JP3405022B2 - Aromatic polyamide composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polyamide composition.

[0002]

BACKGROUND OF THE INVENTION Aromatic polyamide is a polymer useful as an industrial material because of its high heat resistance and electric insulation. In particular, aromatic polyamides represented by PPTA, which are composed of para-oriented aromatic nuclei, give molded articles excellent in strength and elastic modulus in addition to the above-mentioned characteristics due to their rigidity, and thus have high utility value. However, a para-oriented aromatic polyamide such as PPTA has low solubility in a solvent and is only soluble in a very limited solvent such as sulfuric acid, so that there are large process restrictions, and the solution also gives optical anisotropy. There is no major problem in obtaining fibers, but in order to form a molded product having two or more dimensions, such as a film, JP-A-62-39634, JP-A-62-104714 and JP-A-62-115036 are disclosed. It is necessary to use the special molding method described in, etc., and its improvement is required.

On the other hand, the introduction of a structural unit having a bridge such as oxygen or a methylene group is known from JP-A-51-76836 and JP-A-52-98795 as means for improving the solubility. However, the introduction of such a structural unit generally impairs the original mechanical properties such as Young's modulus and strength inherent in the para-oriented aromatic polyamide. Further, as another means, an aromatic polyamide in which a chlorine atom is introduced into an aromatic nucleus is proposed in JP-A-52-84826, JP-A-54-106564 and the like, but such an aromatic polyamide is a monomer. In addition to being expensive, there is a concern that chlorine and dioxins will be generated when the molded product obtained from the product is discarded or incinerated.

[0004]

The present invention solves the above problems and is excellent in the solubility in a solvent and the stability of a solution without impairing the excellent heat resistance and mechanical properties of the aromatic polyamide. Is also soluble in organic solvents,
An object of the present invention is to provide an aromatic polyamide composition suitable for obtaining a molded product such as a fiber, a film or a sheet.

[0005]

That is, the present invention provides a group A comprising structural units having different aromatic nuclei represented by the general formula (I), the general formula (I)

[Chemical 5] Group B consisting of structural units having different aromatic nuclei represented by general formula (II), general formula (II)

[Chemical 6] And a group C comprising structural units having different aromatic nuclei represented by the general formula (III), the general formula (III)

[Chemical 7] (Here, Ar ₁ , Ar ₂ , and Ar ₃ are para-oriented aromatic nuclei, and the compounds of each group include a nitro group represented by Ra, Rb, and Rc, a cyano group, an alkyl group having 1 to 4 carbon atoms, and a carbon atom. Number 1
To 3 may be substituted with a functional group selected from an alkoxy group, a trialkylsilyl group, an oxyaryl group and a thioaryl group. Here, k, l and m are each 0
~ Is a number of 4. From at least three types (provided that at least two types of structural units having different basic aromatic nuclei are selected from the same group) and the general formula (I
Group D consisting of the structural unit represented by V), the general formula (IV)

[Chemical 8] (Here, Ar ₄ and Ar ₅ are para-oriented aromatic nuclei,
X and Y may be the same or different from each other, -CO- or -NH- group. Here, when both X and Y are -CO-, A
Group (B group, D group), when both X and Y are -NH-, (A
Group, D group) and B group, and when different from each other, A group and B group are substantially equimolar. ) Is a main structural unit, and 1% by weight of an oligomer having a molecular weight of 1000 or less is used.
It is the following aromatic polyamide composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION First, the aromatic polyamide of the present invention has the above general formula (I), general formula (II) and general formula (III).
) Structures in which at least 3 kinds are selected from the 3 groups, and at least 2 kinds of them are different from each other in the basic aromatic nucleus selected from the same group (defined as the rest except functional groups and substituents). It consists of units. With such a constitution, the solubility of the polymer and the stability of the polymer solution are dramatically improved. In addition, general formula (I), general formula (II), general formula (III
It is preferable that at least 4 or more, more preferably 5 or more are selected from the 3 groups of 1), and the number of groups in which 2 or more different structural units having different basic aromatic nuclei are selected is 2 or more. preferable. Further, the existence ratio (AR) of each basic aromatic nucleus in a group in which two or more kinds of structural units having different basic aromatic nuclei are selected is n.
1 / n × 0.7 ≦ AR ≦ 1 / n × 1.3
Preferably, 1 / n × 0.8 ≦ AR ≦ 1 / n × 1.2
More preferably, 1 / n × 0.9 ≦ AR ≦ 1 / n × 1.
When it is 1, it is possible to obtain a molded product which is excellent not only in solubility of the composition and stability of the solution but also in mechanical properties.

