JP5668481B2 - Aromatic polyamide and aromatic polyamide film - Google Patents

Description

  The present invention relates to an aromatic polyamide and an aromatic polyamide film that do not contain chlorine or bromine atoms, have excellent solubility, and can exhibit high mechanical properties when formed into a 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 represented by polyparaphenylene terephthalamide (hereinafter sometimes referred to as PPTA) have a molded body with excellent mechanical properties in addition to the above properties due to its rigidity. Because it gives it, its utility value is high. However, para-oriented aromatic polyamides such as PPTA have low solubility in solvents, and are soluble only in very limited solvents such as sulfuric acid, so there is a problem that process restrictions are large, and improvements are required ( For example, Patent Document 1).

  Further, Patent Document 2 discloses a structure in which chlorine atoms are introduced for the purpose of improving solubility in an organic solvent. However, introduction of chlorine has a concern that an environmental load increases.

Studies have also been conducted to introduce fluorine atoms as structural units that have a low environmental burden and an effect of improving solubility. For example, Patent Document 3 discloses an aromatic polyamide into which a fluorine atom called —CF ₃ is introduced. Although the aromatic polyamide disclosed in the document has excellent physical properties, the solubility in a solvent is not sufficient, and it is necessary to add lithium chloride and lithium bromide as a dissolution aid.

  Patent Documents 4 and 5 disclose aromatic polyamides containing fluorine. However, no attempt has been made to achieve both mechanical properties and solubility, and such a film has not been obtained. In addition, aromatic polyamides have been required to have improved light resistance because aromatic rings and amide groups cause oxidative degradation due to light. Patent Document 6 discloses that an ultraviolet absorber is added for the purpose of improving light resistance, but there are many harmful ultraviolet absorbers, and there is a problem of bleeding out during use.

JP-A 62-39634 Japanese Patent No. 4082560 JP 2009-79210 A JP 2004-66716 A Japanese National Patent Publication No. 10-508048 JP 2003-239136 A

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue. That is, an object of the present invention is to obtain an aromatic polyamide and an aromatic polyamide film that do not contain chlorine or bromine atoms, have excellent solubility, and can exhibit high mechanical properties when formed into a film.

The present invention for achieving the above object, the structural units represented by the chemical formula (VI), when the molar fraction of the structural unit represented by the chemical formula (VI) was a, satisfies the following formula (5) It is an aromatic polyamide.
5 ≦ a ≦ 50 (5)

  According to the present invention, an aromatic polyamide having excellent solubility can be obtained although it does not contain chlorine or bromine atoms. In addition, by using the aromatic polyamide of the present invention, high mechanical properties can be expressed when a film is formed. And since a film with a small thermal expansion coefficient can be obtained, it becomes possible to provide an aromatic polyamide film suitable for a circuit board use etc.

  The aromatic polyamide of the present invention contains 5 to 50 mol% of the structural unit represented by the chemical formula (I). Since this structure has a para-oriented aromatic group directly bonded with fluorine atoms adjacent to the carbonyl group, intermolecular hydrogen bonding is inhibited and solubility is improved. Furthermore, it is possible to inhibit hydrogen bonding between the carbonyl group and the water molecule, so that the moisture absorption rate can be reduced. In addition, the light resistance can be improved by reducing the number of C—H bonds on the aromatic ring and increasing the number of C—F bonds that are strong bonds to light.

R ¹ : Para-oriented aromatic group in which fluorine atoms are directly connected R ¹ of the structural unit represented by the chemical formula (I) is preferably selected from the structural units represented by the chemical formula (V).

  Here, e to j satisfy the following (1) to (3).

1 ≦ e ≦ 4 (1)
1 ≦ f + g ≦ 8 (2)
1 ≦ h + i + j ≦ 12 (3)
R ¹ of the structural unit represented by the chemical formula (I) is used for the purpose of reducing light absorption and reducing infrared absorption derived from C—H bonds when the aromatic polyamide of the present invention is used as the core of an optical waveguide, or When the aromatic polyamide of the present invention is used as a proton exchange membrane, it is preferably perfluorinated for the purpose of protecting the aromatic polyamide of the present invention from decomposition by an electrolyte solution. Here, perfluorination refers to the case where e = 4, f + g = 8, and h + i + j = 12, in the case of chemical formula (V).

