WO2005056893A1

WO2005056893A1 - Polybenzazole fiber and article comprising the same

Info

Publication number: WO2005056893A1
Application number: PCT/JP2004/018392
Authority: WO
Inventors: Kohei Kiriyama; Hiroki Murase; Yukihiro Abe
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2003-12-11
Filing date: 2004-12-09
Publication date: 2005-06-23
Also published as: US20070104948A1; EP1693489A1

Abstract

Polybenzazole fibers which have excellent durability under high-temperature high-humidity conditions even after threads thereof are damaged to develop a kink band in a post-processing step for a woven fabric, knitting, braid, rope, cord, etc. Also provided are articles comprising the fibers, especially a spun yarn, rubber-reinforcing material, fiber-reinforced composite material, woven or knit fabric, knifeproof material or bulletproof vest, rope, sailcloth, etc.

Description

Specification

Polybenzazole fiber and article comprising the same

Technical field

[0001] This patent application is filed with Japanese Patent Application No. 2003-412681, No. 2003-424648, No. 2003-424649, No. 2003-424650, No. 2003-424651, No. 2003- No. 424652, No. 2003-424653, No. 2003-424654, No. 2003-424655 claim priority, respectively, and are hereby incorporated by reference in their entirety. Shall be incorporated into

[0002] The present invention provides excellent durability against high temperature and high humidity even after a yarn is damaged and a kink band is generated in the yarn in a post-processing step of a woven fabric, a knitted fabric, a braid, a rope, a cord, or the like. The present invention relates to polybenzazole fibers and articles comprising the same, especially articles such as spun yarns, rubber reinforcements, fiber-reinforced composite materials, woven or knitted materials, blade-proof or bulletproof vests, ropes, sailcloths, and the like. Background art

[0003] As a fiber having high strength and high heat resistance, polybenzoxazole, polybenzothiazole, or a polybenzazole fiber composed of a copolymer thereof is known.

[0004] Normally, polybenzazole fiber is extruded from a spinneret with a dope containing the polymer-copolymer and an acid solvent, and then immersed in a coagulating fluid (water or a mixture of water and an inorganic acid) to coagulate. After thoroughly washing in a washing bath to remove most of the solvent, pass through an aqueous solution of an inorganic base to neutralize the acid remaining in the yarn without being extracted, and then dry. Obtained by this.

[0005] Polybenzazole fibers are excellent in mechanical properties such as strength and high in heat resistance, and are therefore used in various applications. In recent years, further improvement in performance has been desired. In particular, when processing into articles containing polybenzazole fiber, even after kink bands have been formed on the yarn due to damage to the yarn in post-processing steps such as woven fabrics, knitted fabrics, braids, lips, cords, etc. Excellent durability against high temperature and high humidity, that is, high temperature and high humidity There is a strong demand for polybenzazole fibers that can maintain sufficient strength even when exposed to low temperatures for a long time.

[0006] For example, spun yarns using polybenzazole fibers are known. However, there is a demand for further improvement of the performance of spun yarn using polybenzazole fiber, and in particular, the yarn is damaged in post-processing steps such as woven fabric, knitted fabric, braid, rope, and cord, and the kink band is formed on the yarn. Polybenzazole fiber that has excellent durability against high temperature and high humidity even after it occurs, that is, can maintain sufficient strength even when exposed to high temperature and high humidity for a long time Was strongly desired.

[0007] Conventionally, fibers used as rubber reinforcing materials for tires, hoses, belts, and the like have mainly been nylon fibers, polyester fibers, glass fibers, and steel fibers. In recent years, aromatic polyamide fibers represented by Kepler, which have high strength and high elastic modulus, are used as various rubber reinforcing materials. Polybenzazole fiber, which has a much higher strength and elastic modulus than the aromatic polyamide fiber, and also has excellent heat resistance and dimensional stability, has attracted attention as a rubber reinforcing material. Therefore, the use of polybenzazole fiber as a reinforcing fiber in applications requiring higher strength and high heat resistance, which was insufficient in performance with conventional organic fibers in the rubber material field, has been studied. RU

[0008] In particular, when the rubber reinforcement is subject to dynamic fatigue, the strength of the rubber reinforcement can be sufficiently maintained in a high temperature and high humidity environment. Polybenzazole fibers have been strongly desired.

[0009] Conventionally, glass fiber has been used as a fiber-reinforced composite material. Recently, for the purpose of increasing strength and reducing weight, a material using carbon fiber or aramide fiber has been developed and put into practical use. Have been. However, although carbon fiber is very excellent in mechanical performance, it has a problem that it is brittle due to poor impact properties. On the other hand, aramide fibers exhibit relatively good impact resistance, but have a small reinforcing effect because their elastic modulus is lower than that of carbon fibers. Therefore, a fiber-reinforced composite material made of polybenzazole fiber is excellent in both impact resistance and elastic modulus, shows a reinforcing effect exceeding that of carbon fiber, and is expected as a next-generation fiber-reinforced composite material.

[0010] While improving the performance of the fiber-reinforced composite material containing polybenzazole fiber, The above is expected, and in particular, there has been a strong demand for a fiber-reinforced composite material such as polybenzazole fiber which can maintain a sufficient strength when exposed to high temperature and high humidity for a long time.

[0011] Further, as described above, polybenzazole fiber has excellent mechanical properties such as strength and elastic modulus, and is therefore used as a fiber structure constituting protective materials, protective clothing, and industrial materials. While improving the performance of woven and knitted fabrics containing polybenzazole fiber, it is expected that polybenzazole can maintain sufficient strength especially when exposed to high temperature and high humidity for a long time. A woven or knitted fabric having a sol fiber strength has been strongly desired.

[0012] Conventionally, aramide fibers have been used as blade-proof materials or bulletproof vests. Recently, those using high-strength polyethylene fibers have been developed and put into practical use. However, blade-proof materials or bulletproof vests made of aramide fiber require a large amount of fiber in order to exhibit the required protection performance, which makes them heavy and thick, making them uncomfortable to wear. I was always worn. On the other hand, in the case of blade-proof materials or bulletproof vests using high-strength polyethylene fibers, the weight was reduced and the specific gravity was small, which led to a reduction in thickness. Therefore, blade-proof materials or anti-shocks that also have polybenzazole fiber strength show protection performance superior to aramid fiber and high-strength polyethylene fiber, and are expected to be light-weight, thin-walled, and next-generation blade-proof materials or bulletproof vests. Te ru.

[0013] It is expected that the performance of the blade-proof material or bullet-proof vest containing polybenzazole fiber will be further improved, especially when exposed to high temperature and high humidity for a long time. There has been a strong demand for a blade-proof material or bullet-proof chopstick that can maintain polybenzazole fiber strength.

[0014] In addition, as described above, polybenzazole fiber has excellent mechanical properties such as strength and high heat resistance, and is therefore widely used for ropes such as yacht ropes that require strength-abrasion resistance. Has been used. However, polybenzazole fibers have a very highly oriented molecular chain structure and are susceptible to mechanical damage in the rope manufacturing process. Therefore, it has excellent durability against high temperature and high humidity even after the yarn is damaged in the post-processing process such as ropes and cords and a kink band is generated on the yarn, i.e., under high temperature and high humidity. It is possible to maintain sufficient strength even if exposed for a long time. Polybenzazole fibers that can be cut have been strongly desired.

[0015] Sail cloths containing polybenzazole fibers are also widely used. In particular, yacht sails used in yacht races are required to have high tensile resistance and tensile strength so that the designed shape does not change even when exposed to wind. For this reason, in recent years, sailcloths formed by laminating a woven fabric scrim made of high-strength and high-modulus fibers between two films, such as polyester, have become the mainstream. Also, a method of manufacturing a yacht sail by three-dimensional integral molding has been developed, and the sale loss referred to in this specification includes such a three-dimensional integral molded product. Conventionally, paraaramide fibers and carbon fibers have been used in products using these technologies. Carbon fiber has a higher tensile modulus of elasticity than para-aramid fiber and is expected to improve yacht sail performance. However, it has a problem that it is weak in bending and poor in fatigue. For this reason, sailboats containing polybenzazole fiber have been developed and have already been successful in yacht races around the world.