Next, Ar ₁ , Ar ₂ and Ar ₃ are para-oriented aromatic nuclei different from each other. The para-oriented aromatic nucleus referred to here is defined as an aromatic nucleus in which divalent binding chains are coaxial or parallel to each other.

[Chemical 9] However, the present invention is not limited to this. Further, “different from each other” means different kinds and numbers of basic aromatic nuclei or substituents. Ar ₁ ,
The para orientation of Ar ₂ and Ar ₃ is a necessary factor in terms of mechanical requirements. Therefore, the aromatic polyamide of the present invention preferably contains such a binding unit in an amount of 60 mol% or more, preferably 70 mol% or more, and more preferably 75 mol% or more. If it is less than 60 mol%, when it is made into a molded product, it cannot fulfill its sufficient functions as a molded product such as strength, elongation, rigidity and heat resistance.

The aromatic polyamide of the present invention contains two or more different basic aromatic nuclei. It is preferably 3 or more, preferably 4 or more. Among these, as a combination of basic aromatic nuclei, at least two kinds selected from a phenylene group, a biphenylene group, and a naphthylene group, particularly a combination of a biphenylene group and a phenylene group are preferable because they are excellent in mechanical properties and solubility in a solvent.

Furthermore, the aromatic polyamide of the present invention contains a structural unit of group D represented by the general formula (IV).

General formula (IV)

[Chemical 10] (Here, Ar ₄ and Ar ₅ are para-oriented aromatic nuclei which may be different from each other, and X and Y may be the same or different from each other, —CO— or —NH— group. Here, X,
When Y is both -CO-, A group (B group, D group), X, Y
Are both -NH- (groups A and D) and group B, and when they are different from each other, groups A and B are substantially equimolar. ) Ar ₄ and Ar ₅ are para-oriented aromatic nuclei and
_It is defined similarly to _{1 to} Ar _3, and hydrogen on the aromatic nucleus may be substituted with a substituent other than halogen.

The aromatic polyamide containing the structural unit of group D is very excellent in stability of the solution when it is used as an organic solvent solution, for example. When the polymer does not contain the structural unit, even if there is no precipitation of polymer during polymerization, a phenomenon such as gelation after polymerization which is inconvenient for molding occurs.

However, as described above, the introduction of such a structural unit may impair the mechanical properties of the molded product, and preferably 2 to 40% of the wholly aromatic polyamide structural unit,
More preferably 5 to 30%, even more preferably 10 to 25
It is better to use it within the range of%.

Further, each aromatic nucleus of the aromatic polyamide of the present invention has substituents Ra, Rb, which substitute a hydrogen atom of the aromatic nucleus,
Rc is aromatic when substituted with a substituent selected from a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a trialkylsilyl group, an oxyaryl group and a thioaryl group. It is preferably used because a group polyamide having excellent solubility and solution stability can be obtained. The substitution ratio in the above general formula (I), general formula (II) and general formula (III) is 1 <k + l and /
Alternatively, when 1 <m, a clear effect can be obtained. Preferably, 1.5 <k + l, more preferably 2 ≦ k + 1 and 1 ≦ k, 1 ≦ l or 2 ≦ k + l and (1.5 ≦ k
Or 1.5 ≦ l). In the group consisting of a plurality of structural units, k, l, and m can be calculated by the arithmetic average based on the molar ratio. Since the aromatic polyamide having these substituents has the above-mentioned characteristics, it also has an effect of utilizing the polymerization or film forming process.

In addition to the above, hydrogen atoms in the amide bond constituting the polymer may be replaced with other substituents, or a monomer having a relatively large molecular weight may be used in order to reduce the amide group density.

