JPH0681211A - Aromatic polyamide yarn - Google Patents

Abstract

PURPOSE:To obtain aromatic high-tenacity polyamide yarn having improved light resistance by absorption and screening the action of ultraviolet light caused by addition of specified carbon black. CONSTITUTION:Aromatic polyamide yarn contains 0.4-3wt.% based on weight of the whole yarn of carbon black having ultraviolet light absorption ability in a range of 250-500nm wave length and 55-100mmu primary particle diameter, has 0.5-50 denier fineness of single yarn and mechanical characteristics in the following ranges. Strength is >=18g/de, elongation is >=3.5% and initial modulus is >=450/de.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aromatic copolyamide fiber having excellent light resistance.

[0002]

2. Description of the Related Art Para-oriented aromatic polyamide fibers are used in various fields as industrial fibers due to their excellent mechanical properties, but their light resistance is not always at a satisfactory level, and they are exposed to sunlight for use. In this case, there is a problem that the physical properties of the fiber tend to deteriorate.

Although the cause of this is not fully understood, there is a possibility that an amide bond is cleaved and decomposed by a photochemical reaction in the presence of water, a Fries transfer reaction occurs in the amide bond, and a radical is generated by oxidation. It is considered that there is a possibility that it will be generated and decomposed.

Therefore, in the case of ropes and nets of industrial materials, it is necessary to take measures to suppress the light resistance deterioration by covering the surface with other fibers or resins. Further, particularly in the development of lightweight and high-strength textiles for sports clothing using ultrafine fibers, aromatic polyamide fibers having good light resistance have been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-strength aromatic polyamide fiber having improved light resistance due to the effects of blocking ultraviolet rays and absorbing ultraviolet rays.

[0006]

[Means for Solving the Problems] The following measures have been proposed so far as measures for improving the light resistance of aramid fibers, but none of them has been sufficiently satisfied. That is, a benzotriazole-based or substituted benzophenone-based ultraviolet (UV) absorber is used in an amount of 2 to 6% in the fiber by 0.0
In the method of uniformly dispersing and blending without agglomeration of 1 mμ or more (US Pat. No. 3,888,821), there is a problem that the addition efficiency is low because the agent is evenly distributed inside the fiber. Further, a method of canceling the discoloration due to exposure to sunlight by adding 0.02 to 10% of a photobleaching pigment (Japanese Patent Application Laid-Open No. HEI-2)
In the case of Japanese Patent Laid-Open No. 229281), it is difficult in principle to "bend" and there is a problem that the hue is limited. In the method of N-aromatic acylating an amide group to modify it into an imide group (Japanese Patent Laid-Open No. 2-178324), it is necessary to carry out N-aromatic acylation with benzoyl chloride or the like in a state where an aromatic polyamide is dissolved in a solvent. Therefore, there is a problem that the process becomes long.

Regarding the improvement of light resistance by the addition of carbon black, polyparaphenylene terephthalamide fiber (PPTA fiber) having improved light resistance by adding 0.1 to 10% by weight of carbon having a particle size of 10 to 50 mμ. ) (Japanese Patent Laid-Open No. 64-85316), there is a PPT
Although the light resistance improving effect by adding carbon to the A fiber is described, when the particle size is less than 10 mμ or more than 50 mμ, the light resistance improving effect is not seen and dispersion failure is likely to occur.

In addition, there are the following two examples in which carbon black is added to aramid fiber, but there is no description regarding light resistance. That is, a patent for a colored para-type (P-) aramid fiber containing 0.01 to 6% of a completely organic (sulfuric acid-soluble) pigment having no particles or agglomerates larger than 0.01 mμ. 64-14317) discloses an example of addition of carbon black as one of the comparative examples, but there is no description regarding light resistance at all.

A completely organic pigment having particles or agglomerates smaller than 0.5 mμ distributed throughout the fiber can be added to
Comparative example 1 is also disclosed in a patent (JP-A-2-41414) relating to a colored P-aramid fiber containing 01 to 6%.
As an example, an example of adding carbon black is shown, but there is no description regarding light resistance.

As a result of diligent study on an ultraviolet absorber having excellent heat resistance that can withstand hot drawing as a measure for improving the light resistance of aromatic copolyamide fibers obtained by spinning an isotropic solution and then hot drawing, primary particles Specific carbon black having a size of 55 mμ or more is press-fitted into the dope in a slurry state of the same solvent as the polymer solution (referred to as the dope),
The present invention has been achieved in which aramid fibers excellent in light resistance can be obtained by kneading without impairing the mechanical properties of the fibers.