[0016] In addition, while further improving the performance of yacht sails containing polybenzazole fibers, it is expected that the strength will be sufficiently maintained, especially when exposed to high temperatures and high humidity for a long time. There is a strong desire for a sail cloth that can be a polybenzazole fiber. Disclosure of the invention

Problems to be solved by the invention

[0017] The present invention has been made in view of the above circumstances, and has an object to expose a yarn for a long time under high temperature and high humidity even after the yarn is damaged and a kink band is generated in the yarn. An object of the present invention is to provide a polybenzazole fiber having a small strength reduction.

Another object of the present invention is to provide an article comprising the polybenzazole fiber, especially a spun yarn, a woven or knitted fabric, a rubber reinforcing material, a fiber reinforced composite material, a rope, a sail cloth, a blade-proof material, a bulletproof vest, or the like. To provide an article.

Means for solving the problem

That is, the present invention employs the following configuration.

1. A polybenzazole fiber having a strength retention (%) defined by (aZb) X 100 of 80% or more.

However, a: After twisting with S twist so that the twist coefficient becomes 30, leave it for 30 seconds, and then Twist untwisted to a twist factor of 6 and then treated at 80 ° C and 80% relative humidity for 240 hours, taken out at room temperature and measured [cNZdtex]

b: The strength measured after twisting with S twist so that the twist factor is 30 and then leaving it for 30 seconds, then untwisting to twist number 6 with S twist [cNZdtex]

2. The polybenzazole fiber as described in 1 above, wherein the average diameter D of the single yarn is 5 to 22 m and the average strength is measured at a fiber length of 100 mm.

3. The polybenzazole fiber as described in (1) above, wherein the coefficient of variation CV (standard deviation Z average) when measuring the diameter of the single yarn at 10 mm intervals over a fiber length of 500 mm is 0.08 or less. .

4. The polybenzazole fiber according to the above-mentioned 1, wherein the stoichiometric ratio of the inorganic base and the mineral acid remaining in the fiber is 0.8-1.4: 1.

5. The polybenzazole fiber according to the above-mentioned 1, wherein the fiber contains an organic pigment soluble in a mineral acid having a thermal decomposition temperature of 200 ° C or higher.

6. The polybenzazole fiber according to the above item 5, wherein the content of the organic pigment is 2 to 8% by mass.

7. A spun yarn comprising at least a part of the polybenzazole fiber according to any one of the above items 16 to 16.

8. A rubber reinforcing cord comprising at least a part of the polybenzazole fiber according to any one of the above items 1 to 16.

9. A composite material comprising at least a part of the polybenzazole fiber according to any one of the above items 16 to 16.

10. A woven or knitted fabric characterized by using at least a part of the polybenzazole fiber described in any one of the above items 16 to 16.

11. A blade-preventing material characterized in that at least a part of the polybenzazole fiber described in any one of the above items 16 is used.

12. A bulletproof vest comprising at least a part of the polybenzazole fiber described in any one of the above items 1 to 16.

13.Use the polybenzazole fiber according to any one of the above items 1 to 6 at least in part A high-strength fiber rope characterized by comprising:

14. A sail cloth comprising at least a part of the polybenzazole fiber according to any one of the above items 1 to 16.

[0019] The present inventors have found the following, and have completed the invention.

(1) Highly heat-resistant organic pigments having a thermal decomposition temperature of 200 ° C or higher and soluble in mineral acids, preferably those having an N = group and a Z or NH- group in the molecular structure, of which, particularly, perinone And / or by including perylenes, phthalocyanines, and quinacridones in a specific amount in the fiber, the yarn is damaged and the yarn is damaged as compared with the case where the organic pigment is not included in the yarn. That the durability against high temperature and high humidity is improved even after the occurrence of kink bands, specifically, the reduction in strength due to prolonged exposure to high temperature and high humidity is greatly suppressed.

(2) In addition, it is very important to maintain the pH inside the yarn of the polybenzazole fiber to be around 7, so that after the yarn is damaged and a kink band occurs in the yarn. However, the durability against high temperature and high humidity should be improved. Specifically, the reduction in strength due to prolonged exposure to high temperature and high humidity should be greatly suppressed.

Brief Description of Drawings

[FIG. 1] An example of a resin impregnating apparatus and a die for producing a composite material comprising a polybenzazole fiber of the present invention.

Explanation of symbols

A: fiber yarn, B: introduction angle, C: nozzle diameter, D: parallel part length, E: die

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The polybenzazole fiber according to the present invention refers to a fiber containing a polybenzazole polymer. Polybenzazole (hereinafter also referred to as PBZ) polymers are defined as polybenzoxazole (hereinafter also referred to as PBO), polybenzothiazole (hereinafter also referred to as PBT), and polybenzimidazole (hereinafter also referred to as PBI). A group power One or more selected polymers.

In the present invention, PBO refers to a polymer containing an oxazole ring bonded to an aromatic group. In other words, the aromatic group does not need to be a benzene ring. In addition, PBOs broadly include poly (p-phenylbenzobisoxazole) and polymers that are unitary of multiple oxazole rings bonded to aromatic groups. Similar considerations apply to PBT and PBI.

The polybenzazole polymer according to the present invention also includes any mixture of PBO, PBT and PBI, and a block or random copolymer based on two or more of PBO, PBT and PBI.

The structural unit contained in the PBZ polymer is preferably selected from a lyotropic liquid crystal polymer which forms a liquid crystal at a specific concentration in a mineral acid. The polymer comprises monomer units described in structural formulas (a)-(f).

[0025] The polybenzazole fiber can also produce a dope containing a PBZ polymer. Suitable solvents for preparing the dope include non-oxidizing acids capable of dissolving Talesol and its polymers. Examples of suitable non-acidic acids include polyphosphoric acid, methanesulphonic acid and high concentrations of sulfuric acid or mixtures thereof. Among them, polyphosphoric acid and methanesulfonic acid, particularly polyphosphoric acid, are preferable.

[0026] The polymer concentration in the dope is preferably at least about 7% by weight, more preferably at least 10% by weight, particularly preferably at least 14% by weight. The maximum concentration is limited by, for example, the solubility and dope viscosity of the polymer and the practical handling properties. Due to these limiting factors, the polymer concentration usually does not exceed 20% by weight. [0027] In the present invention, suitable polymers or copolymers and dopes can be synthesized by a known method. For example, Wolfe et al. U.S. Patent No. 4,533,693 (1985.8.6), Sybert et al. U.S. Patent No. 4,772,678 (1988.9.22), Harris U.S. Patent No. 4,847,350 (1989.7.11) or Reference may be made to the description in US Pat. No. 5,089,591 to Gregory et al. (1992.2.18).

According to the above references, suitable monomers are prepared in a non-oxidizing, dehydrating acid solution, in a non-oxidizing atmosphere, under high speed stirring and high shear conditions, at a step force of about 60 ° C. or up to 230 ° C. The synthesis is carried out by increasing the temperature at a constant rate and causing the reaction.

[0028] The dope thus obtained is extruded from the spinneret and stretched in space to form a filament. Suitable processes are described in the references mentioned above and in U.S. Pat. No. 5,034,250. The dope that has exited the spinneret enters the space between the spinneret and the washing bath. This space is generally called an air gap, and usually contains a gas such as air, nitrogen, argon, helium, carbon dioxide, etc., but does not dissolve the solvent and does not react with the dope. It is also possible to enter.

[0029] The filament after spinning is washed to avoid excessive drawing, and a part of the solvent is removed. Then, it is further washed and appropriately neutralized with an inorganic base such as sodium hydroxide, calcium hydroxide, potassium hydroxide, etc., and most of the solvent is removed. Washing here refers to removing the acid solvent from the dope by contacting the fibers or filaments with a liquid that is compatible with the mineral acid in which the polybenzazole polymer is dissolved and is not a solvent for the polybenzazole polymer. That is. Suitable washing liquids include, for example, water or a mixture of water and an acid solvent. The filaments are preferably washed to a residual mineral acid concentration of 8000 ppm or less, more preferably 5000 ppm or less. Thereafter, the filament is subjected to drying, heat treatment, winding and the like as required.

