JP2011074106A - Aromatic polyamide and aromatic polyamide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polyamide not containing a chlorine atom in a polymer structure, and keeping polymer soluble in a nonprotonic polar solvent without adding an inorganic salt in a polymerization step, and to provide an aromatic polyamide film containing the aromatic polyamide. <P>SOLUTION: The aromatic polyamide film contains at least ≥1 mol% of an acid chloride component having a specific flexible structure in the polymer structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic polyamide and an aromatic polyamide film.

  Aromatic polyamide is a useful polymer as an industrial material because of its high heat resistance and mechanical strength. In particular, aromatic polyamides composed of para-oriented aromatic nuclei as typified by polyparaphenylene terephthalamide (hereinafter sometimes referred to as PPTA) are molded products having excellent strength and elastic modulus in addition to the above properties due to their rigidity. The utility value is high. However, para-oriented aromatic polyamides such as PPTA have low solubility in solvents and are only limited in very limited solvents such as sulfuric acid, so there are significant process restrictions, and the solution also gives optical anisotropy. When obtaining fibers, there is no major problem, but in order to obtain a two-dimensional or higher shaped article such as a film, it is necessary to use a special molding method described in Patent Document 1, and an improvement is required.

  Thus, as a means for improving the solubility, an aromatic polyamide in which a chlorine atom is introduced into an aromatic nucleus is proposed in Patent Document 2, but there is a concern that the introduction of chlorine increases the burden on the environment.

  On the other hand, Patent Document 3 discloses a colorless and transparent aromatic polyamide obtained by using 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl as a raw material. However, the aromatic polyamide disclosed in the literature requires introduction of chlorine atoms, bending components, and addition of inorganic salts for the purpose of improving solubility.

  Further, Patent Document 4 discloses an aromatic polyamide obtained using 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl and 4,4'-biphenyldicarboxylic acid chloride as raw materials. Although the aromatic polyamide disclosed in the document has extremely excellent physical properties, it is necessary to add an inorganic salt as a solubilizing agent, and thus there is a problem that costs increase due to an increase in raw material cost and polymerization process.

JP-A 62-39634 JP-A-54-106564 Republished patent WO2004 / 039863 JP 2009-79210 A

  The present invention has been achieved as a result of investigations to solve the problems of the above-described conventional techniques. That is, an object of the present invention is to obtain an aromatic polyamide that does not contain a chlorine atom in the polymer structure and that the polymer is soluble in an aprotic polar solvent without adding an inorganic salt in the polymerization step. .

  The present invention for achieving the above object is an aromatic polyamide film containing at least 1 mol% or more of the structural unit represented by the chemical formula (1).

  According to the present invention, by introducing a specific flexible structure into the polymer structure, an inorganic salt added at the time of polymerization to dissolve the polymer becomes unnecessary, and the cost can be reduced. Furthermore, even when formed into a film, an aromatic polyamide film having high rigidity and high heat resistance can be provided.

  The aromatic polyamide of the present invention is an aromatic polyamide containing at least 1 mol% of the structural unit represented by the chemical formula (1).