On the other hand, R ¹ is preferably selected from structural units represented by the chemical formula (X) for the purpose of achieving both the polymerizability of the aromatic polyamide and the physical properties of the resulting aromatic polyamide.

R ¹ of the structural unit represented by the chemical formula (I) is most preferably a 2-fluoro-1,4-phenylene structure. At this time, the structural unit represented by the chemical formula (I) is the structural unit represented by the chemical formula (VI).

  The structural unit represented by the chemical formula (VI) has a very rigid structure and contributes to the improvement of the mechanical strength of the resulting film. Further, when a plurality of fluorine atoms are substituted with an aromatic ring, there is a problem that the reactivity at the time of polymerization is lowered. However, 2-fluoro-terephthalo which is a typical raw material for obtaining a structural unit represented by the chemical formula (VI) Ilchloride has good reactivity, and can obtain a high molecular weight aromatic polyamide. Furthermore, since unsubstituted terephthaloyl chloride is a solid, 2-fluoro-terephthaloyl chloride is a liquid at room temperature, so it can be easily transported, metered, and dropped, and the workability of aromatic polyamide polymerization work Will improve. In addition, if it is solid, it may remain as an unreacted raw material when it adheres to the wall surface of the reaction vessel, but if it is liquid, since there is less such a concern, the accuracy of the reaction rate can be improved. .

  In the aromatic polyamide of the present invention, it is preferable that all aromatic rings contained in the structural unit are bonded at the para position. By bonding at the para position, strong mechanical properties of the aromatic polyamide can be expressed. Conventionally, para-oriented aromatic polyamides may have insufficient solubility, but the present invention has sufficient solubility by including the structural unit represented by the chemical formula (I).

  Moreover, the structural unit constituting the aromatic polyamide of the present invention is preferably selected from the structural units represented by the chemical formulas (I) to (IV).

R ¹ : Para-oriented aromatic group in which fluorine atoms are directly bonded

R ² : Para-oriented aromatic group

R ³ : Para-oriented aromatic group

R ⁴ : a para-oriented aromatic group containing at least one of —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —SiO ₂ —, a structural unit represented by the chemical formula (I) Is as described above.

R ^{2 in the} structural unit represented by the chemical formula (II) is preferably a para-oriented aromatic group for improving mechanical strength. The para-oriented aromatic group is preferably any of phenyl, biphenyl, and terphenyl selected from structural units represented by the chemical formula (XI).

More preferred is phenyl or biphenyl, and most preferred is phenyl. When R ² is phenyl, the structural unit represented by the chemical formula (II) is a structural unit represented by the chemical formula (VII).

  In order to further improve the solubility of the aromatic polyamide while maintaining the mechanical strength, it is preferable that the molecular length of the structural unit represented by the chemical formula (I) is different from that of the structural unit represented by the chemical formula (II). For example, when the structural unit represented by the chemical formula (VI) is used as the structural unit represented by the chemical formula (I), the structural unit represented by the chemical formula (II) is not a phenyl having the same molecular length but a biphenyl having a different molecular length. And terphenyl are preferred. By introducing structural units having different molecular lengths, formation of intermolecular hydrogen bonds is inhibited and solubility is improved.

R ^{3 in the} structural unit represented by the chemical formula (III) is preferably a para-oriented aromatic group for improving mechanical strength. Here, in R ³ , some or all of the hydrogen atoms on the aromatic ring may be substituted with —F, —CF ₃ , —CH ₃ , —NO ₂ , —SO ₃ H, or —SO ₃ Na. .

R ³ is preferably any one of phenyl, biphenyl, and terphenyl selected from the structural unit represented by the chemical formula (XI). Here, a part or all of the hydrogen atoms on the aromatic ring of the structural unit represented by the chemical formula (XI) are —F, —CF ₃ , —CH ₃ , —NO ₂ , —SO ₃ H, and —SO _{3. It} may be substituted with at least one substituent selected from the group consisting of 3Na.

  The structural unit represented by the chemical formula (III) is most preferably a structural unit represented by the chemical formula (VIII).