[0030] The organic pigment having a high heat resistance of 200 ° C or higher and soluble in a mineral acid in the present invention is one which is added during polymerization or during polymer dope and remains in the fiber even after spinning. I just need. Specific examples include insoluble azo pigments, condensed azo pigments, dye lakes, isoindolinones, isoindolines, dioxazines, perinones and Z or perylenes, phthalocyanines, quinacridones, and the like. Among them, N = group and Z Or those having an NH- group are more preferred, and more preferred are perinone and Z or perylenes, phthalocyanines, and quinacridones.

[0031] Examples of perinone and Z or perylenes include bisbenzimidazo [2, 1-b: 2, 1, 1, 4] benzo [lmn] [3, 8] phenanthone phosphorus 1,8,17-dione, Bisbenzimidazo [2,1—b: l ,, 2,1j] benzo [lmn] [3,8] phenanthone 1,6,9-dione, 2,9 bis (p-methoxybenzyl) anthra [ 2,1,9 def: 6,5,10—d, e, f,] diisoquinoline 1,3,8,10 (2H, 9H) tetron, 2,9-bis (p-ethoxybenzyl) anthra [ 2, 1, 9 def: 6, 5, 10— d, 6 ,; [,] diisoquinoline-1, 3, 8, 10 (2H, 9H) tetron, 2, 9 bis (3,5-dimethylbenzyl) anthra [ 2, 1, 9 def: 6, 5, 10—d, e, f,] diisoquinoline 1, 3, 8, 10 (2 H, 9H) tetron, 2, 9 bis (p-methoxyphenyl) anthra [2, 1, 9 def: 6, 5, 10 — d, e, f,] diisoquinoline 1, 3, 8, 10 (2H, 9H) tetron, 2, 9 bis (p-ethoxyf Ale) anthra [2, 1, 9 def: 6, 5, 10—d, e, f,] diisoquinoline 1, 3, 8, 10 (2 H, 9 H) tetron, 2, 9 bis (3 , 5-Dimethylphenyl) anthra [2,1,9 def: 6,5,10-d, e, f,] diisoquinoline 1,3,8,10 (2H, 9H) tetron, 2,9 dimethyl Antler [2,1,9—def: 6,5,10—d, e, f,] diisoquinoline 1,3,8,10 (2H, 9H) —tetrolone, 2,9—bis (4-ferrazofel) anthra [2, 1, 9 def: 6, 5, 10—d, e, f,] diisoquinoline 1, 3, 8, 10 (2H, 9H) tetron, 8, 16—Pirance Range On. There may also be a combination of one or more of these perinones.

[0032] The phthalocyanine is not limited as long as it has a phthalocyanine skeleton, whether or not there is a metal coordinated at the center thereof and the atomic species. Specific examples of these compounds include 29H, 31H-phthalocyanate (2 —) — N29, N30, N31, and N32 copper, and 29H, 31H—phthalocyanate (2 —) — N29, N30, N31, and N32 Iron, 29H, 31H-phthalocyanate-N29, N30, N31, N32 Connorth, 29H, 31H-phthalocyanate (2-)-N29, N30, N31, N32 copper, oxo (29H, 31H-phthalocyanine- (2—) —N29, N30, N31, N32), (SP-5-12) titanium and the like. Further, these phthalocyanine skeletons may have one or more substituents such as a halogen atom, a methyl group and a methoxy group. A combination of one or more of these phthalocyanines may also be used.

[0033] The quinacridones include 5,12-dihydro-2,9-dimethylquino [2,3-b] atalizine 7,14-dione, 5,12-dihydroquino [2,3-b] ataridine-1 7,14-dione, 5,12-dihydro2,9-dichloroquino [2,3-b] atalizine-1,7,14-dione , 5,12-dihydro-2,9-dibromoquino [2,3-b] atalizine-1,7,14-dione. A combination of one or more compounds of these quinatalidones is also possible.

[0034] Further, two or more compounds of perylenes, perinones, phthalocyanines, and quinacridones can be used in combination.

[0035] The method for incorporating these organic compounds into the yarn is not particularly limited, but they can be incorporated at any stage of the polymerization of polybenzazole or at the stage of polymer doping at the end of the polymerization. For example, a method of simultaneously charging an organic pigment when charging a raw material of polybenzazole, a method of increasing the temperature stepwise or at an arbitrary heating rate to cause a reaction! /, A method of adding an organic pigment at any time, It is preferable to add an organic pigment to the reaction system at the end of the polymerization reaction, and stir and mix.

[0036] The greatest feature of the polybenzazole fiber according to the present invention is that, after being twisted at a twist factor of 30, the strength retention after being treated for 240 hours in an environment of 80 ° C and a relative humidity of 80% is 80% or more. That is. That is, in the polybenzazole fiber of the present invention, the value of the strength retention (%) defined by (aZb) × 100 is 80% or more.

However, a: After twisting with S twist so that the twist coefficient becomes 30 and then leaving it for 30 seconds, then untwisting to twist number 6 with S twist and then 80% RH 80% The strength measured by taking out at room temperature after treatment for 240 hours in an environment [cNZdtex]

Strength retention of polybenzazole fibers of the present invention (%) is preferably 80- 100%, further [this 82 one 100 ^_0/0, further [this 84 one 100 ^_0/0, further [this 85 one 100 ⁰ / _0, further [this 80 one 99 ^_0/0, further [this 80 one 98%, further 84-98%.

[0037] Since polybenzazole fiber has high rigidity of the molecule itself and small interaction V between molecular chains, a kink band is generated in a direction perpendicular to the fiber axis direction when bending stress is applied to the fiber. . Although there are differences in the degree of kink band generation depending on the type of post-processing, kink bands usually occur when post-processing is performed. Also, just twisting the yarn As the number increases, a kink band occurs. Exposure of a kink band-generated polybenzazole fiber to high temperature and high humidity for a long time tends to increase the strength decrease due to exposure, compared to the case without a kink band. However, by including the organic pigment in the yarn after spinning, even if a kink band is generated, the yarn is resistant to high temperature and high humidity, that is, when exposed to high temperature and high humidity for a long time. This can reduce the decrease in strength of the steel. As a result, in the post-processing process of fabrics, knits, braids, ropes, cords, etc., even after the yarn is damaged and a kink band is generated, the yarn has excellent durability against high temperature and high humidity. become. As described above, the organic pigment has a thermal decomposition temperature of 200 ° C or higher and is soluble in a mineral acid, and is preferably an organic pigment having N = and Z or NH in its molecular structure. It is a pigment. More preferred are organic pigments of perinone and / or perylenes, phthalocyanines or quinacridones.

[0038] In the above-mentioned polybenzazole fiber according to the present invention, the stoichiometric ratio of the inorganic base and the mineral acid remaining in the fiber is desirably 0.8-1.4: 1. If the stoichiometric ratio of the inorganic base remaining in the fiber to the mineral acid is too small, the pH inside the yarn becomes extremely acidic, and the hydrolysis of PBZ molecules proceeds, and the strength tends to decrease. This tendency is more remarkable in the polybenzazole fiber in which the kink band is generated, as compared with the case where there is no kink band, and the strength decreases due to prolonged exposure to high temperature and high humidity. On the other hand, if the stoichiometric ratio of the inorganic base remaining in the fiber to the mineral acid is too large, the pH inside the yarn becomes extremely basic, and the hydrolysis of PBZ molecules proceeds, and the strength tends to decrease. Become. Compared to the case without a kink band, the tendency of the polybenzazole fiber in which a kink band is generated becomes even more pronounced, and the strength decreases due to prolonged exposure to high temperature and high humidity. From the above, the stoichiometric ratio of the inorganic base and the mineral acid remaining in the fiber is preferably 0.8-1.4: 1, more preferably 1.0-1.3: 1, and It is desirable to realize the above stoichiometric ratio in any part of the fiber. The method of neutralization with an inorganic base during washing includes a guide oiling method, a showering method, a dipping method, and the like. There is no particular limitation.