The aromatic polyamide of the present invention contains 60 mol% or more of the repeating unit represented by the general formula (I), the general formula (II) or the general formula (III). The structural unit having the structure of may be copolymerized or blended. Of course, the aromatic nucleus contained in these structural units also has a substituent such as a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a trialkylsilyl group, an oxyaryl group or a thioaryl group. It may have a group. In particular, the aromatic polyimide represented by the general formula (V) and / or the general formula (VI) is effective in improving mechanical properties and is preferably used.

General formula (V)

[Chemical 11] General formula (VI)

[Chemical 12] Here, Ar ₆ and Ar ₈ include at least one aromatic ring, and two carbonyl groups forming an imide ring are bonded to adjacent carbon atoms on the aromatic ring. This Ar ₆ is derived from an aromatic tetracarboxylic acid or its anhydride.
The following are typical examples.

[0017]

[Chemical 13] Wherein Z is _{-O -, - CH 2 -,} - CO -, - SO
_{2 -, - S -, -} C (CH 3) 2 - is chosen from such,
It is not limited to this.

Ar ₈ is derived from carboxylic acid anhydride or its halide. Ar ₇ and Ar ₉ are, for example,

[Chemical 14] And the like, X ′ and Y ′ are —O—, —CH ₂ —, —
_{CO -, - SO 2 -,} - S -, - C (CH 3) 2 - is chosen from such, but is not limited thereto. Further, a part of hydrogen atoms on these aromatic rings is a substituent such as a halogen group (especially chlorine), a nitro group, an alkyl group having 1 to 4 carbon atoms (especially a methyl group), an alkoxy group having 1 to 3 carbon atoms, and the like. And those in which hydrogen in the amide bond constituting the polymer is replaced by another substituent.

The aromatic polyamide composition of the present invention preferably contains 1% by weight or less, more preferably 0.5% by weight or less, of an oligomer having a molecular weight of 1,000 or less. The oligomers referred to here are those which partially contain the structural units represented by the general formulas (I) to (IV), and include, for example, a reaction product with a solvent. If the content of this oligomer exceeds 1% by weight, the mechanical and thermal properties of the molded product may be impaired, or the product quality may be impaired due to exudation during use.

The aromatic polyamide composition of the present invention may be blended with particles, lubricants, antioxidants and other additives to the extent that the physical properties of the molded article are not impaired.

The aromatic polyamide composition of the present invention has excellent properties such as good mechanical properties and heat resistance, and is preferably made from an organic solvent system into a molded product such as fiber, film or sheet. You can A conventionally known method may be used as a means for obtaining these molded bodies. In particular, a film or sheet obtained from an organic solvent solution has excellent surface properties and thus has high industrial utility value. Furthermore, since the solution has optical isotropy, film formation is possible without a special method. There is particularly preferable. The organic solvent used here dissolves the aromatic polyamide,
There is no particular limitation as long as a stable solution can be formed, but N-
Aprotic organic polar solvents such as methylpyrrolidone, dimethylacetamide, dimethylformamide and hexamethylphosphoramide are preferably used. Of course, these organic solvents may be mixed solvents.

Next, a method for producing the aromatic polyamide composition of the present invention and an example of producing a film as a molded article will be described, but the present invention is not limited thereto.

The aromatic polyamide may be obtained by, for example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method or a solid phase polymerization method. When the aromatic polyamide is obtained from an acid chloride and a diamine, N-methylpyrrolidone (N
MP), dimethylacetamide (DMAc), dimethylformamide (DMF) and the like in an aprotic organic polar solvent. When acid chloride and diamine are used as monomers in the polymer solution, hydrogen chloride is by-produced.When neutralizing this, inorganic neutralizing agents such as calcium hydroxide, calcium carbonate and lithium carbonate, and ethylene Organic neutralizing agents such as oxides, propylene oxide, ammonia, triethylamine, triethanolamine, diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in the presence of a catalyst in an aprotic organic polar solvent.