That is, the present invention has an ultraviolet absorbing ability in the wavelength region of 250 to 500 nm and a primary particle diameter of 55 to 100 m.
The carbon black, which is μ, is 0.
An aromatic copolyamide fiber characterized in that it contains 4 to 3%, has a single yarn fineness of 0.5 to 50 denier, and has mechanical properties within the following ranges. Strength: 18 g / de or more Elongation: 3.5 or more Initial modulus: 450 g / de or more.

The present invention will be described in detail below.

The aromatic copolyamide targeted by the present invention is 80 mol% or more, preferably 90 mol% of the repeating unit.
The above is an aromatic copolyamide composed of the following repeating units.

[0014]

[Chemical 1]

(Wherein Ar ₁ and Ar ₂ are the same or different aromatic residues selected from the following groups, provided that the hydrogen atom of the aromatic residue is replaced with a halogen atom or a lower alkyl group. May have been.)

[0016]

[Chemical 2]

X is selected from the following residues.

[0018]

[Chemical 3]

Regarding the method for producing such an aromatic polyamide, for example, British Patent No. 1501948, US Pat. No. 3,738,964, and Japanese Patent Laid-Open No. 49-100522.
It is described in Japanese Patent Publication No.

The distribution position of carbon in the fiber may be uniform in the cross-sectional direction, but it should preferably be at the surface layer of the fiber. In order to substantially distribute the distribution of carbon in the fiber surface layer, a method of blending a high concentration of carbon into the sheath component as a core-sheath type composite spinning, applying carbon to the swollen fiber and then drying and shrinking the agent There are a method of incorporating into the surface layer, a method of adhering to the surface of the single fiber by static electricity, followed by fixing by fusion or adhesion, a method of coating the fiber surface with a resin blended with a high concentration agent.

It is more effective to use an organic ultraviolet absorber and a radical scavenger (phenolic antioxidant, phosphorus antioxidant, amine antioxidant, hindered amines) together with the above carbon.

The primary particle size of carbon is 55 to 1
It is 00 mμ. In the case of an anisotropic solution such as PPTA, the polymer forms a liquid crystal in the dope to form a dense structure, and therefore it is necessary to have a small size in order to incorporate an additive such as carbon black. On the other hand, in an isotropic solution, since the polymer structure in the dope is loose, incorporation of the additive is easy, and the problem of the additive size is small. However, for the following reasons, one of the carbons that should be added is
The secondary particle size should be 55 to 100 mμ, and it is necessary to devise so that the aggregate particle size in the fiber does not exceed 0.2 mμ.

When the particle size is less than 55 mμ, the primary particle size is 1
In the case of 0 to 20 mμ, the surface energy is high and aggregation is likely to occur. Therefore, it is necessary to use it in combination with an organic dispersion auxiliary agent as a countermeasure, and as a result, the dispersion auxiliary agent is thermally decomposed in the hot drawing step to improve the spinnability Adverse effects of. 20 ~
Even with a primary particle diameter of 55 mμ, so-called shock agglomeration during addition and mixing is likely to occur and defective foreign matter is likely to deteriorate the thread-making condition.

2 if the primary particle size exceeds 100 mμ
The size of the secondary structural unit, which is also called a structure or a cluster that is a secondary structural unit, is 0.2 to 0.4 mμ.
As a result, coarse aggregates in the fibers become defective foreign matter, which causes fuzz and yarn breakage due to single yarn breakage, which is not preferable.

The concentration of carbon added is 0.4 to 3% by weight. If it is less than 0.3% by weight, the effect of shielding ultraviolet rays is almost absent, and if it exceeds 3% by weight, the influence as a foreign substance increases and the physical properties deteriorate.

The single yarn fineness of the fiber is 0.5 to 50 denier. If it is less than 0.5 denier, the added particles act as yarn defects and the spinnability becomes unstable. Further, since the specific surface area of the fiber becomes large, it is susceptible to light resistance deterioration. As a result, this leads to an increase in the amount of particles added, which further adversely affects foreign matter and disturbs the process condition, which is not preferable. Fifty
When it exceeds denier, the specific surface area of the fiber becomes small,
Less susceptible to light resistance deterioration. On the other hand, since the specific surface area is small in the yarn making process, coagulation is likely to be incomplete, and as a result, the process is liable to be disturbed in the spinning and drawing processes and the physical properties are likely to be deteriorated.