[0039] In the polybenzazole fiber according to the present invention, the content of the organic pigment in the fiber is preferably 8% by mass, more preferably 3-6% by mass. Low content If it is too high, the expected effect of incorporating organic pigments into the yarn, i.e., the durability after the kink band occurs in the yarn, specifically, the decrease in strength due to prolonged exposure to high temperatures and high humidity The suppression effect is reduced. On the other hand, if the content is too high, an increase in filament fineness or unevenness of fineness may be caused, and the initial yarn strength may decrease. When the content is in the range of 2 to 8% by mass, the initial strength of the fiber does not decrease due to the organic pigment in the fiber, and the spinnability at the time of spinning is good. No good operability is maintained. This is because the added pigment dissolves in the mineral acid, and is presumed to be based on dissolution even in the polymer dope. The present invention is not limited to this consideration.

The average diameter D of the single yarn of the polybenzazole fiber according to the present invention is preferably 5 to 22 μm, more preferably 10 to 20 μm.

Further, the average strength is preferably 4.5 GPa or more, more preferably 5.0-8. OGPa, when the fiber length is measured at 100 mm.

Further, as described above, the polybenzazole fiber according to the present invention desirably contains an organic pigment in the fiber. Therefore, sufficient control is required for fiber diameter irregularities. The polybenzazole fiber according to the present invention desirably has a coefficient of variation CV (standard deviation Z average value) of 0.08 or less when measuring the diameter of a single yarn at intervals of 10 mm over a fiber length of 500 mm. 0.06 or less is more preferable. If the coefficient of variation (CV) is too large, stress concentration occurs in a thin portion, and fracture is likely to occur.

[0042] Since the polybenzazole fiber of the present invention has excellent durability against high temperature and high humidity, it is suitable for use in various articles as described below. In particular, the polybenzazole fiber of the present invention is suitably applied to articles such as spun yarn, rubber reinforcing material, fiber reinforced composite material, woven or knitted material, blade-proof material, bulletproof vest, rope, and sail cloth.

[0043] The polybenzazole fiber of the present invention is a spun yarn, especially a protective material or protective clothing used for firefighting clothes, heat-resistant clothes, work clothes, etc., which require high strength and high heat resistance, and high strength and high heat resistance. It can be suitably used as a spun yarn for a fiber structure constituting an industrial material used for a transport material, a cushion material, a coating protective material, and the like that require the above.

The spun yarn according to the present invention also includes a composite spun yarn blended with another fiber. Other fibers include natural fibers, organic fibers, metal fibers, inorganic fibers, mineral fibers and the like. The blending method or form is not particularly limited, and a general blended cotton blending method may be used, or a core-sheath structure may be formed.

[0044] The polybenzazole fiber of the present invention can also be suitably used as a rubber reinforcing material for tires, belts, hoses and the like.

The polybenzazole fiber used for the rubber reinforcing cord according to the present invention can be given a single twist or a twin twist using a ring twisting machine or the like from the viewpoint of improving fatigue resistance. In that case, the twist coefficient (K) should be 10-100.

Further, the surface of the polybenzazole fiber for improving the adhesion to rubber may be subjected to corona treatment, plasma treatment or the like. A compound capable of reacting with the fiber, the fiber surface, or the corona-treated fiber surface may be provided to the polybenzazole fiber. In addition, a dip treatment may be applied to the polybenzazole fiber to improve the adhesiveness with rubber. Examples of the treatment liquid include (A) an aqueous dispersion of an epoxy resin, (B) an aqueous dispersion of a blocked isocyanate, (C) an aqueous dispersion of a rubber latex, and (D) a resorcinol-formaldehyde resin-rubber. A latex (RFL) mixed solution may be used alone or in combination, and a method or the like, in which the treatment is generally performed in one stage or two or more stages, may be used.

[0045] The polybenzazole fiber of the present invention can also be suitably used for composite materials. The composite material comprising the polybenzazole fiber of the present invention may be in any of unidirectional reinforcement, quasi-isotropic lamination, and woven lamination. As the matrix resin, any resin such as a thermosetting resin such as an epoxy resin or a phenol resin, a super engineering plastic such as PPS or PEEK, or a general-purpose thermoplastic resin such as PE, PP, or polyamide. May be used.

[0046] The polybenzazole fiber of the present invention is a woven or knitted fabric, in particular, a protective material and protective clothing used for firefighting clothing, heat-resistant clothing, work clothing, etc., which require high strength and high heat resistance, and high strength and high heat resistance. It can also be suitably used as a woven or knitted fabric for a fiber structure constituting an industrial material used for a transport material, a cushion material, a coating protective material, or the like that requires a material.

The woven or knitted fabric according to the present invention also includes a composite woven or knitted fabric combined with other fibers. Other fibers include natural fibers, organic fibers, metal fibers, inorganic fibers, mineral fibers, and the like. Furthermore, in a woven fabric that is not particularly limited in terms of the combination method, For knitting such as cross weaving, double weaving, and ripstop, circular knitting, weft knitting, warp knitting, Russell knitting, and the like can be further employed in cross knitting and double knitting. In addition, the fiber bundles constituting the woven or knitted fabric are not particularly limited, and monofilaments, multifilaments, twisted yarns, ply-twisted yarns, covering yarns, spun yarns, spinning spun yarns, core-sheath structured yarns, braids, and the like are used. be able to.

[0047] The polybenzazole fiber of the present invention can also be suitably used for blade-proof materials such as waistcoats and gloves. The blade-preventing material according to the present invention is formed by laminating woven fabrics having polybenzazole fiber strength. As the structure of the woven fabric, any of a flat structure, a twill structure and other structures usually used for woven fabrics may be used. Preferably, when a misalignment V, such as a flat structure and a twill structure, is used, a high blade-proof performance can be exhibited.

When the fineness of the polybenzazole fiber used in the blade-proof material according to the present invention is 600 dtex or less, preferably 300 dtex or less, high blade-proof performance is easily obtained. Further, the weaving density of the woven fabric used for the blade-proof material according to the present invention is preferably 30 ply Z25mm or more, more preferably 50 ply Z25mm or more. If the density is low, the yarn tends to move easily, and sufficient blade-proof performance may not be obtained. Further, the basis weight of the fabric when is 150GZm ² or more gesture et preferred is der Rukoto LOOgZm ² or more, can exhibit more excellent stab performance. In addition, a resin may be coated or impregnated on a part or the entire surface of the woven fabric used in the present invention. The blade-proof material of the present invention is obtained by laminating the woven fabric, but it is also possible to use the woven fabric in a state where the woven fabrics are integrally sewn with a high-strength sewing thread.

[0048] The polybenzazole fiber of the present invention can also be suitably used for bulletproof vests. The bulletproof vest according to the present invention is configured by laminating a woven fabric made of polybenzazole fiber. As the structure of the woven fabric, any of a flat structure, a twill structure and other structures usually used for woven fabrics may be used. Preferably, when a tissue such as a flat tissue or a twill texture that does not easily cause misalignment is used, high ballistic performance can be exhibited. If the fineness of the polybenzazole fiber used in the bulletproof vest according to the present invention is preferably not more than 11 Odtex, more preferably not more than 60 Odtex, high bulletproof performance can be easily obtained. The weaving density of the woven fabric used for the bulletproof vest according to the present invention is preferably 40 or less Z25 mm or less. In addition, the basis weight of the fabric is a 150GZm ² to gesture et preferred that at 200GZm ² or less, It can exhibit better bulletproof performance. The bulletproof vest of the present invention can be used in a state where the woven fabrics, which are obtained by laminating the woven fabrics, are integrally sewn with a high-strength sewing thread.

[0049] The polybenzazole fiber of the present invention can also be suitably used for sail cloth. The sail cloth according to the present invention can be used in combination with other high-strength fibers such as polyethylene fiber, noralamide fiber, wholly aromatic polyester fiber or carbon fiber. Sailcloth is reinforced with fibers in complex directions. In the present invention, it is important that the durability of the polybenzazole fiber in the fiber axis direction, that is, the strength retention when exposed to high temperature and high humidity for a long time, is improved.

Example

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the following examples, and it is a matter of course that the present invention can be practiced with appropriate modifications within a range that can be adapted to the gist of the preceding and following examples, and all of them are within the technical scope of the present invention. included.