  Polyamide generally has low solubility because the intermolecular cohesive force is increased by the hydrogen bond of the amide group and the polymers are packed together. On the other hand, when a large number of structural units of the bending component are included, the solubility is improved, but there is a problem that the Young's modulus decreases and the thermal expansion coefficient increases when it is formed into a film. As a result of intensive studies, when the polymer unit constituting the film contains a 3,3′-biphenyldicarboxylic acid residue represented by the chemical formula (1), the polymer is aprotic without adding an inorganic salt to the polymer solution. It has been found that it becomes soluble in a polar solvent and has a high Young's modulus and a low thermal expansion coefficient when formed into a film. This is because by introducing 3,3′-biphenyldicarboxylic acid residue, the polymer structure has a slightly flexible structure, prevents the distance between the polymer chains from approaching, inhibits packing between molecules, It is considered that the solubility is improved because pseudo-crosslinking due to bonding can be inhibited. In addition, when the polymer structure contains a 3,3'-biphenyldicarboxylic acid residue, a difference occurs in the molecular length of any amide group and the adjacent amide group, which can inhibit hydrogen bonding of the amide group and improve solubility. It is thought that it contributes to. Although the solubility is improved when a large number of bent structures are included, there is a problem that the Young's modulus decreases and the thermal expansion coefficient increases when it is formed into a film, but the 3,3′-biphenyldicarboxylic acid residue is an isophthalic acid. It is less flexible than a flexible acid chloride component such as a residue. For this reason, there exists an effect which prevents that a polymer chain becomes too flexible. Therefore, when a film is formed using a polymer solution of an aromatic polyamide containing a 3,3'-biphenyldicarboxylic acid residue in the polymer structure, a film having a high Young's modulus and a low thermal expansion coefficient can be obtained. In addition, when the polymer structure contains a 4,4′-biphenyldicarboxylic acid residue in which the carboxylic acid residue is in the para position as disclosed in JP-A-2009-79210, the polymer structure is rigid. Therefore, the solubility was low, and it was necessary to improve the solubility by adding an inorganic salt during polymerization. Among the polymer structures disclosed in this document, increasing the molar ratio of 4,4′-diaminodiphenyl sulfone, which is a diamine component, may improve the solubility because the polymer structure is more bent, If the molar ratio of 4,4′-diaminodiphenylsulfone is slightly increased, the flexibility of the polymer is insufficient and the solubility is insufficient, and there is a problem that the polymer is precipitated during the polymerization process. On the other hand, when the molar ratio of 4,4'-diaminodiphenylsulfone is increased to give more solubility, there arises a problem that the flexibility of the polymer structure increases and the thermal expansion coefficient increases.

  The aromatic polyamide of the present invention preferably contains structural units represented by chemical formulas (1), (2), (3) and (4).

When the polymer structural unit contains a 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl residue represented by the chemical formula (2), the polymer structure becomes rigid. In addition, it contributes to keeping the thermal expansion coefficient low, and furthermore, the electron withdrawing property of the trifluoromethyl group (—CF ₃ group) of the 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl residue Since the spread of the cloud can be divided, it is preferable because it contributes to improving the light transmittance of light having a wavelength of 400 nm.

  When the polymer structure contains the 4,4′-diaminodiphenylsulfone residue represented by the chemical formula (3), the polymer structure can be flexed without significantly increasing the thermal expansion coefficient when formed into a film, and the solubility can be increased. It is preferable because it can be improved.

  When the terephthalic acid chloride residue represented by the chemical formula (4) is contained in the polymer structure, it is preferable because it contributes to a high Young's modulus and a low thermal expansion coefficient when the polymer structure becomes rigid and forms a film.

  In the above, when the molar fractions of the structural units represented by the chemical formulas (1), (2), (3) and (4) are respectively a, b, c and d, the following formulas (1) to (6) By satisfying the above, it is possible to achieve both high rigidity and high heat resistance of the aromatic polyamide and to obtain a colorless and transparent aromatic polyamide, which is preferable.

5 ≦ a ≦ 25 (1)
25 ≦ b ≦ 50 (2)
25 ≦ d ≦ 45 (3)
0.9 ≦ (a + d) / (b + c) ≦ 1.1 (4)
98 ≦ a + b + c + d ≦ 100 (5)
b + c = 50 (6)
More preferably, a, b, c and d satisfy the following formulas (7) to (12).

5 ≦ a ≦ 20 (7)
30 ≦ b ≦ 50 (8)
30 ≦ d ≦ 45 (9)
0.9 ≦ (b + d) / (a + c) ≦ 1.1 (10)
98 ≦ a + b + c + d ≦ 100 (11)
b + c = 50 (12)
Formulas (1) and (7) indicate the introduction amount of the structural unit of the 3,3′-biphenyldicarboxylic acid residue represented by the chemical formula (1), and a may be 1 or more, but less than 5 In some cases, the rigid component increases, the solubility decreases, the polymer solution gels, and the solubility cannot be maintained. When a is larger than 25, the bending component of the polymer structure increases, and the thermal expansion coefficient may increase when the resulting polymer solution is formed into a film. a is preferably 5 or more and 25 or less, more preferably 6 or more and 23 or less, and most preferably 8 or more and 20 or less. Here, keeping the solubility means keeping the fluidity after leaving the polymer solution obtained by polymerization at 25 ° C. for 2 weeks. “Maintaining fluidity” means a state in which 50 ml or more flows out within one hour when 100 ml of a polymer solution is placed in a 100 ml beaker at 25 ° C. and tilted 90 °.