The strength is 18 g / de or more. The higher the strength, the more preferable, but the strength tends to decrease as the concentration of the additive increases, and if it is less than 18 g / de, the characteristics of the aramid fiber as a high strength fiber are insufficient.

The elongation is 3.5% or more. If it is less than 3.5%, twisting strain becomes large when used by twisting,
The strength utilization of the twisted cord is reduced. Therefore, in the case of ropes and nets for outdoor use where light resistance is particularly required, high strength and durability become a problem.

The initial modulus is 450 g / d or more. If it is less than 450 g / d, the characteristics as an anti-modulus fiber are insufficient.

[0030]

Industrial Applicability The present invention provides an aramid fiber having excellent light resistance while maintaining the same fiber physical properties as the conventional ones.

The present invention will be described below with reference to examples.
The preparation of the polymer solution (dope) used for the test and the blending of carbon black yarn were carried out by the following methods. Preparation of dope N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 2051 having a water content of about 20 ppm was charged into a mixing tank having an anchor-shaped stirring blade in which nitrogen was flown, and 2764 g of paraphenylenediamine and 3, 5114 g of 4'-diaminodiphenyl ether was precisely weighed and added, and dissolved. The temperature of this diamine solution was 30 ° C. and the stirring speed was 64.
Terephthalic acid chloride 1032 at times / minute
0 g was precisely weighed and charged. The temperature of the solution rose to 53 ° C. due to the heat of reaction and was then heated for 60 minutes to 85 ° C. The polymerization reaction was terminated when the increase in the viscosity of the solution was completed by continuing stirring at 85 ° C for a further 15 minutes.

After this, 22.5% by weight of calcium hydroxide
16.8 kg of NMP slurry containing was added, and stirring was continued for 20 minutes to filter the dope adjusted to pH 5.4 with a filter having an opening of 30 microns to prepare a polymer solution having a polymer concentration of 6% (hereinafter referred to as a dope). Completed. Blending of carbon black A NMP slurry of carbon black is quantitatively pressed into the above dope being fed to the spinning head at a pressure of 10 to 20 kg / cm ² , and immediately subjected to dynamic mixing, followed by a static mixer of 20 stages or more. After giving a sufficient mixing action by the above, it is discharged from the pack / spinning nozzle through a lightweight pump, then taken up by dry jet spinning, and the product is wound after coagulation / drying / hot drawing / finishing oil application.

[0033]

COMPARATIVE EXAMPLE 1 Using the dope prepared by the above-mentioned polymerization method, the fiber obtained by spinning under the following conditions was evaluated for light resistance. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, and a spinneret with 1000 holes is used.
The yarn was discharged at a discharge rate of 1350 g / min and a dope temperature of 107 ° C. Coagulate at 50 ° C. in 30% NMP aqueous solution, draw out from coagulation bath at spinning speed of 47 m / min, wash with water, apply hydrated gel-forming inorganic compound, dry and heat stretch at 510 ° C. to 500 m / min. The product was wound in minutes to yield 1500 denier yarn. The physical properties of this aramid fiber were as follows. Total fineness: 1502 denier Strength: 42.7 kg Strength: 28.4 g / d Elongation at break: 4.84% Modulus: 587 g / d Sunshine light resistance deterioration evaluation of this sample under the condition of 63 degrees * 300 hours revealed that residual strength Was 12.8 kg, and the maintenance rate was 30%.

[0034]

[Comparative Example 2] In the carbon black blend spinning method shown in the text, the primary particle diameter is 62 mμ and the specific surface area is 27 m.
² / g, oil supply amount of 87 ml / 100 g, 10% NMP slurry of carbon black was press-fitted and mixed at a rate of 97 cc / hr so that the carbon concentration in the fiber was 0.2% by weight under the following conditions. I made yarn. Spinning is a dry jet spinning method, and the nozzle shape is a circular section with a diameter of 0.3 mm, 10
Using a 00-hole spinneret, the yarn was discharged at a discharge rate of 1350 g / min and a dope temperature of 107 ° C. Coagulate at 50 ° C. in 30% NMP aqueous solution, draw it out from the coagulation bath at a spinning speed of 47 m / min, wash it with water, apply a hydrated gel-forming inorganic compound, dry it, and heat stretch it at 510 ° C. to 500 m / min. The product was wound to obtain 1500 denier yarn.