R ⁴ of the structural unit represented by the chemical formula (IV) includes at least —flexible structural unit —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, —SiO ₂ —. A para-oriented aromatic group containing one is preferable. Note that some or all of the hydrogen atoms on the aromatic ring may be substituted with -F, -CF ₃ , -CH ₃ , -NO ₂ , -SO ₃ H, or -SO ₃ Na. Since the structural units represented by the chemical formulas (I) to (III) are para-oriented aromatic groups having no bent structure, they contribute to the improvement of mechanical properties. On the other hand, the degree of freedom is small. May be a small and brittle film. For this reason, it is preferable to introduce a flexible structural unit represented by the chemical formula (IV) within a range that does not inhibit the rigidity.

  The structural unit represented by the chemical formula (IV) is more preferably a structural unit represented by the chemical formula (IX).

R ⁵ : —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, —SiO ₂ —, or —O—Ph—SO ₂ —Ph—O—
R ⁵ is most preferably —SO ₂ —.

  In the present invention, the molar fraction of the structural unit represented by the chemical formula (I) is a, the molar fraction of the structural unit represented by the chemical formula (II) is b, and the structural unit represented by the chemical formula (III) is When the molar fraction is c and the molar fraction of the structural unit represented by the chemical formula (IV) is d, it is preferable that a, b, c and d satisfy the following formulas (4) to (8).

a + b + c + d = 100 (4)
5 ≦ a ≦ 50 (5)
0 ≦ b ≦ 45 (6)
35 ≦ c ≦ 50 (7)
0 ≦ d ≦ 15 (8)
a is preferably 9.9 or more and 45 or less, more preferably 20 or more and 40 or less. b is preferably 5 or more and 40.1 or less, more preferably 10 or more and 30 or less. c is preferably 40 or more and 45 or less. d is preferably 5 or more and 10 or less.

  Moreover, it is preferable that the rigid unit ratio (R) defined by the following formula (9) satisfies the following formula (10) because both high mechanical strength and elongation can be achieved.

R = 100− (100 × d × k) / (a + b + c + d × k) (9)
30 ≦ R ≦ 100 (10)
K represents the total number per unit structure of —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —SiO ₂ — contained in R ⁴ .

  R is preferably 50 or more, more preferably 70 or more.

  Moreover, it is also preferable that the fluorine ratio (F) of the carbonyl group adjacent aromatic ring defined by the following formulas (11) and (12) satisfies the following formula (13).

F = (100 × a × p) / (a + b) (11)
p = e + f + g + h + i + j (12)
10 ≦ F ≦ 400 (13)
In the above, e to j represent the number of substituted fluorines in the chemical formula (V), but when R ¹ or R ² is an aromatic polyamide having a plurality of types of structures, The rate is multiplied by the number of substituted fluorines, and the sum is taken as the value of p described above.

  F is preferably 20 or more and 100 or less, more preferably 40 or more and 80 or less.

  The aromatic polyamide film using the aromatic polyamide of the present invention has large mechanical properties due to the rigid structure of the polymer.

  In the measurement based on JIS-K7127-1999, the aromatic polyamide film of the present invention has a Young's modulus in at least one direction of 5 GPa or more, and can resist the force applied at the time of processing and has flatness. It is preferable because it becomes even better. Further, when the Young's modulus in at least one direction is 5 GPa or more, the film can be thinned.

  If the Young's modulus in all directions is less than 5 GPa, deformation may occur during processing. Moreover, although there is no upper limit in Young's modulus, when Young's modulus exceeds 20 GPa, the toughness of a film will fall and film formation and a process may become difficult. The Young's modulus is more preferably 7 GPa or more in at least one direction, and still more preferably 10 GPa or more in at least one direction.

  Moreover, it is preferable that the ratio of the maximum Young's modulus (Em) to the Young's modulus (Ep) in the direction orthogonal thereto, Em / Ep, is 1 to 3, because the cutting property during processing is improved. More preferably, it is 1-2.5, More preferably, it is 1-2. When Em / Ep exceeds 3, it may be easy to break.