(Method of twisting filament)

According to JIS-L1013, a sample is attached to the tester under a predetermined load obtained from the following formula using a tester with a gripping interval of 50 cm and twisted so that the twist factor is 30. went. The twist was S twist. After standing for 30 seconds, the sample was untwisted to a twist number of 6 with S twisting to obtain a sample with a twist factor of 6 for S twisting. The formula for calculating the predetermined load (a) when twisting and the relationship between the twist coefficient (K) and the number of twists (Tw) are shown below.

a = (l / 10) DK = 0.124 XTwX D ²

a: Prescribed load (g)

Tw: Number of twists (times Zinch)

D: Filament fineness (Dtex)

(Method of evaluating durability under high temperature and high humidity)

The durability at high temperature and high humidity was evaluated by the retention ratio of the tensile strength after the treatment to the tensile strength before the high temperature and high humidity storage treatment. After winding the sample (state of twist coefficient 6 of S twist) around the resin bobbin with a diameter of 10 cm with the twisting method, it was stored in a thermo-hygrostat at high temperature and high humidity. A sample was taken. A (cNZdtex) is the measured tensile strength value obtained by conducting a tensile test at room temperature, and a tensile test is performed at room temperature on a sample twisted by the above twisting method (with a twist coefficient of S twist of 6). The measured value of the tensile strength obtained by the above was divided by b (cN / dtex) ta by b and multiplied by 100 to obtain the strength retention. For storage under high temperature and high humidity, use Hamadic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd., and completely shield the light from entering the constant temperature and humidity chamber at 80 ° C and 80% relative humidity. A 240 hour treatment was performed below. The tensile strength was measured using a tensile tester (manufactured by Shimadzu Corporation, Model AG-50KNG) according to JIS-L1013.

(Method for evaluating residual phosphorus concentration and sodium concentration in filament)

The residual phosphorus concentration in the filament was determined by colorimetric analysis using the molybdenum blue method after wet digestion of the sample. The sodium concentration in the filament was determined by atomic absorption method after carbonizing, ashing and dissolving the acid in a 1.2N-HC1 solution.

(Method of Measuring Fiber Diameter)

The measurement of the fiber diameter may be performed by any of an optical method and a mechanical method such as a micrometer. From the viewpoint of simplicity of the measuring operation, an optical method such as a scanning electron microscope (SEM) or a laser complete diameter measuring instrument is preferable. In addition, it is necessary to measure a large number of single yarns in order to reflect the overall image of the fiber population. First, it is necessary to measure as many single yarns as possible. At least 5% of the total number of filaments, more preferably 7% of the total number of filaments, is measured. As for the fluctuation of polybenzazole fiber, the fluctuation in the yarn length direction is often larger than the fluctuation between filaments, so it is necessary to perform a sufficient number of measurements in the yarn length direction. Therefore, the measurement is performed over at least 500 mm or more, more preferably at least 750 mm in the yarn length direction, and the measurement interval at that time is 25 mm or less, more preferably 12 mm or less even if the interval is wide. If the measurement interval is long, the fiber diameter of the narrow part may leak from the measurement point. However, considering the realistic fluctuation pattern, the change in diameter is very small at the measurement interval of less than 5 mm. From the viewpoint of force, in the present invention, the yarn diameter is 10 mm at intervals of 10 mm over a fiber length of 500 mm. The method of performing actual measurement was adopted. Using a scanning electron microscope (SEM), the yarn diameter was measured at a magnification of 5000 times, the average value and the standard deviation assuming a normal distribution were calculated, and the coefficient of variation (CV) was calculated by the following formula. . The measurement was performed after correcting the magnification of the scanning electron microscope using latex beads having a known diameter in advance.

CV = Standard deviation of single yarn diameter [; z m] Average value of Z single yarn diameter [m]

(Method of evaluating durability of sail cloth sample under high temperature and high humidity)

To evaluate the durability of sailcloth samples under high temperature and high humidity conditions, store the samples in a high-temperature and high-humidity oven at constant temperature and high humidity, and then use them under standard conditions (temperature: 20 ± 2 ° C, relative humidity: 65 ± 2). %), And a tensile test was performed within 30 minutes, and evaluation was made based on the retention ratio of the bow I tensile strength after the treatment to the bow I tensile strength before the high temperature and high humidity storage treatment. Use Hamadic Chamber 1G43M (manufactured by Yamato Scientific Co., Ltd.) for high temperature and high humidity storage, and completely block light from entering the thermo-hygrostat at 80 ° C and 80% relative humidity. For 240 hours. The tensile strength was measured with a sample width of 2.5 cm using a tensile tester (Model: AG-50KNG, manufactured by Shimadzu Corporation) according to JIS-L1096.

[0056] (Method for evaluating durability of rubber reinforcing cord or composite material sample under high temperature and high humidity)

To evaluate the durability of a rubber reinforcing cord or a composite material sample at high temperature and high humidity, store the sample in a high-temperature and high-humidity oven at high temperature and high humidity, and then use the standard condition (temperature: 20 ± 2 ° C, relative humidity). (Humidity: 65 ± 2%), taken out in a test room, and conducted a tensile test within 30 minutes, and evaluated the retention ratio of the tensile strength after the treatment to the tensile strength before the storage treatment at high temperature and high humidity. For storage under high temperature and high humidity, use Hamadic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd., and completely block light from entering the thermo-hygrostat at 80 ° C and 80% relative humidity. For 240 hours. The tensile strength was measured using a tensile tester (model AG-50KNG, manufactured by Shimadzu Corporation) in accordance with JIS-L1013.

(Method of Evaluating Durability of High-Strength Fiber Rope at High Temperature and High Humidity)

The evaluation of the durability of the high-strength fiber rope was performed without performing the above twisting treatment. To evaluate the strength decrease under high temperature and high humidity, store the sample in a constant temperature and humidity chamber at high temperature and high humidity and then place it in a standard condition (temperature: 20 ± 2 ° C, relative humidity 65 ± 2%) test chamber. Then, a tensile test was performed within 30 minutes, and the strength before the treatment was compared with the strength retention after the treatment. For storage tests under high temperature and high humidity, use Hamadic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd., and completely block light from entering the thermo-hygrostat at 80 ° C and 80% relative humidity. The treatment was performed under the conditions for 240 hours. The strength retention was determined by measuring the tensile strength before and after storage at high temperature and high humidity, dividing the tensile strength after storage test at high temperature and high humidity by the tensile strength before storage test at high temperature and high humidity, and multiplying by 100.

(Method for Evaluating Durability of Woven / Knitted Sample at High Temperature and High Humidity)

To evaluate the durability of the woven or knitted fabric sample under high temperature and high humidity, store the sample in a constant temperature and humidity chamber at high temperature and high humidity, and then use the standard condition (temperature: 20 ± 2 ° C, relative humidity: 65 ± 2). %), A tensile test was performed within 30 minutes, and evaluation was made based on the retention ratio of the tensile strength after the treatment to the tensile strength before the high-temperature and high-humidity storage treatment. For storage at high temperature and high humidity, use Hamadic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd., and completely block light from entering the thermo-hygrostat at 80 ° C and 80% relative humidity. For 240 hours. The tensile strength of the woven fabric was measured in accordance with JIS-L1096, and the tensile strength of the knitted fabric was measured in accordance with JIS-L1018 using a tensile tester (manufactured by Shimadzu Corporation, Model AG-50KNG).

(Method for Producing Composite Material Sample)

The fiber yarn is unwound in a horizontal manner so as not to be twisted, and is alternately brought into contact with the surface of five stainless steel cylinders with a diameter of 100 mm to open the fiber.Then, a curved die with a radius of 1 mm and a radius of 50 mm is used. A slit was formed at the entrance of the curved die with respect to the traveling direction of the running fiber yarn, and the resin was coated by discharging the resin and tension was applied on the curved surface. The fiber yarn was run as it was to impart shear resistance to impregnate the resin. Thereafter, the fiber yarn impregnated with the resin was passed through a die having an introduction portion and a nozzle portion, and cooled to obtain a mouth-shaped composite material. FIG. 1 shows an example of a resin impregnation apparatus and a die. The resin used was Ebara (registered trademark) (105B), an ethylene vinyl alcohol copolymer manufactured by Kuraray Co., Ltd., and the die was introduced at an angle of 30.ゝ Nose, a die with a diameter of 0.6 mm φ ゝ parallel part length 0.5 mm was used.