At the time of this polymerization, the oligomer content can be set within the preferred range of the present invention. It is of course possible to use a high-purity raw material and use a solvent from which impurities such as water have been removed, but especially when carrying out on an industrial scale, apply appropriate shear stress to the solution during polymerization and mix efficiently. Is extremely important. The formation reaction of the aromatic polyamide is extremely exothermic at the initial stage of the reaction. This reaction heat causes reaction with solvent molecules and deactivation of active terminals,
Oligomer molecules are generated. Therefore, it is important to remove the heat by mixing at a high speed in the initial stage of the polymerization. Further, the viscosity of the polymerization solution increases with the reaction, but under such a condition, mixing at a high speed will result in a non-uniform mixed state, resulting in an insufficiently reacted oligomer component. Therefore, it is preferable to control the mixing speed to decrease from the beginning to the end of the polymerization as the viscosity of the solution increases.

These polymer solutions may be directly used as a stock solution for obtaining a molded product, or the polymer may be isolated once and then redissolved in the above-mentioned organic solvent or an inorganic solvent such as sulfuric acid to prepare a stock solution. You may.

The intrinsic viscosity of the polymer (0.5 g of the polymer
Value measured at 30 ° C. as a 100 ml solution in sulfuric acid) is preferably 0.5 or more.

Inorganic salts such as calcium chloride, magnesium chloride, lithium chloride and lithium nitrate may be added as a dissolution aid to the stock solution for obtaining the molded product. The polymer concentration in the stock solution is preferably 2 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably 10 to 25% by weight. If it falls below this range, it is economically disadvantageous because the ejection is required to be large, and if it exceeds it, it is difficult to obtain a thin or thin product due to the ejection amount or the solution viscosity.

If necessary, for example, SiO ₂ , TiO _2
The content of particles of inorganic particles such as ₂ , TiN, Al ₂ O ₃ , ZrO ₂ , zeolite and other fine metal powders and organic particles is 0.01-5% by weight, preferably 0.05-
Add 3% by weight.

The method of adding particles is not particularly limited, but when adjusting the degree of aggregation, for example, a method of previously dispersing the particles in a solvent of 10 poise or preferably 1 poise or less can be mentioned. The solvent is preferably the same as that used for film formation, but other solvents may be used unless particularly adverse effects are observed. Further, additives such as a dispersion aid may be used in these solvents within a range that does not adversely affect dispersion. A stirring disperser, a ball mill, an ultrasonic disperser, or the like is used for dispersing the particles, and
Adjust the degree of cohesion.

The dispersed particles are mixed with the above-mentioned polymer solution. In mixing, they may be added to a solvent before polymerization, added after polymerization, or added at the time of preparing a polymer solution, and may be just before discharge. It is very important that it is uniformly dispersed in the stock solution.

Next, film formation will be described. The stock solution for film formation prepared as described above is formed into a film by a so-called solution film forming method. The solution casting method is a dry-wet method,
There is no problem even if the film is formed by any method such as a dry method and a wet method, but here, the dry-wet method will be described as an example.

When a film is formed by a dry-wet method, the stock solution is extruded from a spinneret onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer until the thin film has a self-holding property. To do. Drying conditions are, for example:
It can be performed at room temperature to 220 ° C. for 60 minutes or less. If the surface of the drum or endless belt used in this drying step is as smooth as possible, a film having a smooth surface can be obtained. The film that has undergone the dry process is peeled from the support and introduced into the wet process, desalting, desolventizing, etc. are carried out, and further stretching, drying and heat treatment are carried out to obtain a film.

Stretching is carried out at a surface draw ratio of 0.8 to
The area ratio is preferably 8.0 (defined as a value obtained by dividing the area of the film after stretching by the area of the film before stretching. 1 or less means relaxing), and more preferably 1 .3 to 8.0. Further, the heat treatment is 200 ° C to 500 ° C, preferably 250 ° C to 400 ° C.
The heat treatment is preferably carried out at the temperature of several seconds to several minutes.
Further, it is effective to gradually cool the film after stretching or heat treatment, and it is effective to cool the film at a rate of 50 ° C./second or less.

The aromatic polyamide composition of the present invention has a tensile Young's modulus E20 in at least one direction at 20 ° C. and a relative humidity of 60% as a film of E20 ≧ 7.8.
It is preferable that E 20 ≧ 8.82 GPa, more preferably E 20 ≧ 9.80 GPa.

Since the aromatic polyamide composition of the present invention has excellent mechanical properties, it exhibits excellent effects not seen in other materials, especially when formed into a thin film. The preferable thickness is 0.5 to 50 μm, more preferably 1 to 20 μm, and further preferably 2 to 10 μm.