The physical properties of this aramid fiber were as follows. Total fineness: 1503 denier Strength: 41.0 kg Strength: 27.3 g / d Elongation at break: 4.80% Modulus: 591 g / d Sunshine light resistance deterioration evaluation of this sample under the condition of 63 degrees * 300 hours shows the residual strength. Was 13.6 kg, and the maintenance rate was 33%.

[0036]

[Comparative Example 3] In the carbon black blend spinning method shown in the text, the primary particle diameter is 13 mμ, and the specific surface area is 250.
A 10% by weight NMP slurry of carbon black with m ² / g and oil supply amount of 80 ml / 100 g was press-mixed at a rate of 500 cc / hr to produce a carbon concentration in the fiber of 1.0% by weight under the following conditions. Was carried out.

Spinning was carried out by a dry jet spinning method, a nozzle having a round cross section with a diameter of 0.3 mm and a spinneret with 1,000 holes was used, and the yarn was discharged at a discharge rate of 1350 g / min and a dope temperature of 107 ° C. Coagulate in 50% C, 30% aqueous solution of NMP, draw out from coagulation bath at spinning speed of 47 m / min, wash with water, apply hydrated gel-forming inorganic compound, and dry at 510 ° C. and draw at a draw ratio of 8.7. However, the yarn was frequently broken and continuous operation was not possible. Then, coarse aggregated particles of carbon were observed at the ends of the yarn breaks.

[0038]

[Comparative Example 4] In the carbon black blend spinning method shown in the text, the primary particle diameter is 13 mμ and the specific surface area is 250.
m ² / g, oil supply amount 80 ml / 100 g of a mixture of carbon black and phthalocyanine blue as a carbon dispersion aid, 10 wt% NMP slurry was pressed and mixed at a rate of 1250 cc / hr to make the carbon concentration in the fiber 1.0. weight%
Was carried out under the following conditions.

Spinning is performed by a dry jet spinning method, a nozzle having a round cross section with a diameter of 0.3 mm and a spinneret with 1000 holes is used, and the yarn is discharged at a discharge rate of 1350 g / min and a dope temperature of 107 ° C., then at 50 ° C., NMP30. % Solidified in aqueous solution,
After withdrawing from the coagulation bath at a spinning speed of 47 m / min, it was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and hot-stretched at a stretching ratio of 8.7 at 510 degrees. The obtained aramid fiber had no coarse agglomeration of carbon and the physical properties were as follows, but a large amount of decomposed sublimate of phthalocyanine blue was generated during stretching, and scum accumulated, which is acceptable for continuous operability and process contamination. It wasn't something. Denier: 152 Denier Yarn Strength: 40.0 kg Strength: 26.2 g / d Elongation at break: 4.52% Modulus: 587 g / d

[0040]

Example 1 In the carbon black blend yarn making method shown in the present text, the same 10 wt% NMP slurry of 62 mμ of carbon black as in Comparative Example 2 was pressed and mixed at a rate of 250 cc / hr to make the carbon concentration in the fiber 0. 5% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, a 1000-hole spinneret is used, and the discharge rate is 1350 g /
Min, after spinning at a dope temperature of 107 ° C, then at 50 ° C, NM
After coagulating in a 30% aqueous solution of P30 and withdrawing from the coagulation bath at a spinning speed of 47 m / min, the product was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and heat-stretched at 510 ° C. to wind the product at 500 m / min. Yarn of 1500 denier was obtained.

The physical properties of this aramid fiber were as follows. Denier: 1509 Denier yarn Strength: 38.5 kg Strength: 25.5 g / d Elongation at break: 4.63% Modulus: 581 g / d This sample was evaluated for sunshine light resistance deterioration of 63 degrees * 300 hours. 14.4kg, maintenance rate is 37
%Met.