Formulas (2) and (8) show the introduction amount of the constituent unit of the 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl residue represented by the chemical formula (2), and b is smaller than 25 The polymer structure loses its rigidity, and when the obtained polymer solution is formed, not only does the Young's modulus decrease and the thermal expansion coefficient increase, but also 2,2′-ditrifluoromethyl-4 , 4'-diaminobiphenyl residue trifluoromethyl group (-CF ₃ group) has a weak effect of dividing the electron cloud spread due to the electron withdrawing property, the light transmittance of the light of the wavelength of 400nm becomes low There is. On the other hand, when b is larger than 50, the polymer structure becomes rigid and hydrogen bonds are likely to be generated, so that the solubility may be lowered and the polymer solution may gel and the solubility may not be maintained. The lower limit of b is 25, more preferably 30, but when the range of b is 30 or more, when the obtained polymer solution is formed into a film, it has a higher Young's modulus and a low thermal expansion coefficient. Moreover, an aromatic polyamide film having a high light transmittance for light having a wavelength of 400 nm is obtained, which is preferable. b is preferably 25 or more and 50 or less, more preferably 30 or more and 45 or less, and most preferably 35 or more and 45 or less.

  Formulas (3) and (9) show the introduction amount of the structural unit of the terephthalic acid chloride residue represented by the chemical formula (3), and when d is smaller than 25, the rigidity of the polymer structure is lost. When the obtained polymer is formed, there is a risk that the Young's modulus of the film is lowered or the thermal expansion coefficient is increased. On the other hand, when d is larger than 45, the polymer structure becomes rigid and hydrogen bonds are likely to occur, so that the solubility is lowered and the polymer solution is gelled and the solubility may not be maintained. The lower limit of d is 25, more preferably 30, but when the range of d is 30 or more, when the obtained polymer solution is formed into a film, it has a higher Young's modulus and a low thermal expansion coefficient. This is preferable because an aromatic polyamide film can be obtained. d is preferably 25 or more and 45 or less, more preferably 30 or more and 45 or less, and most preferably 35 or more and 45 or less.

  When the ratio of the dicarboxylic acid residue and the diamine residue represented by the formulas (4) and (10) is less than 0.9, the diamine residue is excessive and the degree of polymerization is not increased, and the molecular weight is reduced to form a film. The film may become brittle. In addition, when the ratio of the dicarboxylic acid residue to the diamine residue is larger than 1.1, the dicarboxylic acid residue is excessive, the degree of polymerization is not sufficiently increased, the molecular weight is decreased, and the formed film becomes brittle. is there. The ratio of the dicarboxylic acid residue to the diamine residue is preferably from 0.9 to 1.1, more preferably from 0.95 to 1.05, and most preferably from 0.97 to 1.03.

  When the total number of mole fractions of the diamine residue and dicarboxylic acid residue represented by the formulas (5) and (11) is smaller than 98, the diamine residue becomes excessive, the degree of polymerization does not increase, and the molecular weight becomes small. Films that are filmed may become brittle. The total number of mole fractions of the diamine residue and the dicarboxylic acid residue is preferably 98 or more and 100 or less, more preferably 99 or more and 100 or less, and most preferably 99.5 or more and 100 or less.

  The aromatic polyamide of the present invention is preferable because an intrinsic viscosity of 1.5 dl / g or more can provide a high elongation film. When the intrinsic viscosity is less than 1.5 dl / g, the solubility is improved, but the resulting film tends to be brittle. The intrinsic viscosity is more preferably 2.5 dl / g or more, and still more preferably 3.5 dl / g or more. There is no upper limit of the intrinsic viscosity, but if it is too large, there is a problem that it becomes cloudy in a dry and wet film forming process or gels in a polymerization process. Therefore, the intrinsic viscosity is preferably 10 dl / g or less, more preferably 8 dl / g or less, and still more preferably 7 dl / g or less. In order to set the intrinsic viscosity to 1.5 dl / g or more, for example, the structural unit of the aromatic polyamide is set to the specific molar fraction described above, and the stirring is sufficiently performed at a low temperature so that no side reaction occurs during the polymerization. It can be realized by the method.