The film obtained from the aromatic polyamide composition of the present invention may be a single layer film or a laminated film. In the case of a laminated film, the base film and the base layer portion (film constituting portion other than the laminated base film of the present invention) of the magnetic recording medium of the present invention may be the same kind or different. For example, in the case of two layers, the polymerized aromatic polyamide solution is divided into two, and different particles are added, respectively, and then laminated. The same applies to the case of three or more layers. As a method of stacking these, there are known methods such as stacking in a die, stacking in a composite tube, and a method in which one layer is once formed and then another layer is formed thereon.

The metal ion contained in the molded article is preferably 3000 ppm or less, more preferably 1 ppm or less.
When it is at most 00 ppm, particularly preferably at most 30 ppm, it is possible to obtain an excellent molded product that does not affect the corrosion of the contact member.

This not only raises the purity of the raw materials including the solvent, but prevents the formation of a dense layer on the surface in the step of extracting the polymerization solvent and the inorganic salt when forming the molded product. It is preferable to use, for example, an extraction tank in which a solvent of the same kind as the polymerization solvent is mixed with the coagulation solvent at a certain gradient ratio, or to adjust the extraction temperature, for example, to provide a temperature gradient in a plurality of extraction layers. That's the method.

[0039]

EXAMPLES The methods of measuring physical properties and evaluating effects of the present invention are as follows.

(1) Strength, elongation, Young's modulus Tensilon manufactured by Orientec Co., Ltd.
It was carried out at a pulling speed of 300 mm / min.

(2) A molecular chain solution size-separated by a GPC device by incorporating a low-angle laser light scattering photometer (LALLS) and a differential refractometer (RI) into a weight fraction gel permeation chromatograph (GPC) of an oligomer. By measuring the light scattering intensity and the difference in refractive index along with the elution time, the molecular weight of the solute and its content were sequentially calculated, and finally the absolute molecular weight distribution of the high molecular weight substance was calculated.
Diphenylmethane was used for absolute molecular weight calibration.

As a simple method, it is also possible to simply collect the fractions having a molecular weight of 1000 or less in the size-sorted solution and remove the solvent to obtain the fraction.

(3) 2 g of aromatic polyamide fiber or film as a metal ion content sample was burnt and incinerated, dissolved in nitric acid and hydrofluoric acid, and then solubilized in dilute nitric acid.

Next, using an atomic absorption spectrometer, quantification was performed based on a calibration curve prepared in advance. Here, the unit ppm is (μg / g).

Examples 1 to 9 and Comparative Examples 1 to 4 The abbreviations of the raw materials used in the following Examples or Comparative Examples are as follows.

Aromatic diamine component: PPD: Paraphenylenediamine DPX: 2,5-Dimethylparaphenylenediamine DMB: 3,3'-Dimethylbenzidine DOB: 3,3'-Dimethoxybenzidine DBA: 4,4'-Diaminobenz Anilide DPE: 4,4'-diaminodiphenyl ether acid chloride component: TPC: terephthalic acid dichloride MPC: 2-methylterephthalic acid dichloride NPC: 2,6-naphthalenedicarboxylic acid dichloride BPC: 4,4'-biphenyldicarboxylic acid dichloride DPC: 4,4'-Diphenyl ether dicarboxylic acid dichloride anhydride component: PAH: pyromellitic anhydride

Example 1 Using a polymerization tank equipped with an anchor-type stirring blade and having a tank diameter of 1.8 m and having a cooling jacket, 50 mol% DOB and 30 mol% of DOB were added to dehydrated N-methylpyrrolidone (hereinafter abbreviated as NMP). Dissolve PPD, 20 mol% DPE and cool the solution. Then, 100 mol% of TPC was added, the mixture was stirred for 2 hours while controlling the linear velocity from 4.5 m / sec to 1.5 m / sec, and neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 10% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks.
The oligomer content in this solution was 0.2% by weight.

The linear velocity is 4.5 m / sec or 1.5
Polymerization was performed in the same manner as above except that the stirring was performed at a constant speed of m / sec. The polymer concentration was 10% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. However, due to the broadening of the molecular weight distribution or the increase in the components which are considered to be the reaction product with the solvent, the content of oligomers having a molecular weight of 1,000 or less was more than 1% by weight.