[0042]

[Example 2] In the carbon black blend spinning method shown in the text, the same 10% by weight NMP slurry of 62 mμ of carbon black as in Comparative Example 2 was pressed and mixed at a rate of 500 cc / hr to obtain a carbon concentration of 1. 0% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, a 1000-hole spinneret is used, and the discharge rate is 1350 g /
Min, after spinning at a dope temperature of 107 ° C, then at 50 ° C, NM
After coagulating in a 30% aqueous solution of P30 and withdrawing from the coagulation bath at a spinning speed of 47 m / min, the product was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and heat-stretched at 510 ° C. to wind the product at 500 m / min Taking 1500 denier yarn was obtained.

The physical properties of this aramid fiber were as follows. Denier: 1511 Denier yarn Strength: 38.7 kg Strength: 25.6 g / d Elongation at break: 4.55% Modulus: 578 g / d This sample was evaluated for sunshine light resistance deterioration for 63 degrees * 300 hours. .3kg, maintenance rate 42%
Met.

[0044]

[Example 3] In the carbon black blend spinning method shown in the text, 10 wt% NMP slurry of 62 mμ of carbon black, which was the same as in Comparative Example 2, was pressed and mixed at a rate of 750 cc / hr to obtain a carbon concentration of 1. 5% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, a 1000-hole spinneret is used, and the discharge rate is 1350 g /
Min, after spinning at a dope temperature of 107 ° C, then at 50 ° C, NM
After coagulating in a 30% aqueous solution of P30 and withdrawing from the coagulation bath at a spinning speed of 47 m / min, the product was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and heat-stretched at 510 ° C. to wind the product at 500 m / min. Yarn of 1500 denier was obtained.

The physical properties of this aramid fiber were as follows. Denier: 1531 Denier yarn Strength: 38.7 kg Strength: 25.3 g / d Elongation at break: 4.40% Modulus: 584 g / d The distribution of carbon particles was found to be evenly distributed in the fiber by a transmission electron microscope. confirmed.

As a result of evaluating the sunshine light resistance deterioration of this sample for 63 degrees * 300 hours, the residual strength was 15.9 kg and the maintenance rate was 41%.

[0047]

[Example 4] In the carbon black blend spinning method shown in the present text, the same 10 wt% NMP slurry of 62 mμ of carbon black as in Comparative Example 2 was pressed and mixed at a rate of 750 cc / hr to obtain a carbon concentration of 1. 5% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, a 1000-hole spinneret is used, and the discharge rate is 1350 g /
Min, after spinning at a dope temperature of 107 ° C, then at 50 ° C, NM
After coagulating in a 30% aqueous solution of P30 and withdrawing from the coagulation bath at a spinning speed of 47 m / min, the product was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and heat-stretched at 510 ° C. to wind the product at 500 m / min Yarn of 1500 denier was obtained.

The physical properties of this aramid fiber were as follows. Denier: 1506 Denier yarn Strength: 32.4 kg Strength: 21.5 g / d Elongation at break: 3.98% Modulus: 584 g / d The distribution of carbon particles was found to be evenly distributed in the fiber by a transmission electron microscope. confirmed.

As a result of evaluating the sunshine light resistance deterioration of this sample for 63 degrees * 300 hours, the residual strength was 22.9 kg and the maintenance rate was 71%.

[0050]

[Example 5] In the carbon black blend spinning method shown in the text, the same 10 wt% NMP slurry of 62 mμ of carbon black as in Comparative Example 2 was pressed and mixed at a rate of 500 cc / hr to obtain a carbon concentration of 1. 5% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a circular cross section with a diameter of 0.3 mm, a 133-hole spinneret is used, and the discharge rate is 1350 g /
Min, after spinning at a dope temperature of 107 ° C, then at 50 ° C, NM
After coagulating in a 30% aqueous solution of P30 and withdrawing from the coagulation bath at a spinning speed of 47 m / min, the product was washed with water, applied with a hydrated gel-forming inorganic compound, dried, and heat-stretched at 510 ° C. to wind the product at 500 m / min. Yarn of 1000 denier was obtained.

The physical properties of this aramid fiber were as follows. Denier: 1003 Denier yarn Strength: 21.3 kg Strength: 21.2 g / d Elongation at break: 3.69% Modulus: 574 g / d The distribution of carbon particles was found to be evenly distributed in the fiber by a transmission electron microscope. confirmed.

As a result of evaluating the sunshine light resistance deterioration of this sample for 63 degrees * 300 hours, the residual strength was 16.5 kg and the maintenance rate was 77%.