  The Young's modulus of the aromatic polyamide film of the present invention is preferably 5 GPa or more in at least one direction in the measurement based on JIS-K7127-1999. More preferably, it is 6 GPa or more, More preferably, it is 8 GPa or more. When the Young's modulus is less than 5 GPa, the handling property tends to be lowered. In addition, the Young's modulus can be further improved by stretching at the time of film formation. However, if the stretching is too strong, the elongation decreases, so that the upper limit of the Young's modulus is about 20 GPa.

  The average coefficient of thermal expansion of 100 ° C. to 200 ° C. in at least one direction of the aromatic polyamide film of the present invention is preferably −15 ppm / ° C. or more and 15 ppm / ° C. or less. More preferably, it is -12 ppm / ° C or more and 15 ppm / ° C or less, and further preferably -12 ppm / ° C or more and 13 ppm / ° C or less. When the average thermal expansion coefficient of 100 ° C. to 200 ° C. is out of the range of −15 ppm / ° C. or more and 15 ppm / ° C. or less, curling may increase when laminated with a low thermal expansion coefficient such as glass or ITO.

  The average coefficient of thermal expansion in the film plane is preferably 5 ppm / ° C. or less in the difference between the average coefficient of thermal expansion in one direction and the direction perpendicular thereto. More preferably, it is 3 ppm / ° C. or less, and further preferably 1 ppm / ° C. or less. Examples of a method for reducing the difference in average thermal expansion coefficient in two directions in the film plane include a method of performing stretching during film formation. Specifically, the difference in average thermal expansion coefficient between the two directions in the film plane is reduced by stretching in the film forming direction (longitudinal direction, MD direction) and in the orthogonal direction (width direction, TD direction). Can do.

  The light transmittance of light having a wavelength of 400 nm of the aromatic polyamide of the present invention is preferably 70% or more. More preferably, it is 80% or more, More preferably, it is 85% or more. When the light transmittance at 400 nm in the near-ultraviolet region is 70% or more, the transparency is further improved.

  The haze of the aromatic polyamide of the present invention is preferably 2.0% or less. More preferably, it is 1.5% or less, More preferably, it is 1.0% or less.

  The aromatic polyamide of the present invention includes structural units represented by chemical formulas (1), (2), (3) and (4), and has the chemical formulas (1), (2), (3) and (4). When the mole fractions of the structural units shown are a, b, c, and d, respectively, high light transmittance and low haze can be achieved by satisfying the following formulas (1) to (6).

5 ≦ a ≦ 25 (1)
25 ≦ b ≦ 50 (2)
25 ≦ d ≦ 45 (3)
0.9 ≦ (a + d) / (b + c) ≦ 1.1 (4)
98 ≦ a + b + c + d ≦ 100 (5)
b + c = 50 (6)
Although the manufacturing method of the aromatic polyamide composition of this invention and the example which manufactures a film are demonstrated below, this invention is not limited to this.

  Various methods can be used for obtaining the aromatic polyamide. For example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method, and the like can be used. When it is obtained from a low temperature solution polymerization method, that is, from acid dichloride and diamine, it is synthesized in an aprotic organic polar solvent. When acid dichloride and diamine are used as monomers in the polymer solution, hydrogen chloride is by-produced. To neutralize this, inorganic neutralizers such as calcium hydroxide, calcium carbonate, lithium carbonate, and ethylene Organic neutralizers such as oxide, propylene oxide, ammonia, triethylamine, triethanolamine, diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst.