  The aromatic polyamide film of the present invention preferably has a thermal expansion coefficient in at least one direction of 10 ppm / ° C. or less. The coefficient of thermal expansion is measured in the temperature lowering process after the temperature is raised to 250 ° C. The initial sample length at 25 ° C. and 75 RH% is L0, the sample length at temperature T1 is L1, the sample length at temperature T2 is L2, and the thermal expansion coefficient from T1 to T2 is determined by the following equation.

Thermal expansion coefficient (ppm / ° C)
= (((L2-L1) / L0) / (T2-T1)) × 10 ⁶
Since the aromatic polyamide film of the present invention has a rigid structure, the degree of freedom is small, and the thermal expansion coefficient can be 10 ppm / ° C. or less. When the thermal expansion coefficient is 10 ppm / ° C. or less (small), stress between layers can be reduced when laminated with a material having a low thermal expansion coefficient such as ITO, glass, or semiconductor, and the occurrence of curling and cracking can be suppressed.

The aromatic polyamide film of the present invention preferably has a light transmittance of light having a wavelength of 400 nm of 70% or more. For example, a structural unit represented by the chemical formula (VII) is employed as the structural unit represented by the chemical formula (III), and a structural unit represented by the chemical formula (IX) is employed as the structural unit represented by the chemical formula (IV). ⁵ is -SO ₂ - if, the transmittance of light with a wavelength of 400nm can be 70% or more. When the light transmittance of light having a wavelength of 400 nm is 70% or more, an ultraviolet curable adhesive can be used. In addition, there is an advantage that it can be used for applications requiring colorless and transparent, such as displays and solar cells.

  Furthermore, the aromatic polyamide of this invention can enlarge haze by making small the molar fraction d of the structural unit represented by Chemical formula (IV). In applications such as a display substrate, it is preferable that the haze is small. On the other hand, there is an application such as a reflector in which the haze is greatly controlled. In this case, the haze is preferably 5% or more. This is considered to be because the polymer is precipitated during film formation, and it is preferable to use a polymer solution that does not use a solubilizing agent for applications where a large haze is preferred. On the other hand, for applications in which the haze is preferably small, a film having a small haze can be obtained by increasing the molar fraction d of the structural unit represented by the chemical formula (IV) or by adding a dissolution aid.

  It is also preferable that the aromatic polyamide film of the present invention is halogen-free in measurement based on JPCA-ES01-2003. In the present invention, “having no halogen in the measurement according to JPCA-ES01-2003” is sometimes referred to as “containing no chlorine or bromine atoms”. By being halogen-free in the measurement based on JPCA-ES01-2003, the concern about environmental load can be reduced.

  The aromatic polyamide film of the present invention is also preferably soluble in N-methyl-2-pyrrolidone in an amount of 5% by mass or more. Here, “it is possible to dissolve 5% by mass or more in N-methyl-2-pyrrolidone” (hereinafter sometimes referred to as “solubility is“ ◯ ””) means that a polymer is added to N-methyl-2-pyrrolidone. It means that it dissolves by mass% or more and then maintains fluidity after being left at 25 ° C. for 2 weeks. When the polymer is dissolved in excess of 5% by mass and the solubility is “◯”, the solubility is “◯” even at 5% by mass.

  “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 °.

  Although the example which manufactures the aromatic polyamide and aromatic polyamide film of this invention below is demonstrated, this invention is not limited to this.

  When the aromatic polyamide of the present invention contains 5 to 50 mol% of the structural unit represented by the chemical formula (I), 5 mass% or more can be dissolved in N-methyl-2-pyrrolidone. Thereby, film formation by a solution film-forming method becomes possible, and a film excellent in surface smoothness can be obtained. In addition, it is also possible to add a dissolution aid as appropriate for the purpose of reducing the haze.

  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.

  The molar ratio of all diamines to all acid dichlorides is preferably 95 to 105: 105 to 95, and if this value is exceeded, it will be 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 Phenolic solvents such as p-cresol, xylenol, halogenated phenol, and catechol, or hexamethylphosphoramide, γ-butyrolactone, and the like can be used. These are preferably used alone or as a mixture, but more preferably xylene, toluene The use of aromatic hydrocarbons such as are possible. Furthermore, for the purpose of accelerating the dissolution of the polymer, 50% by mass or less of an alkali metal or alkaline earth metal salt can be added to the solvent as a dissolution aid. Examples of the dissolution aid include lithium bromide and lithium chloride.