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[Procedure amendment]

[Submission date] April 23, 1993

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

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[Correction target item name] 0001

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[0001]

The present invention relates to a fragrance Zokupo <br/> polyamide fibers excellent in light resistance.

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[Correction target item name] 0006

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[0006]

[Means for Solving the Problems] The following measures have been proposed so far as measures for improving the light resistance of aramid fibers, but none of them has been sufficiently satisfied. That is, a benzotriazole-based or substituted benzophenone-based ultraviolet (UV) absorber is used in an amount of 2 to 6% in the fiber by 0.0
In the method of uniformly dispersing and blending so as not to have agglomerates of 1 μm or more (US Pat. No. 3,888,821), there is a problem that the addition efficiency is low because the agent is evenly distributed inside the fiber. Further, a method of canceling discoloration due to exposure to sunlight by adding 0.02 to 10% of a photobleaching pigment (Japanese Patent Laid-Open No. 2-
In the case of Japanese Patent No. 229281), it is difficult in principle to "bend" and there is a problem that the hue is limited. In the method of N-aromatic acylating an amide group to modify it into an imide group (Japanese Patent Laid-Open No. 2-178324), it is necessary to carry out N-aromatic acylation with benzoyl chloride or the like in a state where an aromatic polyamide is dissolved in a solvent. Therefore, there is a problem that the process becomes long.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

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Regarding the improvement of light resistance by the addition of carbon black, polyparaphenylene terephthalamide fiber (PPTA fiber) having improved light resistance by adding 0.1 to 10% by weight of carbon having a particle size of 10 to 50 mμ. ) (Japanese Patent Laid-Open No. 64-85316), there is a PPT
Although the light resistance improving effect by adding carbon to the A fiber is described, the carbon particle diameter is less than 10 mμ or 50.
When it exceeds mμ, the effect of improving the light resistance is not observed, and it is said that defective dispersion is likely to occur.

[Procedure Amendment 7]

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In addition, there are the following two examples in which carbon black is added to aramid fiber, but there is no description regarding light resistance. That is, the completely organic no 0.0 1 [mu] larger particles or agglomerates (the sulfuric acid soluble) pigments 0.
An example of the addition of carbon black is shown as one of the comparative examples in a patent (JP-A-64-14317) relating to a colored para-type (P-) aramid fiber containing 01 to 6%. There is no description about light resistance.

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Distributed throughout the fiber, 0.0% fully organic pigment with particles or agglomerates smaller than 5μ
An example of addition of carbon black is also shown as one of the comparative examples in a patent relating to a colored P-aramid fiber containing 1 to 6% (Japanese Patent Application Laid-Open No. 2-41414), which also describes the light resistance. There is no.

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[0013] aromatic Zokupo polyamide to which the present invention is directed at least 80 mol% of the repeating units, Oh preferably aromatic copolyamide more than 90 mol% is composed of the following repeating units

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(Here, Ar ₁ and Ar ₂ are the same or different aromatic residues selected from the following groups and may be single or multiple.
It can be a number . However, the hydrogen atom of the aromatic residue may be substituted with a halogen atom or a lower alkyl group. )

[Procedure Amendment 11]

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The primary particle size of carbon is 55 to 1
It is 00 mμ. In the case of an anisotropic solution such as PPTA, the polymer forms a liquid crystal in the dope to form a dense structure, and therefore it is necessary to have a small size in order to incorporate an additive such as carbon black. On the other hand, in an isotropic solution, since the polymer structure in the dope is loose, incorporation of the additive is easy, and the problem of the additive size is small. However, for the following reasons, one of the carbons that should be added is
The secondary particle size is 55 to 100 mμ, and the aggregate particle size in the fiber is 0. It is necessary to devise not to exceed 2μ .

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2 if the primary particle size exceeds 100 mμ
The size of a secondary structural unit, which is also called a structure or a cluster which is a secondary structural unit, is 0.2 to 0. Since it is about 4 μ, it becomes a coarse aggregate in the fiber and becomes a defective foreign matter, which causes fluff and yarn breakage due to single yarn breakage, which is not preferable.

