 30 mm × horizontal 8 mm Sinusoidal load: amplitude 98 mN, frequency 1.0 Hz Heating rate: 2 ° C / min

From the above results, it was confirmed that the polyimine film obtained in the present example exhibited excellent heat resistance, transparency, strength, and colorless and transparent polythene as conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. <<Example 2》

The same as in Example 1, except that the amount of addition of BPDA was replaced by 18.53 g, the amount of addition of BPADA was replaced by 0.84 g, the amount of addition of TFMB was changed to 19.65 g, and the amount of addition of 4,4'-DDS was replaced by 0.80 g. A polyimine film was prepared by preparing a polyimine precursor solution (solid content: 20 wt%) in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA of all the tetracarboxylic dianhydrides at this time were 97.5 mol% and 2.5 mol%, respectively; TFMB and 4,4' with respect to all diamines. The molar fraction of -DDS is 95 mol % and 5 mol %, respectively. Further, the film thickness of the obtained polyimide film was 25 μm.

When the haze 全, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.5 was 0.5%; the total light transmittance was 90.5. %; tensile strength was 175 MPa; tensile elongation in the state of methyl ethyl ketone wet was 15.2%; glass transition temperature was 342 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.1 GPa; and the tensile elongation was 20.0%. In addition, b*値 was 2.4 in comparison with haze and total light transmittance; the yellowness was 3.9.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, strength, and colorless and transparent polyamide as in the conventional use. The amine film has a higher tolerance to methyl ethyl ketone. Example 3

In addition, the amount of addition of BPDA was replaced by 14.39 g, the amount of addition of BPADA was replaced by 1.34 g, the amount of addition of TFMB was replaced by 14.84 g, the amount of addition of 4,4'-DDS was replaced by 1.28 g, and the amount of addition of DMAc was replaced by 118.15. A polyimine film (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 95 mol% and 5 mol%, respectively; TFMB and 4,4 relative to all diamines. The molar fraction of '-DDS was 90 mol % and 10 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze 全, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.6 was 0.6%; the total light transmittance was 90.4. %; tensile strength was 156 MPa; tensile elongation in the state of methyl ethyl ketone wet was 8.9%; glass transition temperature was 335 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.3 GPa; and the tensile elongation was 14.1%. Further, b*値 measured simultaneously with haze and total light transmittance was 2.3; yellowness was 3.9.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also a colorless and transparent polypeptene which is conventionally used. The imine membrane has a higher tolerance to methyl ethyl ketone. Example 4

In addition, the amount of addition of BPDA was replaced by 13.54 g, the amount of addition of BPADA was replaced by 2.66 g, the amount of addition of TFMB was replaced by 13.10 g, the amount of addition of 4,4'-DDS was replaced by 2.54 g, and the amount of addition of DMAc was replaced by 118.16. A polyimine film (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 90 mol% and 10 mol%, respectively; TFMB and 4,4 relative to all diamines. The molar fraction of '-DDS was 80 mol % and 20 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze 全, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.5 was 0.5%; the total light transmittance was 90.3. %; tensile strength was 143 MPa; tensile elongation in the state of methyl ethyl ketone wet was 5.1%; glass transition temperature was 328 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.0 GPa; and the tensile elongation was 9.2%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 2.4; the yellowness was 4.0.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had a colorless and transparent polypene than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 5"

A polyimide quinone precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that 4,4'-DDS was replaced by 3,3'-DDS. A polyimide film was produced. In addition, the molar fractions of BPDA and BPADA with respect to all of the tetracarboxylic dianhydrides at this time were 99 mol% and 1 mol%, respectively; TFMB and 3,3 with respect to all diamines. The molar fraction of '-DDS was 98 mol % and 2 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.7 was 0.7%; the total light transmittance was 90.5%. The tensile strength was 207 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 20.7%; and the glass transition temperature was 339 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.4 GPa; and the tensile elongation was 22.0%. In addition, the haze and the total light transmittance were measured simultaneously with b*値 of 1.9; the yellowness was 3.6.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polycondensation than conventionally used. The quinone imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 6"