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. Examples of additives for surface formation include inorganic particles such as SiO ₂ , TiO ₂ , Al ₂ O ₃ , CaSO ₄ , BaSO ₄ , CaCO ₃ , carbon black, carbon nanotubes, fullerene, zeolite, and other metal fine powders. Etc. Preferred organic particles include, for example, particles made of an organic polymer such as crosslinked polyvinylbenzene particles, crosslinked acrylic particles, crosslinked polystyrene particles, polyester particles, polyimide particles, polyamide particles, and fluororesin particles, or the above-mentioned organic particles on the surface. Inorganic particles that have been subjected to a treatment such as coating with a polymer are exemplified.

  Next, film formation will be described.

  Since the aromatic polyamide of the present invention is easily dissolved 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 formed into a film by a so-called solution casting method. Solution casting methods include dry and wet methods, dry methods, and wet methods, and any of these methods can be adopted. However, the aromatic polyamide of the present invention is excellent in solubility, so that the film forming process is easily controlled. Is preferred. Hereinafter, a dry and wet method will be described as an example.

  In the case of film formation by a dry-wet method, the film-forming 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 self-holding properties. Drying conditions can be performed in the range of room temperature to 220 ° C. and within 60 minutes, for example. In addition, an aromatic polyamide film having a smooth surface can be obtained by smoothing the surface of a support such as a drum, an endless belt, or a film used in the drying step. A microlens array is formed on a part or all of the surface of the support. By pressing a mold such as a prism sheet, a film having a shape such as a microlens array or a prism sheet can be obtained. The film after the dry process is peeled off from the support, introduced into the wet process, subjected to desalting, desolvation and the like, and further subjected to stretching, drying and heat treatment to become an aromatic polyamide 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. It is preferable that it is in 1.3, More preferably, it is 1.3-8. In addition, the heat treatment is preferably performed at a temperature of 200 ° C. to 500 ° C., preferably 250 ° C. to 400 ° C. for several seconds to several minutes. 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 aromatic polyamide film of the present invention can be used alone, or can be used in a state of being formed into a film on some support.

  When used alone, the thickness is preferably 1 μm to 100 μm. When the thickness is less than 1 μm, it may break due to the tension during film formation or use. On the other hand, when the thickness exceeds 100 μm, it may be difficult to remove the solvent and the dissolution aid in the film forming process. The thickness is preferably 1 μm to 80 μm, more preferably 2 μm to 60 μm, and most preferably 5 μm to 30 μm.

  On the other hand, when the film is used in the form of a film on some support, the thickness of the film (the thickness excluding the support) is preferably 10 μm or less. When a film-like material is formed on the support, the solvent is removed from one side, and therefore removal of the solvent may be difficult when the thickness exceeds 10 μm. Although there is no particular lower limit to the thickness of the film-like portion, for example, it is preferable to use a method such as vapor deposition polymerization in order to apply uniformly with a thickness of about 0.0001 μm, thereby forming an extremely thin film. Is possible. When a polymer solution is applied onto a support and dried to obtain a film, the thickness of the film-like portion is preferably 0.01 μm or more and 10 μm or less, more preferably 0.1 μm or more and 5 μm or less, most preferably 0. .5 μm or more and 3 μm or less.

  As a form to be used by forming a film on the support, specifically, for example, a film that fills the sensor part of an uneven CCD (charge coupled device) to flatten the surface, that is, a so-called CCD flattening film. be able to. In this case, one side of the film-like object has a concavo-convex shape in accordance with the sensor part of the CCD. Of course, both surfaces of the film-like material may be uneven.

  Moreover, it is also preferable to set it as the laminated body containing at least 1 layer containing the aromatic polyamide mentioned above or its copolymer. In this case, examples of the layer other than the layer containing the aromatic polyamide or the copolymer thereof include metal foil such as copper foil and stainless steel foil, tin oxide (ITO) doped with glass, silicon, and indium. Moreover, it is also preferable to set it as the molded object containing the aromatic polyamide mentioned above and its copolymer. In this case, examples of the molded body include a microlens array and a prism sheet.