  When performing polymerization using two or more kinds of diamines, diamines are added one by one, 10 to 99 mol% of acid dichloride is added to the diamine and reacted, and then another diamine is added, Further, a stepwise reaction method in which acid dichloride is added and reacted, a method in which all diamines are mixed and added, and then acid dichloride is added and reacted can be used. Similarly, when two or more kinds of acid dichlorides are used, a stepwise method, a method of simultaneously adding them, and the like can be used. In any case, the molar ratio of the total diamine to the total acid dichloride is preferably 95 to 105: 105 to 95, and if it is outside this value, it is difficult to obtain a polymer solution suitable for molding.

  Examples of the aprotic polar solvent used in the production of the aromatic polyamide of the present invention include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Examples thereof include phenol solvents such as p-cresol, xylenol, halogenated phenol, and catechol, hexamethylphosphoramide, and γ-butyrolactone, and these are preferably used alone or as a mixture. Furthermore, aromatic hydrocarbons such as xylene and toluene can be used.

The aromatic polyamide of the present invention may contain 10% by mass or less of an inorganic or organic additive for the purpose of surface formation and processability improvement. The additives for the purpose of surfacing _{example, SiO 2, TiO 2, Al} 2 O 3 _in the inorganic _{particles, CaSO 4, BaSO 4, CaCO} 3, carbon black, carbon nanotube, fullerene, zeolite, other metallic powder Etc. Preferred organic particles include, for example, particles made of an organic polymer such as crosslinked polyvinylbenzene, crosslinked acrylic, crosslinked polystyrene, polyester particles, polyimide particles, polyamide particles, and fluororesin particles, or the above organic polymer on the surface. Inorganic particles that have been subjected to treatment such as coating may be mentioned.

  In addition, various end-capping agents can be used for the purpose of preventing coloring and suppressing the formation of a polymer having a very high molecular weight. For example, benzoyl chloride, substituted benzoyl chloride and acetic anhydride are preferable, and benzoyl chloride and substituted benzoyl chloride are more preferable. As the substituent of the substituted benzoyl chloride, fluorine compounds such as fluorine and trifluoromethyl, and bulky hydrocarbon groups such as t-butyl and adamantane are preferable. The addition amount of the terminal blocking agent is preferably 1.0 mol% or less when the total molar fraction of the dicarboxylic acid residue and the diamine residue is 100 mol%. If it exceeds 1.0 mol%, the intrinsic viscosity may not be sufficiently increased, and the resulting film may become brittle.

  Next, film formation will be described.

  Since the aromatic polyamide of the present invention is soluble in an organic solvent, a special film forming method using concentrated sulfuric acid like PPTA is not necessarily required. The film-forming stock solution prepared as described above is preferably formed into a film by a so-called solution film-forming method. The solution casting method includes a dry-wet method, a dry method, a wet method, and any method may be used. However, the aromatic polyamide of the present invention is excellent in solubility, so that the film-forming process can be controlled. It is possible to form a film by an easy dry-wet method. Here, a dry and wet method will be described as an example.

  In the case of forming a film by a dry-wet method, the stock solution is extruded from a die onto a support such as a drum, an endless belt, or a film to form a thin film, and then dried until the thin film layer has a self-holding property. Drying conditions can be performed in the range of room temperature to 220 ° C. and within 60 minutes, for example. If a polymer solution with insufficient solubility is used, it becomes cloudy in this step. Further, a film having a smooth surface can be obtained by making the surfaces of the drum, endless belt and film used in this drying process as smooth as possible. The film after the dry process is peeled off from the support and introduced into the wet process, desalted, desolvated, etc., and further stretched, dried and heat treated to form a film.

  Stretching is in the range of 0.8 to 8 (drawing ratio is defined by dividing the film area after stretching by the area of the film before stretching. 1 or less means relaxation) as the stretching ratio. Preferably, it is 1.1-8. Moreover, as heat processing, the heat processing for several seconds to several minutes is preferably implemented at the temperature of 200 to 500 degreeC, Preferably it is 250 to 400 degreeC. Furthermore, it is effective to gradually cool the film after stretching or heat treatment, and it is effective to cool at a rate of 50 ° C./second or less.

  The structure of the aromatic polyamide is determined by the raw material diamine and carboxylic acid dichloride. When the raw material is unknown, structural analysis is performed from the aromatic polyamide composition. As this method, mass analysis, analysis by nuclear magnetic resonance method, spectroscopic analysis, or the like can be used.