The 4,4'-DDS was replaced with 0.80 g of 3,3'-DDS, except that the amount of addition of BPDA was replaced by 18.53 g, the amount of addition of BPADA was replaced by 0.84 g, and the amount of addition of TFMB was replaced by 19.65 g and 0.32 g of 4,4'-DDS. The polyimine precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 97.5 mol% and 2.5 mol%, respectively; TFMB and 3,3 relative to all diamines. The molar fraction of '-DDS was 95 mol % and 5 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.6 was 0.6%; the total light transmittance was 90.4%. The tensile strength was 176 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 17.9%; and the glass transition temperature was 323 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.2 GPa; and the tensile elongation was 20.0%. In addition, the haze and the total light transmittance were measured simultaneously with b*値 of 2.0; the yellowness was 3.7.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polycondensation than conventionally used. The quinone imine membrane is also more resistant to methyl ethyl ketone. <<Example 7》

The 4,4'-DDS was replaced with 1.28 g of 3,3'-DDS, and the amount of BPDA was replaced by 14.39 g, the amount of BPADA added was replaced by 1.34 g, and the amount of TFMB was replaced by 14.84 g and 0.32 g of 4,4'-DDS. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.15 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 95 mol% and 5 mol%, respectively; TFMB and 3,3 with respect to all diamines. The molar fraction of '-DDS was 90 mol % and 10 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.6 was 0.6%; the total light transmittance was 90.4%. The tensile strength was 180 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 12.5%; and the glass transition temperature was 312 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.4 GPa; and the tensile elongation was 16.6%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 1.9; the yellowness was 3.6.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 8"

The 4,4'-DDS was replaced with 2.54 g of 3,3'-DDS, and the amount of BPDA was changed to 13.54 g, the amount of BPADA added was replaced by 2.66 g, and the amount of TFMB was replaced by 13.10 g and 0.32 g. A polyimine precursor solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.16 g. A polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time are 90 mol% and 10 mol%, respectively, and TFMB and 3 with respect to all diamines. The molar fraction of 3'-DDS is 80 mol % and 20 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.5 was 0.5%; the total light transmittance was 90.6%. The tensile strength was 184 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 8.2%; and the glass transition temperature was 297 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.3 GPa; and the tensile elongation was 27.4%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 2.2; the yellowness was 3.8.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 9"

The 4,4'-DDS was replaced with 3.78 g of 3,3'-DDS, except that the amount of BPDA added was replaced by 12.70 g, the amount of BPADA added was changed to 3.97 g, and the amount of TFMB was replaced by 11.38 g and 0.32 g. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.17 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 85 mol% and 15 mol%, respectively; TFMB and 3,3 with respect to all diamines. The molar fraction of '-DDS was 70 mol % and 30 mol %, respectively. Further, the obtained polyimide film had a film thickness of 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.6 was 0.6%; the total light transmittance was 90.5%. The tensile strength was 164 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 7.9%; and the glass transition temperature was 290 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.1 GPa; and the tensile elongation was 25.8%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 2.2; the yellowness was 4.0.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polycondensation than conventionally used. The quinone imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 10"

In addition to replacing the amount of BPDA with 13.42 g, 0.34 g of BPADA was replaced with 2.50 g of 5,5'-oxybis(isobenzofuran-1,3-dione) (ODPA), and the amount of TFMB was replaced with A polybendimimine precursor solution was prepared in the same manner as in Example 1 except that 12.03 g and 0.32 g of 4,4'-DDS were replaced with 4.00 g of 3,3'-DDS and DMAc were added in an amount of 118.07 g. Solid content: 20 wt%); and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and ODPA with respect to all tetracarboxylic dianhydrides at this time were 85 mol% and 15 mol%, respectively; TFMB and 3,3 relative to all diamines. The molar fraction of '-DDS was 70 mol % and 30 mol %, respectively. Further, the obtained polyimide film had a film thickness of 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.8 was 0.8%; the total light transmittance was 90.3%. The tensile strength was 209 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 14.8%; and the glass transition temperature was 297 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.2 GPa; and the tensile elongation was 27.0%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 4.0; the yellowness was 7.4.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polycondensation than conventionally used. The quinone imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 11"