  The film (aromatic polyamide film) obtained from the above-mentioned aromatic polyamide may be a single layer film or a laminated film. In addition, the aromatic polyamide film of the present invention is a circuit board such as a flexible printed circuit board, a photoelectric composite circuit board, an optical waveguide board, a semiconductor mounting board, a multilayer laminated circuit board, a display material board, a transparent conductive film, a retardation film, It is preferably used for various applications such as display materials such as touch panels, reflective materials, capacitors, printer ribbons, acoustic diaphragms, solar cells, optical recording media, and magnetic recording media base films.

  In general, glass is used as the display material substrate. However, when the aromatic polyamide film of the present invention is used as the display material substrate, there are great merits such as thinning, lightening, and no cracking. The type of the display material of the present invention is not particularly limited, but is preferably a thin film, a thin film display that is advantageous in light weight, or a thin film display. Examples of the thin film display include a liquid crystal display, an organic EL display, an inorganic EL display, a plasma display, a field emission display, and electronic paper.

  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 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) Haze It measured using the following measuring device.

Apparatus: Direct reading haze meter HGM-2DP (for C light source) (manufactured by Suga Test Instruments Co., Ltd.)
Light source: halogen lamp 12V, 50W
Light receiving characteristics: 395 to 745 nm
Optical conditions: Based on JIS-K7105-1981 (2) Light transmittance of light having a wavelength of 400 nm Measured with the following apparatus and conditions. The calculation formula is as follows.

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: Permeation (3) Thermal expansion coefficient The thermal expansion coefficient was measured in the temperature lowering process after the temperature was raised to 250 ° C. in accordance with JIS K7197-1991. The initial sample length at 25 ° C. and 75 RH% is L0, the sample length at temperature T1 is L1, the sample length at temperature T2 is L2, and the average thermal expansion coefficient from T1 to T2 is obtained by the following formula, and the thermal expansion Coefficient. Note that T2 = 100 (° C.) and T1 = 200 (° C.).

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

(4) Young's modulus, tensile strength, elongation at break In measurement according to JIS-K7127-1999, measurement was performed at a temperature of 23 ° C. and a relative humidity of 65% using Robot Tensilon RTA (manufactured by Orientec). The test piece was a sample having a width of 10 mm and a length of 50 mm in the MD direction or 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.

(5) Solubility 5 mass% of the polymer was dissolved in N-methyl-2-pyrrolidone, and the one that maintained fluidity after being allowed to stand at 25 ° C. for 2 weeks was evaluated as solubility “◯”.

  “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 °.

(6) Halogen free Measured according to JPCA-ES01-2003.

Example 1
In a 200 ml three-necked flask equipped with a stirrer, 4.87 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Toray Fine Chemical Co., Ltd.) and 88 ml of N-methyl-2-pyrrolidone were placed under a nitrogen atmosphere. Then, 3.33 g of 2-fluoroterephthaloyl dichloride (manufactured by Ihara Nikkei) was added dropwise using a dropping funnel over 30 minutes while cooling to 0 ° C. and 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 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 shown in the table.

(Example 2)
1.39 g of anhydrous lithium bromide was placed in a 200 ml three-necked flask equipped with a stirrer, and heated to 120 ° C. with stirring under a nitrogen stream to dry. After cooling to 30 ° C., 4.50 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (manufactured by Toray Fine Chemical), 4,4′-diaminodiphenylsulfone (manufactured by Wakayama Seika Co., Ltd.) 44DDS ”) 0.39 g and 86 ml of N-methyl-2-pyrrolidone were put in a nitrogen atmosphere, cooled to 0 ° C., stirred for 30 minutes with 0.69 g of 2-fluoroterephthaloyl dichloride (manufactured by Ihara Nikkei) over 30 minutes. It dropped using the dropping funnel. Further, 2.53 g of terephthaloyl 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 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 shown in the table.

(Examples 3 to 5)
A polymer and a film were obtained in the same manner as in Example 1 except that the diamine and acid chloride used were changed to those described below. Various physical properties are shown in Tables 1 and 2.