  The film (aromatic polyamide film) obtained from the aromatic polyamide of the present invention may be a single layer film or a laminated film. The aromatic polyamide film of the present invention is a flexible printed circuit board, a photoelectric composite circuit board, an optical waveguide board, a semiconductor mounting board, a multilayer laminated circuit board, a capacitor, a printer ribbon, an acoustic diaphragm, a solar cell, and a magnetic recording medium. It is preferably used for various applications such as a base film.

  The present invention will be described more specifically with reference to the following examples.

  The measurement method of physical properties and the evaluation method of effects in the present invention were performed according to the following methods.

(1) Intrinsic viscosity Using an Ubbelohde viscometer, 0.5 g of sample was dissolved in 100 ml of N-methyl-2-pyrrolidone (NMP) containing 2.5% by mass of lithium bromide, and the following was performed at a temperature of 30 ° C. Calculated from the formula.

Intrinsic viscosity = ln (t / t0) /0.5 (dl / g)
t0: Flowing time of NMP containing 5% by mass of lithium bromide (seconds)
t: Flowing time of the solution in which the sample is dissolved (seconds)
(2) Young's modulus Using a Robot Tensilon RTA (Orientec Co., Ltd.), the Young's modulus was measured at a temperature of 23 ° C and a relative humidity of 65%. The test piece was a sample having a width of 10 mm and a length of 50 mm in the TD direction, where the film forming direction or the moving direction of the bar coater was the MD direction, and the direction orthogonal thereto was the TD direction. The tensile speed is 300 mm / min. However, the point where the load passed 1 N after the start of the test was taken as the origin of elongation.

(3) Average thermal expansion coefficient The average thermal expansion coefficient was measured in the temperature lowering process after the temperature was raised to 250 ° C. according to JIS K7197-1991. When the initial sample length at 25 ° C. and 75 RH% is L0, the sample length at the temperature T1 is L1, and the sample length at the temperature T2 is L2, the average thermal expansion coefficient from T1 to T2 was obtained by the following equation.

  Note that T2 = 100 (° C.), T1 = 200 (° C.), and L0 = 15 mm.

Thermal expansion coefficient (ppm / ° C.) = (((L2-L1) / L0) / (T2-T1)) × 10 ⁶
Temperature rise / fall rate: 5 ° C / min
Sample width: 4mm
Load: 44.5 mN when the film thickness is 10 μm
The load is changed in proportion to the film thickness.

Weight = 44.5 (mN) × d (μm) / 10 (μm)
d (μm): film thickness (4) Light transmittance Measured using the following apparatus, the transmittance corresponding to light having a wavelength of 400 nm was determined.

Transmittance (%) = (T1 / T0) × 100
However, T1 is the intensity | strength of the light which passed the sample, and T0 is the intensity | strength of the light which passed the air of the same distance except not passing a sample.

Apparatus: UV measuring instrument U-3410 (manufactured by Hitachi Instruments)
Wavelength range: 300 nm to 800 nm (of which 400 nm is used)
Measurement speed: 120 nm / min Measurement mode: Transmission (5) Haze Haze (%) of film at 23 ° C. according to JIS-K7136 (2000) using haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) ) Was measured at three locations, and the average value was determined.

(6) Solubility A polymer solution obtained by polymerization was evaluated as a solubility “◯” if it remained fluid after being allowed to stand at 25 ° C. for 2 weeks.

  “Maintaining fluidity” means a state in which 50 ml or more flows out within one hour when 100 ml of a polymer solution is placed in a 100 ml beaker at 25 ° C. and tilted 90 °.