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The present invention will be described below with reference to examples.
The preparation of the polymer solution (dope) used for the test and the blending of carbon black yarn were carried out by the following methods. Preparation of dope 205 l of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) having a water content of about 20 ppm was put into a mixing tank having an anchor-shaped stirring blade in which nitrogen was flown, and 2764 g of paraphenylenediamine and 3 , 4'-diaminodiphenyl ether (5114 g) was precisely weighed and added to dissolve. The temperature of this diamine solution was 30 ° C. and the stirring speed was 64.
Terephthalic acid chloride 1032 at times / minute
0 g was precisely weighed and charged. The temperature of the solution rose to 53 ° C. due to the heat of reaction and was then heated for 60 minutes to 85 ° C. The polymerization reaction was terminated when the increase in the viscosity of the solution was completed by continuing stirring at 85 ° C for a further 15 minutes.

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After this, 22.5% by weight of calcium hydroxide
16.8 kg of NMP slurry containing was added, and stirring was continued for 20 minutes to adjust the pH to 5.4, and the dope was filtered through a filter with an opening of 20 microns to prepare a polymer solution having a polymer concentration of 6% (hereinafter referred to as dope). Completed. Blending of carbon black A NMP slurry of carbon black is quantitatively pressed into the above dope being fed to the spinning head at a pressure of 10 to 20 kg / cm ² , and immediately subjected to dynamic mixing, followed by a static mixer of 20 stages or more. After giving a sufficient mixing action by the above, it is discharged from the pack / spinning nozzle through a lightweight pump, then taken up by dry jet spinning, and the product is wound after coagulation / drying / hot drawing / finishing oil application.

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[0034]

[Comparative Example 2] In the carbon black blend spinning method shown in the text, the primary particle diameter is 62 mμ and the specific surface area is 27 m.
² / g, reeling in manner following conditions 10% NMP slurry of Ca over carbon black of the intake oil amount 87 ml / 100 g were pressed in a ratio of 97cc / hr in a 0.2 wt% of carbon concentration in the fiber did. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, a spinneret with 1000 holes is used, the discharge rate is 1350 g / min, and the dope temperature is 1
The yarn was spun at 07 ° C. After coagulation at 50 ° C. in 30% NMP aqueous solution and drawing from the coagulation bath at a spinning speed of 47 m / min,
After washing with water, applying a hydrated gel-forming inorganic compound, and drying, 51
Winding the product at 500 m / min through heat drawing at 0 degree 15
A yarn of 00 denier was obtained.

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[0036]

[Comparative Example 3] In the carbon black blend spinning method shown in the text, the primary particle diameter is 13 mμ, and the specific surface area is 250.
m ² / g, under the following conditions as the carbon concentration of 10 wt% NMP slurry of carbon black of the intake oil amount 80 ml / 100 g was pressed at a ratio of 500 cc / hr in the fiber becomes 1.0 wt% The yarn was made.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Comparative Example 4] In the carbon black blend spinning method shown in the text, the primary particle diameter is 13 mμ and the specific surface area is 250.
m ² / g, the carbon concentration of the press-mixed to fibers a mixture of 10 wt% NMP slurry at a rate of 1250cc / hr and phthalocyanine blue as carbon black and carbon dispersion aids of the intake oil amount 80 ml / 100 g 1. 0% by weight
Was carried out under the following conditions.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

Example 5 In the carbon black blend spinning method shown in the text, 10 wt% NMP slurry of 62 mμ of carbon black, which is the same as in Comparative Example 2, was pressed and mixed at a rate of 334 cc / hr to make the carbon concentration in the fiber 1 0.5% by weight
Was carried out under the following conditions. Spinning is a dry jet spinning method, the nozzle shape is a round cross section with a diameter of 0.3 mm, and a 133-hole spinneret is used. The discharge rate is 900 g / min.
After spinning at a dope temperature of 107 ° C, 50 ° C, NMP3
Coagulate in 0% aqueous solution, draw out from coagulation bath at spinning speed of 47 m / min, wash with water, apply hydrated gel-forming inorganic compound, dry and wind at 510 ° C. to wind the product at 500 m / min. Yarn of 1000 denier was obtained.

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Claims (1)

[Claims] 1. Carbon black having an ultraviolet absorbing ability in a wavelength range of 250 to 500 nm and a primary particle diameter of 55 to 100 mμ is contained in an amount of 0.4 to 3% based on the weight of the whole fiber, and a single yarn fineness is An aromatic copolyamide fiber having a mechanical property of 0.5 to 50 denier in the following range. Strength: 18 g / de or more Elongation: 3.5 or more Initial modulus: 450 g / de or more