Reference Example 1 The aromatic polyamide solution obtained in Example 1 was treated with a pore size of 0.15 m.
Take a cylinder with a cap of m and 40 holes, 8
It was extruded into a coagulation bath consisting of a saturated aqueous calcium chloride solution kept at 0 ° C. At this time, the distance between the cap surface and the coagulation bath surface was 10 mm. The spun fiber was washed with water, dried, and then drawn on a hot plate at 300 ° C. and 480 ° C. at a total draw ratio of 5.0 times to obtain a fiber. The strength, elongation and Young's modulus of this fiber were 21.0 g / d, 3.5% and 810 g / d, respectively. The metal ion content was 200 ppm.

Fibers were obtained in the same manner by using a polymer solution having the above-mentioned oligomer content of more than 1% by weight. In this solution, the spinnability was decreased, and the strength of the obtained fibers was 3
It decreased by g / d or more. In addition, the coloring of the fibers was large and the appearance was poor.

Example 2 As in Example 1, 40 mol% DMB, 40 mol% PPD and 20 mol% DPE were dissolved in NMP, the solution was cooled and then 100 mol% TPC was added. The mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 12% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.2% by weight.

Reference Example 2 The aromatic polyamide solution of Example 2 was passed through a filter with a cut of 5 μm, cast on a stainless steel belt, the solvent was evaporated in a dryer, and a film having self-supporting property was belted. Peeled off and introduced into a water bath to extract residual solvent, etc.,
Then, it was dried in a tenter and heat-treated. At this time, stretched 1.25 times in the longitudinal direction and 1.3 times in the width direction to obtain a thickness of 8
A film of μm was obtained. The strength, elongation and Young's modulus of this film were 540 MPa, 35% and 12.26, respectively.
It was GPa. Also, the metal ion content is 200 pp
It was m. Although this film had no problem in the initial mechanical properties, it showed remarkable discoloration in a high heat environment.

Example 3 As in Example 1, 45 mol% DOB, 40 mol% PPD and 15 mol% DPE were dissolved in NMP and the solution was cooled. Then, 100 mol% of MPC was added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 14% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.2% by weight.

Reference Example 3 The aromatic polyamide solution of Example 3 was passed through a filter of 5 μm cut, cast on a stainless steel belt, the solvent was evaporated in a dryer, and the film having self-supporting property was belted. Peeled off and the NMP / water ratio was 30/70,
It was introduced into the extraction bath of 20/80, 10/90, 0/100 successively to extract the residual solvent and the like, and then dried and heat-treated with a tenter. At this time, the film was stretched 1.25 times in the longitudinal direction and 1.3 times in the width direction to obtain a film having a thickness of 4.5 μm. The strength, elongation and Young's modulus of this film are
It was 568 MPa, 32%, and 12.74 GPa. The metal ion content was 20 ppm.

Example 4 As in Example 1, 60 mol% DOB, 20 mol% PPD and 20 mol% DPE were dissolved in NMP and the solution was cooled. Then, 100 mol% of TPC was added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 8% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.2% by weight.

Reference Example 4 Using the aromatic polyamide solution of Example 4, a film having a thickness of 4.5 μm was obtained in the same manner as in Reference Example 3. The strength, elongation and Young's modulus of this film were 490 MPa and
It was 32% and 8.34 GPa. The metal ion content was 21 ppm.

Example 5 As in Example 1, 40 mol% DOB, 40 mol% DPX and 20 mol% DPE were dissolved in NMP and the solution was cooled. Then, 100 mol% of TPC was added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 14% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.2% by weight.

Reference Example 5 Using the aromatic polyamide solution of Example 5, a film having a thickness of 4.5 μm was obtained in the same manner as in Reference Example 3. The strength, elongation and Young's modulus of this film were 549 MPa and
It was 46% and 12.75 GPa. The metal ion content was 21 ppm.

Example 6 As in Example 1, 100 mol% of PPD was dissolved in NMP and the solution was cooled. Then, 40 mol% TPC,
40 mol% BPC and 20 mol% DPC were added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. The polymer concentration was 12% by weight, and the polymer was obtained as a transparent solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.3% by weight.