(7) Presence or absence of chlorine When the molecular structure is known, the presence or absence is judged from the molecular structure. In this case, chlorine at the acid chloride site of the aromatic dicarboxylic acid chloride is removed from the molecular structure during the reaction and does not remain. Moreover, when a raw material composition is not known, it measures based on JISK7229-1995, and when a chlorine content rate is less than 1 mol%, it judges that it does not contain chlorine.
Example 1
In a 300 ml three-necked flask equipped with a stirrer, 6.63 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (Wakayama Seika Co., Ltd.), 4,4′-diaminodiphenyl sulfone (Wakayama Seiki) 0.57 g and N-methyl-2-pyrrolidone (191 ml) were added, cooled to 0 ° C. in a nitrogen atmosphere, and stirred for 30 minutes with 3.70 g of terephthalic acid dichloride (manufactured by Tokyo Kasei Co., Ltd.) and 3 , 3′-biphenyldicarbonyl chloride (Toray Fine Chemical Co., Ltd.) 1.27 g was added in 5 portions. After stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. Moreover, this polymer solution maintained fluidity after being left for 2 weeks.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

(Example 2)
In a 300 ml three-necked flask equipped with a stirrer, 6.41 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 209 ml of N-methyl-2-pyrrolidone were placed and nitrogen was added. Under the atmosphere, 1.11 g of 3,3′-biphenyldicarbonyl chloride (manufactured by Toray Fine Chemical Co., Ltd.) was added in 5 portions over 30 minutes while cooling to 0 ° C. and stirring. After stirring for 30 minutes, 3.22 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions over 30 minutes with stirring. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. Moreover, this polymer solution maintained fluidity after being left for 2 weeks. A part of the polymer solution obtained on a support on which a PET film (T60 (100 μm) manufactured by Toray Industries, Inc.) was pasted on a SUS plate was taken, and a uniform film was formed using a bar coater. This was heated at 80 ° C. for 20 minutes to obtain a self-holding film. The obtained film was peeled off from the PET film, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

(Example 3)
Into a 300 ml three-necked flask equipped with a stirrer was charged 3.27 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 91 ml of N-methyl-2-pyrrolidone. A mixture of 1.04 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.42 g of 3,3′-biphenyldicarbonyl chloride (manufactured by Toray Fine Chemical Co., Ltd.) is taken over 30 minutes with cooling and stirring to 0 ° C. in an atmosphere. It was added in 5 portions. After stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. Moreover, this polymer solution maintained fluidity after being left for 2 weeks.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

Example 4
In a 300 ml three-necked flask equipped with a stirrer, 2.61 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.), 4,4′-diaminodiphenyl sulfone (Wakayama Seiki) 0.51 g and N-methyl-2-pyrrolidone 82 ml, cooled to 0 ° C. under nitrogen atmosphere and stirred for 3,3′-biphenyldicarbonyl chloride (manufactured by Toray Fine Chemical) 1.27 g was added in 5 portions. After stirring for 30 minutes, 3.70 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions over 30 minutes with stirring. After stirring for 1 hour, hydrogen chloride generated in the reaction was neutralized with lithium carbonate. As a result, a polymer was deposited, so that the film could not be formed. The physical properties of the obtained polymer were measured and are shown in Table 1.

(Comparative Example 1)
In a 300 ml three-necked flask equipped with a stirrer, 8.85 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.), 4,4′-diaminodiphenylsulfone (Wakayama Seiki) (Made by Kasei Co., Ltd.) 0.76 g and N-methyl-2-pyrrolidone 177 ml were added, cooled to 0 ° C. in a nitrogen atmosphere, stirred with stirring for 30 minutes, 4.94 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 4 , 4'-biphenyldicarbonyl chloride (Tokyo Kasei Co., Ltd.) 1.70 g of the mixture was added in 5 portions. After stirring for 15 minutes, the polymer solution was solidified in a gel state, so that the film could not be formed. The physical properties of the polymer were measured and measured and are shown in Table 1. Since no film was obtained, film physical properties could not be measured.

(Comparative Example 2)
In a 300 ml three-necked flask equipped with a stirrer, 9.83 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 180 ml of N-methyl-2-pyrrolidone were placed, and nitrogen was added. Under the atmosphere, 1.70 g of 4,4′-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions over 30 minutes while cooling to 0 ° C. and stirring. After stirring for 30 minutes, 4.94 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions over 30 minutes with stirring. After stirring for 15 minutes, the polymer solution was solidified in a gel state, so that the film could not be formed. The physical properties of the polymer were measured and measured and are shown in Table 1. Since no film was obtained, film physical properties could not be measured.