(Method of Evaluating Durability of Spun Yarn under High Temperature and High Humidity) The evaluation of the durability of the spun yarn was performed without performing the above twisting treatment. After the spun yarn is wound around a resin bobbin and stored in a thermo-hygrostat at high temperature and high humidity, the sample is taken out, and a tensile test is performed at room temperature. The tensile strength of the spun yarn subjected to high-humidity storage was divided by the measured tensile strength obtained by conducting a tensile test at room temperature and multiplied by 100 to determine the strength retention. For storage at high temperature and high humidity, use Hamadic Chamber 1G43M manufactured by Yamato Scientific Co., Ltd. as in the case of the filament before cutting, and completely block light from entering the thermo-hygrostat. The treatment was carried out at 80 ° C. and a relative humidity of 80% for 240 hours. The tensile strength was measured using a tensile tester (Model: AG-50KNG, manufactured by Shimadzu Corporation) with a yarn length of 200 mm according to JIS-L 1095.

(Example 1)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 14.8 g of sulene was added to 2.Okg of the poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 29 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing.

Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the obtained polybenzazole fiber by the above method, the phosphorus concentration was 4600 ppm, the sodium concentration was 3600 ppm, and the molar ratio of Na / P was 1.05. The durability was evaluated at a high temperature and high humidity by the above method, and as a result, the strength retention was 86%.

[0062] Six of the obtained polybenzazole fibers are not twisted! / Together to form a total denier of 1,500 yarns, and the warp direction and the weft direction are 5 / inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 87%.

[0063] Furthermore, the obtained six polybenzazole fibers were twisted together with a twist of 32TZlOcm in the Z direction, and then they were joined together to give a twist of 32TZ1Ocm in the S direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 89%.

[0064] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while twisting 80 times per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. When the durability of the obtained rope under high temperature and humidity was evaluated, the strength retention was 87%.

[0065] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was manufactured, the twist coefficient was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4220 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The tensile strength of the obtained circular knitted fabric in the vertical direction is 16 It was 60NZ5cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated. The strength retention was 85%.

[0066] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were prepared in each of the vertical and horizontal directions.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5850NZ3cm. When the durability of the obtained woven fabric under high temperature and high humidity was evaluated, the strength retention was 84%.

[0067] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.29 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

[0068] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The tensile strength of the obtained spun yarn was 15.3 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 84%.

[0069] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5600NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 83%.

(Example 2)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 14.8 g of copper phthalocyanine was added to 2.Okg of the poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 30 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing. Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ.

The wound yarn was neutralized with a 1% aqueous NaOH solution for 10 seconds, washed with water for 120 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4500 ppm, the sodium concentration was 2400 ppm, and the NaZP molar ratio was 0.72.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 83%.

[0071] Six of the obtained polybenzazole fibers were not twisted! / Together to form a total denier of 1500 yarns, and the yarns were warped in a warp direction and a weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 82%.

[0072] Further, after twisting the obtained six polybenzazole fibers in the Z direction while twisting 32 TZ10 cm, the two are combined, and a twist of 32 TZ1 Ocm is applied in the S direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 85%.

[0073] Further, the obtained polybenzasol fiber 12 was twisted while being twisted 80 times per lm. A plied yarn having a combined thickness of 3000 denier was obtained. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 85%.

[0074] Also, a staple fiber having a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, a twist factor was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The obtained fabric had a tensile strength in the vertical direction of 4250 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted product had a tensile strength in the vertical direction of 1710 NZ5 cm. Continued evaluation of the durability of the obtained circular knitted product under high temperature and high humidity showed that the strength retention was 80%.

[0075] Further, using the obtained polybenzazole fiber yarn, 60 yarns were prepared in each of the vertical and horizontal directions.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 134 gZm ² . The tensile strength in the warp direction was 5890NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and the strength retention was 82%.

[0076] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a yarn having a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 80%.

[0077] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The tensile strength of the obtained spun yarn was 14.8 cNZdtex. Further, the strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 81%. [0078] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 136 gZm2. The tensile strength in the warp direction was 5580 NZ3 cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 80%.

(Example 3)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 14.8 g of copper phthalocyanine was added to 2.Okg of the poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 30 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing. Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. The spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4400 ppm, the sodium concentration was 3600 ppm, and the NaZP molar ratio was 1.10.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 88%.

[0080] Six of the obtained polybenzazole fibers were not twisted! / The yarn was twisted in such a manner that the yarn had a total denier of 1,500 and the warp direction and the weft direction were 5 / inch. Book inserted Scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 90%.

[0081] Further, the obtained six polybenzazole fibers were twisted together in a Z-direction with a twist of 32TZlOcm, and then the two were put together to give a twist of 32TZ1Ocm in the S-direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 91%.

[0082] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while twisting 80 times per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. When the durability of the obtained rope under high temperature and humidity was evaluated, the strength retention was 90%.

[0083] Also, a staple fiber having a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, a twist coefficient was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The obtained fabric had a tensile strength in the vertical direction of 4250 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 87%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted product had a tensile strength in the vertical direction of 1670 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated. The strength retention was 85%.

[0084] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were set in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The resulting fabric Had a weight of 136 gZm ² . The tensile strength in the warp direction was 5800NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

[0085] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. In addition, the durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 87%.

[0086] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was manufactured, the twist coefficient was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 15.8 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 85%.

[0087] Further, two obtained polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5620 NZ3 cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 85%.

(Example 4)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 14.8 g of copper phthalocyanine was added to 2.Okg of the poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 30 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing. Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. Air between the spinning nozzle and the first cleaning bath In the gap, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 3 seconds, and dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4700 ppm, the sodium concentration was 5400 ppm, and the NaZP molar ratio was 1.55.

The durability was evaluated at a high temperature and high humidity by the above-mentioned method. As a result, the strength retention was 86%.

[0089] Six of the obtained polybenzazole fibers were twisted so that they were not twisted! / To obtain a total denier of 1,500 yarns, and the warp direction and the weft direction were 5 / inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 86%.

[0090] Further, the obtained six polybenzazole fibers were twisted together in a Z-direction with a twist of 32TZlOcm, and then the two were combined to form a twist of 32TZ1 Ocm in the S-direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 87%.

[0091] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 88%.

[0092] In addition, a staple fiber having a cut length of 5 lmm was obtained from the obtained polybenzazole fiber. Was set to a twist factor of 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and two yarns were twisted to obtain a 20Z2Ne twin yarn.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4190 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 84%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The tensile strength in the warp direction of the obtained circular knitted fabric was 1660 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 83%.

[0093] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were prepared in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5700NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 83%.

[0094] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 83%.

[0095] A staple fiber having a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, the twist coefficient was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 15. lcNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 84%.

[0096] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained fabric was 136gZm ^2. The tensile strength in the warp direction was 5550NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

(Example 5)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 4.4 g of copper phthalocyanine was added to 2. Okg of a poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 30 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing.

Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. The spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4500 ppm, the sodium concentration was 4000 ppm, and the NaZP molar ratio was 1.20.

The durability was evaluated at a high temperature and high humidity by the method described above. As a result, the strength retention was 81%.

[0098] Six of the obtained polybenzazole fibers were not twisted! / In this manner, the yarns were combined into a yarn having a total denier of 1,500, and the yarn was warped in a warp direction and a weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so that five reinforcing fiber yarns were included, and the durability was evaluated under high temperature and high humidity. The strength retention was 82%.

[0099] Further, after twisting the obtained six polybenzazole fibers while twisting 32 TZ10 cm in the Z direction, two of them were combined, and a twist of 32 TZ1 Ocm was applied in the S direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 83%.

[0100] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. When the durability of the obtained rope under high temperature and humidity was evaluated, the strength retention was 81%.

[0101] Also, a staple fiber with a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, the twist factor was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4300 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 83%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted product had a tensile strength in the warp direction of 1740 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 83%.

[0102] In addition, using the obtained polybenzazole fiber yarn, the length of 60

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 133 gZm ² . The tensile strength in the warp direction was 5920NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and the strength retention was 80%.