Reference Example 6 Using the aromatic polyamide solution of Example 6 in the same manner as in Reference Example 3, a film having a thickness of 4.5 μm was obtained. The strength, elongation and Young's modulus of this film are 510MPa, respectively.
a, 35%, and 12.26 GPa. The metal ion content was 18 ppm.

Example 7 In the same manner as in Example 1, 45 mol% DOB, 40 mol% DBA and 15 mol% DPE were dissolved in NMP, and the solution was cooled. Then, 50 mol% MPC and 50 mol% BPC were added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. Polymer concentration is 1
5% by weight, the polymer was obtained as a clear solution.
The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.3% by weight.

Reference Example 7 By using the aromatic polyamide solution of Example 7 in the same manner as in Reference Example 3, a film having a thickness of 4.5 μm was obtained. The strength, elongation and Young's modulus of this film are 549MP, respectively.
a, 35%, and 12.75 GPa. The metal ion content was 18 ppm.

Example 8 As in Example 1, 47 mol% DOB, 47 mol% PPD and 6 mol% DPE were dissolved in NMP and the solution was cooled. Then 50 mol% TPC and 50 mol% B
PC was added and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. Polymer concentration is 11
Stabilized at wt%, the polymer was obtained as a clear solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.3% by weight.

Reference Example 8 Using the aromatic polyamide solution of Example 8 in the same manner as in Reference Example 3, a film having a thickness of 4.5 μm was obtained. The strength, elongation and Young's modulus of this film are 559MP, respectively.
a, 22%, and 12.73 GPa. The metal ion content was 18 ppm.

Example 9 In the same manner as in Example 1, 50 mol% DOB and 50 mol% PPD were dissolved in NMP, and the solution was cooled. Then 4
0 mol% TPC, 40 mol% NPC and 20 mol% DPC were added, and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. Polymer concentration is 1
3% by weight, and the polymer was obtained as a clear solution.
The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.3% by weight.

Reference Example 9 Using the aromatic polyamide solution of Example 9 in the same manner as in Reference Example 3, a film having a thickness of 5 μm was obtained. The strength, elongation and Young's modulus of this film were 510 MPa and 3 respectively.
It was 8% and 11.77 GPa. The metal ion content was 18 ppm.

Example 10 In the same manner as in Example 1, 45 mol% DMB, 45 mol% PPD, 10 mol% DPE were dissolved in NMP, 6 mol% PAH was added and the mixture was stirred for 30 minutes, and then the solution was added. To cool. Next, 47 mol% TPC and 47 mol% B
PC was added and the mixture was stirred for 2 hours while controlling the stirring speed, and then neutralized with lithium hydroxide to obtain a polymer. Polymer concentration is 12
% By weight, and the polymer was obtained as a clear solution. The solution was stable even after being left for 2 weeks. The oligomer content in this solution was 0.3% by weight.

Reference Example 10 A film having a thickness of 4.5 μm was obtained by using the aromatic polyamide solution of Example 10 in the same manner as in Reference Example 3. Also,
At this time, thermal cyclization was also performed. The strength, elongation and Young's modulus of this film were 569 MPa, 28% and 14.22, respectively.
It was GPa. The metal ion content is 19 ppm
Met.

Comparative Example 1 50 wt% of lithium bromide per polymer was dissolved in NMP, then 100 mol% of PPD was dissolved, and the solution was cooled. Then, 100 mol% of TPC was added to carry out the reaction.
The product formed a precipitate shortly after the initiation of polymerization, and a molded product could not be obtained.

Comparative Example 2 50% by weight of lithium bromide per polymer was dissolved in NMP, then 100 mol% of DOB was dissolved, and the solution was cooled. Then, 100 mol% of TPC was added to carry out the reaction.
The product formed a precipitate shortly after the initiation of polymerization, and a molded product could not be obtained.

Comparative Example 3 DMB 50 mol% and PPD 50 mol% were dissolved in NMP and the solution was cooled. Then, 100 mol% of TPC was added, and the mixture was stirred for 2 hours and neutralized with lithium hydroxide to obtain a polymer.
Although the polymerization could be completed without generating a precipitate during the polymerization, this solution was an unstable solution that gelled after standing for 2 weeks even when the polymer concentration was 5%.