(Comparative Example 3)
Lithium bromide (2.88 g) was placed in a 300 ml three-necked flask equipped with a stirrer, and heated and dried using a mantle heater under a nitrogen stream. After cooling to 30 ° C., 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (Wakayama Seika Co., Ltd.) 8.85 g, 4,4′-diaminodiphenyl sulfone (Wakayama Seika Co., Ltd.) 0 .76 g, 174 ml of N-methyl-2-pyrrolidone was added, cooled to 0 ° C. in a nitrogen atmosphere, 4.94 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) over 30 minutes with stirring, 4,4′-biphenyldicarbonyl A mixture of 1.70 g of chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. This polymer solution maintained fluidity after being left for 2 weeks. A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

(Comparative Example 4)
In a 300 ml three-necked flask equipped with a stirrer, 3.73 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (Wakayama Seika Co., Ltd.), 4,4′-diaminodiphenyl sulfone (Wakayama) 2.89 g, N-methyl-2-pyrrolidone (141 ml) were added, cooled to 0 ° C. in a nitrogen atmosphere, stirred for 30 minutes with stirring, and terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.78 g, 4 , 4′-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.30 g of the mixture was added in 5 portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. This polymer solution maintained fluidity after being left for 2 weeks. A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

(Comparative Example 5)
In a 300 ml three-necked flask equipped with a stirrer, 7.86 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.), 4,4′-diaminodiphenyl sulfone (Wakayama Seiki) 1.53 g and N-methyl-2-pyrrolidone (154 ml) were added, cooled to 0 ° C. in a nitrogen atmosphere, and stirred, 4,4′-biphenyldicarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) over 30 minutes. 4.94 g was added in 5 portions. After stirring for 30 minutes, 1.70 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in 5 portions over 30 minutes with stirring. Further, after stirring for 15 minutes, the polymer solution was solidified in a gel state, so that the film could not be formed. The physical properties of the polymer were measured and measured and are shown in Table 1. Since no film was obtained, film physical properties could not be measured.

(Comparative Example 6)
6.41 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) and 56 ml of N-methyl-2-pyrrolidone are placed in a 300 ml three-necked flask equipped with a stirrer. Cooling to 0 ° C. under nitrogen atmosphere, stirring, stirring over 30 minutes, 2.84 g of terephthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.22 g of isophthalic acid dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added in 5 portions. did. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with lithium carbonate to obtain a polymer solution. This polymer solution maintained fluidity after being left for 2 weeks. A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further subjected to heat treatment at 280 ° C. for 1 minute to obtain an aromatic polyamide film (dry and wet film formation). The physical properties of the obtained polymer and film were measured and are shown in Table 1.

Claims (8)

An aromatic polyamide containing at least 1 mol% or more of the structural unit represented by the chemical formula (1).

Mole fraction of structural units containing structural units represented by chemical formulas (1), (2), (3) and (4) and represented by chemical formulas (1), (2), (3) and (4) The aromatic polyamide according to claim 1, wherein the following formulas (1) to (6) are satisfied:

5 ≦ a ≦ 25 (1)
25 ≦ b ≦ 50 (2)
25 ≦ d ≦ 45 (3)
9 ≦ (a + d) / (b + c) ≦ 1.1 (4)
98 ≦ a + b + c + d ≦ 100 (5)
b + c = 50 (6) The aromatic polyamide according to claim 1 or 2, having an intrinsic viscosity of 1.5 dl / g or more. The aromatic polyamide film containing the aromatic polyamide in any one of Claims 1-3. The aromatic polyamide film according to claim 4, wherein the Young's modulus in at least one direction is 5 GPa or more. The aromatic polyamide film according to claim 4 or 5, wherein an average coefficient of thermal expansion at 100 ° C to 200 ° C in at least one direction is -15 ppm / ° C or more and less than 15 ppm / ° C. The aromatic polyamide film according to any one of claims 4 to 6, wherein the light transmittance of light having a wavelength of 400 nm is 70% or more. The aromatic polyamide film according to any one of claims 4 to 7, wherein the haze is 2.0% or less.