[0103] Further, the obtained four polybenzazole fibers were combined so that no twist was applied, and 1000 yarns were obtained. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.29 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 79%.

[0104] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was manufactured, a twist factor was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 14.5 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 80%.

[0105] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 133 gZm ² . The tensile strength in the warp direction was 5690NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 79%.

(Example 6)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, the temperature was slowly raised and the reaction was performed at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. 32.5 g of copper phthalocyanine was added to 2.Okg of the poly (p-phenyl-benzobenzoxoxazole) dope having an intrinsic viscosity of 30 dL / g measured with the obtained methanesulfonic acid solution at 30 ° C., followed by stirring and mixing. Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ. The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4400 ppm, the sodium concentration was 3400 ppm, and the molar ratio of NaZP was 1.04.

As a result of evaluating durability under high temperature and high humidity by the method described above, the strength retention was 87%.

[0107] Six of the obtained polybenzazole fibers were not twisted! / The yarn was plied to obtain a total denier of 1,500, and the warp and weft directions were 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 89%.

[0108] In addition, after twisting the obtained six polybenzazole fibers in a Z direction while twisting 32TZlOcm, two of these are combined and a twist of 32TZ1 Ocm is applied in the S direction to produce a raw material. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 85%.

[0109] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 88%.

[0110] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, a twist factor of 3.5 was set, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric is 401 ON It was Z3cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 87%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted fabric had a tensile strength in the vertical direction of 15 to 90 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated. The strength retention was 85%.

[0111] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were set in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 138 gZm ² . The tensile strength in the warp direction was 5610NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

[0112] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.31 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 85%.

[0113] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The tensile strength of the obtained spun yarn was 15.5 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 85%.

[0114] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained fabric was 138gZm ^2. The tensile strength in the warp direction was 5280 NZ3 cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 84%.

(Example 7)

Under a nitrogen stream, 122,5% polyphosphoric acid in 216.5 g of 4,6-diaminoresorcinol dihydrochloride Add 344.5 g of salt and 252.7 g of terephthalic acid and stir at 60 ° C for 1 hour, then slowly raise the temperature to 120 ° C for 4 hours, 135 ° C for 20 hours, and 150 ° C for 5 hours. Let it react for hours. Further, a dispersion liquid obtained by adding 5.6 g of terephthalic acid and 19.5 g of copper phthalocyanine to 74.4 g of 116% polyphosphoric acid was added to the oligomer dope, and the dispersion was added at 170 ° C for 5 hours and at 200 ° C for 10 hours. After reacting for an hour, a poly (p-phenylbenzobenzoxazonole) dope having an intrinsic viscosity of 29 dL / g measured with a methanesulfonic acid solution at 30 ° C. was obtained.

The wound yarn was neutralized with a 1% aqueous NaOH solution for 10 seconds, washed with water for 120 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4600 ppm, the sodium concentration was 2400 ppm, and the molar ratio of Na / P was 0.70.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 84%.

[0116] Six of the obtained polybenzazole fibers were twisted so as not to be twisted to obtain a total denier of 1,500 yarns, and the yarns were inserted into the warp direction and the weft direction at 5 lines per inch. Scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 81%.

[0117] Also, do not twist the obtained polybenzazole fiber into a twist of 32 TZ10 cm in the Z direction. After twisting together, two of them were combined and twisted in the S direction at 32 TZ 1 Ocm to obtain a raw cord. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 86%.

[0118] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 86%.

[0119] Also, a staple fiber with a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, a twist factor of 3.5 was set, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The obtained fabric had a tensile strength in the vertical direction of 4240 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 83%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The resulting circular knitted product had a tensile strength in the vertical direction of 1690 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 82%.

[0120] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were set in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 136 gZm ² . The tensile strength in the warp direction was 5820NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and the strength retention was 82%.

[0121] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material is volume The fraction was 0.29. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 81%.

[0122] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a 20Ne spun yarn was produced with a cotton count. The tensile strength of the obtained spun yarn was 15. OcNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 83%.

[0123] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5500NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 80%.

(Example 8)

In a nitrogen stream, 334.5 g of 4,6-diaminoresorcinol dihydrochloride and 252.7 g of terephthalic acid were added to 225.5 g of 122% polyphosphoric acid, and the mixture was stirred at 60 ° C for 1 hour, and then slowly heated. The reaction was performed at 120 ° C for 4 hours, at 135 ° C for 20 hours, and at 150 ° C for 5 hours. Further, a dispersion liquid obtained by adding 5.6 g of terephthalic acid and 19.5 g of copper phthalocyanine to 74.4 g of 116% polyphosphoric acid was added to the oligomer dope, and the dispersion was added at 170 ° C for 5 hours and at 200 ° C for 10 hours. After reacting for an hour, a poly (p-phenylbenzobenzoxazonole) dope having an intrinsic viscosity of 29 dL / g measured with a methanesulfonic acid solution at 30 ° C. was obtained.

Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ. The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4900 ppm, the sodium concentration was 4200 ppm, and the NaZP monolith ratio was 1.15.

The durability was evaluated at a high temperature and high humidity by the above-mentioned method. As a result, the strength retention was 89%.

[0125] Six of the obtained polybenzazole fibers were not twisted! / In this manner, the yarn was twisted to a total denier of 1,500, and the warp and weft directions were 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 88%.

[0126] Further, after twisting the obtained six polybenzazole fibers while twisting 32TZlOcm in the Z direction, the two fibers were combined and twisted 32TZ1Ocm in the S direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 91%.

[0127] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting 12 obtained polybenzasol fibers while twisting 80 times per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 92%.

[0128] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, the twist coefficient was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric is 421 ON It was Z3cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 88%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The tensile strength in the warp direction of the obtained circular knitted fabric was 1660 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated. The strength retention was 85%.

[0129] In addition, using the obtained polybenzazole fiber yarn, 60 fibers were set in each of the vertical and horizontal directions.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5780NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

[0130] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 89%.

[0131] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was manufactured, a twist factor was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 16. OcNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 86%.

[0132] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained fabric was 136gZm ^2. The tensile strength in the warp direction was 5480 N / 3 cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 84%.

(Example 9)

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 3 seconds, and dried at 80 ° C for 4 hours. The residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn were measured by the method described above. As a result, the phosphorus concentration was 4800 ppm, the sodium concentration was 5600 ppm, and the molar ratio of NaZP was 1.57.

[0134] Six of the obtained polybenzazole fibers were not twisted! / In this manner, the yarns were combined into a yarn having a total denier of 1,500, and the yarn was warped in a warp direction and a weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 84%.

[0135] Also, do not twist the obtained polybenzazole fiber into a twist of 32 TZ10 cm in the Z direction. After twisting together, two of them were combined and twisted in the S direction at 32 TZ 1 Ocm to obtain a raw cord. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 86%.

[0136] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 88%.

[0137] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, the twist factor was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4150 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 85%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted product had a tensile strength in the vertical direction of 1670 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 83%.

[0138] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were set in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 136 gZm ² . The tensile strength in the warp direction was 5790NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and the strength retention was 82%.

[0139] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material is volume The fraction was 0.30. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

[0140] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The tensile strength of the obtained spun yarn was 15. OcNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 84%.

[0141] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5560NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

[0142] (Example 10)

In a nitrogen stream, 334.5 g of 4,6-diaminoresorcinol dihydrochloride and 252.7 g of terephthalic acid were added to 225.5 g of 122% polyphosphoric acid, and the mixture was stirred at 60 ° C for 1 hour, and then slowly heated. The reaction was performed at 120 ° C for 4 hours, at 135 ° C for 20 hours, and at 150 ° C for 5 hours. Further, a dispersion obtained by adding 5.6 g of terephthalic acid and 5.6 g of copper phthalocyanine to 74.4 g of 116% polyphosphoric acid was added to the oligomer dope, and then the mixture was cooled at 170 ° C for 5 hours and at 200 ° C for 10 hours. After the reaction, a poly (p-phenylenebenzobisoxazolone) dope having an intrinsic viscosity of 30 dLZg measured with a methanesulfonic acid solution at 30 ° C. was obtained.