The 4,4'-DDS was replaced with 5.01 g of 3,3'-DDS, and the amount of BPDA was changed to 11.87 g, the amount of BPADA added was replaced by 5.25 g, and the amount of TFMB was replaced by 9.69 g and 0.32 g of 4,4'-DDS. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.18 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 80 mol% and 20 mol%, respectively; TFMB and 3,3 with respect to all diamines. The molar fraction of '-DDS was 60 mol % and 40 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.5 was 0.5%; the total light transmittance was 90.5%. The tensile strength was 155 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 6.2%; and the glass transition temperature was 281 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.0 GPa; and the tensile elongation was 25.2%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 2.3; the yellowness was 4.1.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polycondensation than conventionally used. The quinone imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 12"

In addition to replacing the amount of BPDA with 12.77 g, 0.34 g of BPADA was replaced by 3.37 g of ODPA, and the amount of TFMB was replaced by 10.43 g, 0.32 g of 4,4'-DDS was replaced by 5.39 g of 3,3'- A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DDS and DMAc was changed to 118.05 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and ODPA with respect to all tetracarboxylic dianhydrides at this time were 80 mol% and 20 mol%, respectively; TFMB and 3,3' relative to all diamines. The molar fraction of -DDS is 60 mol % and 40 mol %, respectively. Further, the obtained polyimide film had a film thickness of 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.7 was 0.7%; the total light transmittance was 90.4%. The tensile strength was 177 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 12.1%; and the glass transition temperature was 293 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.1 GPa; and the tensile elongation was 24.3%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 4.2; the yellowness was 7.6.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 13"

The 4,4'-DDS was replaced with 6.22 g of 3,3'-DDS, except that the amount of addition of BPDA was replaced by 11.05 g, the amount of addition of BPADA was changed to 6.52 g, and the amount of addition of TFMB was changed to 8.02 g and 0.32 g. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.20 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA of all tetracarboxylic dianhydrides at this time were 75 mol % and 25 mol %, respectively; TFMB and 3,3'- relative to all diamines. The molar fraction of DDS is 50 mol % and 50 mol %, respectively. Further, the obtained polyimide film had a film thickness of 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.5 was 0.5%; the total light transmittance was 90.4%. The tensile strength was 140 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 4.1%; and the glass transition temperature was 275 °C. Further, the tensile modulus measured at the same time as the tensile strength was 3.6 GPa; and the tensile elongation was 10.2%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 1.7; the yellowness was 2.8.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. <<Example 14》

The 4,4'-DDS was replaced with 4.83 g of 3,3'-DDS, and the amount of BPDA was changed to 10.01 g, the amount of BPADA added was replaced by 7.59 g, and the amount of TFMB was replaced by 9.33 g and 0.32 g. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.25 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 70 mol% and 30 mol%, respectively; TFMB and 3,3 with respect to all diamines. The molar fraction of '-DDS was 60 mol % and 40 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.4 was 0.4%; the total light transmittance was 90.4%. The tensile strength was 137 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 3.8%; and the glass transition temperature was 269 °C. Further, the tensile modulus measured at the same time as the tensile strength was 3.3 GPa; and the tensile elongation was 9.0%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 1.6; the yellowness was 2.6.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone. "Embodiment 15"

The 4,4'-DDS was replaced with 7.41 g of 3,3'-DDS, and the amount of BPDA was changed to 10.24 g, the amount of BPADA was changed to 7.77 g, and the amount of TFMB was replaced by 6.37 g and 0.32 g of 4,4'-DDS. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.21 g, and a polyimide film was produced in the same manner as in Example 1. In addition, the molar fractions of BPDA and BPADA with respect to all tetracarboxylic dianhydrides at this time were 70 mol% and 30 mol%, respectively; TFMB and 3,3 relative to all diamines. The molar fraction of '-DDS was 40 mol % and 60 mol %, respectively. Further, the obtained polyimide film had a film thickness of 25 μm.