Reference Example 11 A film having a thickness of 9 μm was obtained in the same manner as in Reference Example 3 using the solution of Comparative Example 3 immediately after polymerization. The strength of this film,
The elongation and Young's modulus are 539 MPa, 8%, and 12.
It was 75 GPa, and although it could have a film shape, it had a low elongation and was difficult to handle.

Comparative Example 4 70 mol% PPD and 30 mol% DPE were dissolved in NMP and the solution was cooled. Then, 100 mol% of TPC was added, and the mixture was stirred for 2 hours and neutralized with lithium hydroxide to obtain a polymer.
DP can be used to complete the polymerization without the formation of precipitates
The minimum amount of E used was 30 mol%. Although the polymer concentration was 8%, this solution was an unstable solution that gelled after standing for 2 weeks.

Reference Example 12 A film having a thickness of 4.5 μm was obtained in the same manner as in Reference Example 3 using the solution of Comparative Example 4 immediately after polymerization. The strength, elongation and Young's modulus of this film were 412 MPa, 18%,
It was 7.06 GPa. Although it could be made into a film, the mechanical properties inherent to the para-oriented aromatic polyamide were lost.

[0075]

Industrial Applicability The aromatic polyamide composition of the present invention is excellent in solubility and solvent stability while maintaining its original excellent properties such as mechanical properties and heat resistance. It is easy to obtain as a molded product such as. Therefore, the industrial utility value in various applications is extremely high.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 69/00-69/50

Claims (8)

(57) [Claims] 1. A group consisting of structural units having different aromatic nuclei represented by the general formula (I), the general formula (I): Group B consisting of structural units having different aromatic nuclei represented by general formula (II), general formula (II) And a group C comprising structural units having different aromatic nuclei represented by the general formula (III), the general formula (III): (Here, Ar ₁ , Ar ₂ , and Ar ₃ are para-oriented aromatic nuclei, and the compounds of each group include a nitro group represented by Ra, Rb, and Rc, a cyano group, an alkyl group having 1 to 4 carbon atoms, and a carbon atom. Number 1
To 3 may be substituted with a functional group selected from an alkoxy group, a trialkylsilyl group, an oxyaryl group and a thioaryl group. Here, k, l and m are each 0
~ Is a number of 4. From at least three types (provided that at least two types of structural units having different basic aromatic nuclei are selected from the same group) and the general formula (I
Group D consisting of the structural unit represented by V), the general formula (IV): (Here, Ar ₄ and Ar ₅ are para-oriented aromatic nuclei,
X and Y may be the same or different from each other, -CO- or -NH- group. Here, when both X and Y are -CO-, A
Group (B group, D group), when both X and Y are -NH-, (A
Group, D group) and B group, and when different from each other, A group and B group are substantially equimolar. ) Is a main structural unit, and 1% by weight of an oligomer having a molecular weight of 1000 or less is used.
An aromatic polyamide composition that is: 2. The aromatic polyamide composition according to claim 1, wherein the substituents substituting the aromatic nuclei represented by the general formulas (I) to (III) satisfy the following formula. 1 <
k + 1 and / or 1 <m 3. The group according to claim 1 or 2 , wherein at least two kinds of phenylene group, biphenylene group and naphthylene group are used as the para-oriented basic aromatic nucleus in the group where two or more kinds of structural units are selected. Aromatic polyamide composition. 4. In a group in which two or more kinds of structural units are selected, 3,3 'as aromatic nuclei having different para orientations are formed.
-Disubstituted-4,4'-biphenylene group and / or 2,
2'-disubstituted-4,4'-biphenylene group and 2,5-di-substituted - and / or 2,3-disubstituted - paraphenylene using group claim 1 aromatic according to any one of 3 Polyamide Composition. The organic solvent solution of 5. aromatic polyamide composition according to any one of claims 1 to 4. 6. A fiber comprising the aromatic polyamide composition according to any one of claims 1 to 4 . 7. A composed of an aromatic polyamide composition according to any of claims 1 4 film. 8. A sheet comprising an aromatic polyamide composition according to any one of claims 1 to 4.