(Comparative Example 1)
In Example 1, except that 3.33 g (15.2 mmol) of 2-fluoroterephthaloyl dichloride (manufactured by Ihara Nikkei) is changed to 3.06 g (15.2 mmol) of terephthaloyl dichloride (manufactured by Tokyo Chemical Industry Co., Ltd.). Polymerization was conducted in the same manner. 2-Fluoroterephthaloyl dichloride could be dropped because it was liquid, while terephthaloyl dichloride was solid, so a dropping funnel could not be used, and it was necessary to add it manually using a powder funnel. Sex deteriorated. In the middle of the polymerization, a viscous polymer solution was obtained, but when all the amount of terephthaloyl dichloride was added, the viscosity increased so much that a gel-like solid having no fluidity was obtained.

(Comparative Example 2)
Polymerization was carried out in the same manner as in Comparative Example 1 except that the diamine and acid chloride used were changed to those described below. When the total amount of terephthaloyl dichloride was added, the viscosity increased so much that a gel-like solid having no fluidity was obtained.

Claims (17)

The structural units represented by the chemical formula (VI), when the molar fraction of the structural unit represented by the chemical formula (VI) was a, aromatic polyamide satisfying the following equation (5).

5 ≦ a ≦ 50 (5) 2. The aromatic polyamide according to claim 1, wherein all aromatic rings are bonded at the para position. Mole fraction of the structural unit represented by Structural Formula a molar fraction of the structural unit represented by (VI) a, a molar fraction of the structural unit represented by Formula (II) b, formula (III) the c, when the molar fraction of the structural unit represented by formula (IV) was d, a, b, c and d satisfy the following formulas (4) to (8), according to claim 2 Aromatic polyamide.
a + b + c + d = 100 (4)
5 ≦ a ≦ 50 (5)
0 ≦ b ≦ 45 (6)
35 ≦ c ≦ 50 (7)
0 ≦ d ≦ 15 (8)

R ² : Para-oriented aromatic group

R ³ : Para-oriented aromatic group

R ⁴ : a para-oriented aromatic group containing at least one of —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —SiO ₂ —. The aromatic polyamide according to claim 3 , comprising a structural unit represented by the chemical formula (IV) and having a rigid unit ratio (R) defined by the following formula (9) satisfying the following formula (10):
R = 100− (100 × d × k) / (a + b + c + d × k) (9)
However, k represents the total number per unit structure of —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —SiO ₂ — contained in R ⁴ .
30 ≦ R ≦ 100 (10) The structural units represented by Formula (II), a structural unit a structural unit represented by the formula (II) is represented by the chemical formula (VII), an aromatic polyamide according to claim 3 or 4.

The structural units represented by Formula (III), a structural unit a structural unit represented by the formula (III) is represented by the chemical formula (VIII), aromatic polyamide according to any one of claims 3-5.

The structural units represented by the formula (IV), a structural unit a structural unit represented by the formula (IV) is represented by the chemical formula (IX), aromatic polyamide according to any one of claims 3-6.

R ⁵ : —CH ₂ —, —O—, —SO ₂ —, —C (CF ₃ ) ₂ —, —SiO ₂ —, or —O—Ph—SO ₂ —Ph—O— Aromatic polyamide film with an aromatic polyamide according to any one of claims 1-7. The aromatic polyamide film according to claim 8 , wherein the haze is 5% or more. The aromatic polyamide film according to claim 8 or 9 , 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 8 to 10 , wherein a coefficient of thermal expansion in at least one direction is 10 ppm / ° C or less. The aromatic polyamide film according to any one of claims 8 to 11 , wherein Young's modulus in at least one direction is 5 GPa or more. The aromatic polyamide film according to any one of claims 8 to 12 , which is halogen-free in measurement according to JPCA-ES01-2003. The aromatic polyamide film according to any one of claims 8 to 13 , which is soluble in N-methyl-2-pyrrolidone by 5% by mass or more. The display material using the aromatic polyamide film in any one of Claims 8-14 . The circuit board using the aromatic polyamide film in any one of Claims 8-14 . The reflective material using the aromatic polyamide film in any one of Claims 8-14 .