When the haze 全, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.6 was 0.6%; the total light transmittance was 90.3%. The tensile strength was 129 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 3.5%; and the glass transition temperature was 272 °C. Further, the tensile modulus measured at the same time as the tensile strength was 3.3 GPa; and the tensile elongation was 8.4%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 1.7; the yellowness was 2.7.

From the above results, it was confirmed that the polyimide film obtained in the present example also exhibited the same excellent heat resistance, transparency, and strength as conventionally used; and also had colorless and transparent polypime than conventionally used. The imine membrane is also more resistant to methyl ethyl ketone.

(Comparative Example 1) Except that BPADA and 4,4'-DDS were not added, the amount of BPDA added was replaced by 15.26 g, the amount of TFMB added was replaced by 16.61 g, and the amount of DMAc added was replaced by 118.13 g. 1 A polyimine precursor solution (solid content: 20 wt%) was prepared in the same manner, and a polyimide film was produced in the same manner as in Example 1. The film thickness of the obtained polyimide film was 25 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 7.0 was 7.0%; the total light transmittance was 87.2%. The tensile strength was 203 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 20.4%; and the glass transition temperature was 335 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.3 GPa; and the tensile elongation was 20.2%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 3.0; the yellowness was 5.2.

From the above results, it can be understood that although the polyimide film obtained in this comparative example exhibits the same excellent heat resistance and strength as conventionally used, and has a colorless and transparent polyimine which is conventionally used. The membrane is also more resistant to methyl ethyl ketone; however, there is a significant lack of transparency.

(Comparative Example 2) Except that BPDA and 4,4'-DDS were not added, the amount of BPADA added was replaced by 19.41 g, the amount of TFMB added was replaced by 11.94 g, and the amount of DMAc added was replaced by 118.66 g. 1 A polyimine precursor solution (solid content: 20 wt%) was prepared in the same manner, and a polyimide film was produced in the same manner as in Example 1. The film thickness of the obtained polyimide film was 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 0.9 was 0.9%; the total light transmittance was 90.4%. The tensile strength was 158 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 2.6%; and the glass transition temperature was 242 °C. Further, the tensile modulus measured at the same time as the tensile strength was 3.8 GPa; and the tensile elongation was 34.1%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 1.8; the yellowness was 3.5.

From the above results, it can be understood that although the polyimide film obtained in this comparative example exhibits excellent transparency and strength similar to those conventionally used, it is not only poor in heat resistance, but also cannot be exhibited and used. The colorless transparent polyimide film has the same methyl ethyl ketone resistance.

(Comparative Example 3) The amount of BPDA added was replaced with 15.85 g, the amount of TFMB added was replaced with 12.08 g, and 0.32 g of 4,4'-DDS was replaced with 4.01 g of 3,3'-DDS, except that BPADA was not added. A polyimide film solution (solid content: 20 wt%) was prepared in the same manner as in Example 1 except that the amount of DMAc was changed to 118.06 g, and a polyimide film was produced in the same manner as in Example 1. The film thickness of the obtained polyimide film was 24 μm.

When the haze, total light transmittance, tensile strength, and glass transition temperature of the obtained polyimide film were measured in the same manner as in Example 1, the haze 7.5 was 7.5%; the total light transmittance was 85.8%. The tensile strength was 162 MPa; the tensile elongation in the state of methyl ethyl ketone wet was 8.1%; and the glass transition temperature was 300 °C. Further, the tensile modulus measured at the same time as the tensile strength was 4.3 GPa; and the tensile elongation was 21.2%. In addition, the b*値 measured at the same time as the haze and the total light transmittance was 3.1; the yellowness was 5.6.

From the above results, it can be understood that although the polyimide film obtained in this comparative example exhibits the same excellent heat resistance and strength as conventionally used, and has a colorless and transparent polyimine which is conventionally used. The film is also more resistant to methyl ethyl ketone; however, there is a significant lack of transparency. In addition, for the sake of reference, the "synthesis conditions of the polyimine precursor solution and the film thickness of the polyimide film obtained from the polyimide precursor solution" in the above examples and comparative examples, The "physical properties of the polyimide film" are summarized in Tables 1 and 2 below.

"Table 1"

"Table 2" "Utilization possibilities in industry"

The polyimine film system according to the present invention can exhibit excellent heat resistance, transparency, strength, and can be produced at a lower cost than conventionally used; and has a colorless and transparent polyphthalate than conventionally used. The amine film is also more resistant to methyl ethyl ketone; it can be suitably used, for example, for a circuit board, a cover layer, or a bar code printing substrate for luminescent element mounting.

Claims (11)

A polyimine film composed of a polyimide resin and having a haze of 0.1 or more and 2.0 or less; wherein the polyimide resin comprises at least: a biphenyl tetracarboxylic acid compound (BPDA) a derivative site, and a tetracarboxylic acid compound-derived site derived from an aromatic tetracarboxylic acid compound-derived moiety having an ether group; and at least: an aromatic diamine-derived moiety having a fluorine group, and an aromatic having a sulfo group A diamine-derived moiety of a family diamine-derived moiety. The polyimine film according to claim 1, wherein the molar fraction of the biphenyltetracarboxylic acid compound (BPDA)-derived moiety relative to all of the tetracarboxylic acid-based compound-derived sites is 70 mol. % above 99 mol % or less. The polyimine film according to claim 1 or 2, wherein the molar fraction of the aromatic tetracarboxylic acid-derived compound-derived moiety having an ether group with respect to all of the tetracarboxylic acid-based compound-derived sites is 1 mol% or more and 30 mol% or less. The polyimine film according to any one of claims 1 to 3, wherein the molar fraction of the aromatic diamine-derived moiety having a fluorine group with respect to all of the diamine-derived sites is 40 mol. % above 98 mol % or less. The polyimine film according to any one of claims 1 to 4, wherein the molar fraction of the aromatic diamine-derived moiety having a sulfo group relative to all of the diamine-derived sites is 2 mol. % or more in the range of 60 mol % or less. The polyimine film according to any one of claims 1 to 5, wherein the aromatic tetracarboxylic acid compound-derived moiety having an ether group is derived from 2,2-bis[3,4-(dicarboxybenzene) At least one selected from the group consisting of an oxy)phenyl]propane-based compound (BPADA)-derived site and a 4,4'-oxodioic acid-based compound (ODPA)-derived moiety. The polyimine film according to any one of claims 1 to 6, wherein the aromatic diamine-derived moiety having a fluorine group is derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB). Part. The polyimine film according to any one of claims 1 to 7, wherein the aromatic diamine-derived moiety having a sulfo group is 3,3'-diaminodiphenylanthracene (3,3'- DDS) Derivatized moiety, 4,4'-diaminodiphenylphosphonium (4,4'-DDS)-derived moiety, and bis[4-(3-aminophenoxy)phenyl]anthracene (BAPS- M) The derivative site constitutes at least one selected portion of the group. The polyimine film according to any one of claims 1 to 8, wherein the tensile strength is in a range of from 100 MPa to 500 MPa. The polyimine film according to any one of claims 1 to 9, wherein the glass transition temperature of the polyimine resin is in a range of from 260 ° C to 350 ° C. The polyimine film according to any one of claims 1 to 10, wherein the tensile elongation in the case of dampening methyl ethyl ketone (MEK) on one side is in the range of 3.5% or more and 35% or less. .