Thereafter, spinning was performed under the condition that the single filament diameter became 11.5 / ζπι and 1.5 denier. A spinning dope is extruded from a nozzle having a hole diameter of 0.18 mm and a number of holes of 166 at a spinning temperature of 175 ° C to form a filament, and then is converged at an appropriate position to form a multifilament in a first cleaning bath. Dipped and allowed to solidify. In the air gap between the spinning nozzle and the first washing bath, a tench chamber was installed so that the filament could be drawn at a more uniform temperature. The temperature was set at 65 ° C. Thereafter, the filament was washed with water until the residual phosphorus concentration in the polybenzazole fiber became 5000 ppm or less, and the filament was wound around a resin bobbin without drying. The winding speed was 200 mZ. The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4500 ppm, the sodium concentration was 3800 ppm, and the NaZP molar ratio was 1.14.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 82%.

[0143] Six of the obtained polybenzazole fibers were not twisted! / In this manner, the yarns were combined into a yarn of a total denier of 1,500, and the yarn was warped in a warp direction and a weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 81%.

[0144] Further, the obtained polybenzazole fibers were twisted together with a twist of 32TZlOcm in the Z direction while being twisted, and then the two were put together to form a twist of 32TZ1Ocm in the S direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 82%.

[0145] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while twisting 80 times per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 84%.

[0146] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, a twist factor of 3.5 was set, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The obtained fabric has a tensile strength of 4380N in the vertical direction. It was Z3cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The resulting circular knitted product had a tensile strength in the vertical direction of 1760 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 83%.

[0147] Using the resulting polybenzazole fiber yarn, a plain weave was manufactured using a Levia loom with a vertical and horizontal number of 60 inches per inch. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 6040NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 81%.

[0148] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 78%.

[0149] A staple fiber having a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, the twist coefficient was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 14.6 cNZdtex. Further, the strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 81%.

[0150] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 134 gZm ² . The tensile strength in the warp direction was 5770 NZ3 cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 78%.

[0151] (Example 11)

Under a nitrogen stream, 122,5% polyphosphoric acid in 216.5 g of 4,6-diaminoresorcinol dihydrochloride Add 344.5 g of salt and 252.7 g of terephthalic acid and stir at 60 ° C for 1 hour, then slowly raise the temperature to 120 ° C for 4 hours, 135 ° C for 20 hours, and 150 ° C for 5 hours. Let it react for hours. Further, 5.6 g of terephthalic acid and 41.lg of copper phthalocyanine added to 74.4 g of 116% polyphosphoric acid were added to the oligomer dope to obtain a dispersion, which was then added at 170 ° C for 5 hours and at 200 ° C for 10 hours. After a reaction for 30 hours, a poly (p-phenylbenzobenzoxazonole) dope having an intrinsic viscosity of 28 dL / g measured with a methanesulfonic acid solution at 30 ° C. was obtained.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4800 ppm, the sodium concentration was 3900 ppm, and the molar ratio of Na / P was 1.09.

[0152] Six of the obtained polybenzazole fibers are not twisted! / The yarn is plied to give a total denier of 1,500 yarns, and the yarns are warped in the warp direction and the weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and durability was evaluated under high temperature and high humidity. The rate was 87%.

[0153] Also, do not twist the obtained polybenzazole fiber into a twist of 32 TZ10 cm in the Z direction. After twisting together, two of them were combined and twisted in the S direction at 32 TZ 1 Ocm to obtain a raw cord. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 88%.

[0154] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. When the durability of the obtained rope under high temperature and humidity was evaluated, the strength retention was 89%.

[0155] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, a twist factor of 3.5 was set, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The obtained fabric had a tensile strength of 3990 N Z3 cm in the vertical direction. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted product had a tensile strength in the vertical direction of 1560 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated. The strength retention was 85%.

[0156] In addition, using the obtained polybenzazole fiber yarn, 60 yarns were set in each direction.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 138 gZm ² . The tensile strength in the warp direction was 5590NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 86%.

[0157] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material is volume The fraction was 0.29. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 85%.

[0158] A staple fiber having a cut length of 5 lmm was produced from the obtained polybenzazole fiber, the twist factor was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The tensile strength of the obtained spun yarn was 15.3 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 85%.

[0159] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 137 gZm ² . The tensile strength in the warp direction was 5310NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated, and as a result, the strength retention was 84%.

(Example 12)

Under a nitrogen stream, 334.5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, 19.2 g of quinacridone, and 2078.2 g of 122% polyphosphoric acid were stirred at 60 ° C for 1 hour, and then slowly raised. After heating at 135 ° C for 25 hours, at 150 ° C for 5 hours, and at 170 ° C for 20 hours, the poly (p-phenylene) having an intrinsic viscosity of 24 dLZg measured with a methanesulfonic acid solution at 30 ° C was used. A benzobisoxazonole) dope was obtained.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. By the method described above, the residual phosphorus in the fiber of the obtained yarn is As a result of measuring the concentration and the sodium concentration, the phosphorus concentration was 4900 ppm, the sodium concentration was 3900 ppm, and the NaZP molar ratio was 1.07.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 85%.

[0161] Six of the obtained polybenzazole fibers were not twisted! / The yarn was plied to obtain a total denier of 1,500, and the warp direction and the weft direction were 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and the durability was evaluated under high temperature and high humidity. The rate was 83%.

[0162] Further, the obtained six polybenzazole fibers were twisted together in a Z-direction with a twist of 32TZlOcm, and then the two were combined to give a twist of 32TZ1Ocm in the S-direction. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. The durability of the obtained dip cord under high temperature and high humidity was 84%.

[0163] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting 12 obtained polybenzasol fibers while twisting them 80 times per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. When the durability of the obtained rope under high temperature and humidity was evaluated, the strength retention was 87%.

[0164] From the obtained polybenzazole fiber, a staple fiber with a cut length of 5 lmm was manufactured, the twist coefficient was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4120 NZ3 cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 84%. Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The tensile strength in the warp direction of the obtained circular knit was 1610 NZ5 cm. The durability of the obtained circular knitted product under high temperature and high humidity was evaluated, and the strength retention was 83%.

[0165] Also, using the obtained polybenzazole fiber yarn, 60 yarns in each direction were prepared.

Plain fabrics were produced using a Levia loom with the number of Z inches to be driven. The weight of the obtained woven fabric was 136 gZm ² . The tensile strength in the warp direction was 5830NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 81%.

[0166] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

[0167] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was manufactured, the twist coefficient was set to 3.5, and a spun yarn of 20Ne was manufactured with a cotton count. The tensile strength of the obtained spun yarn was 15. OcNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 84%.

[0168] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 135 gZm ² . The tensile strength in the warp direction was 5500NZ3cm. The durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 82%.

[0169] (Comparative Example 1)

Under a nitrogen stream, 33,5 g of 4,6-diaminoresorcinol dihydrochloride, 260.8 g of terephthalic acid, and 2078.2 g of 122% polyphosphoric acid were added. After stirring at C for 1 hour, slowly raise the temperature and react at 135 ° C for 25 hours, 150 ° C for 5 hours, and 170 ° C for 20 hours. A poly (p-phenylbenzobenzoxazole) dope having an intrinsic viscosity of 30 dLZg measured with an acid solution was obtained.

The wound yarn was neutralized with a 1% aqueous solution of NaOH for 10 seconds, washed with water for 15 seconds, and then dried at 80 ° C for 4 hours. As a result of measuring the residual phosphorus concentration and sodium concentration in the fiber of the obtained yarn by the method described above, the phosphorus concentration was 4400 ppm, the sodium concentration was 4000 ppm, and the NaZP molar ratio was 1.22.

The durability was evaluated at high temperature and high humidity by the method described above. As a result, the strength retention was 77%.

[0170] Six of the obtained polybenzazole fibers were not twisted! / In this manner, the yarns were combined into a yarn having a total denier of 1,500, and the yarn was warped in a warp direction and a weft direction at a rate of 5 per inch. The inserted scrim was manufactured. The resulting scrim was sandwiched between a biaxially stretched polyester film having a thickness of 12 microns coated with a polyurethane adhesive and cured and dried to produce a sail cloth. The obtained sail cloth was cut into a size of 2.5 cm in width and 50 cm in length so as to include five reinforcing fiber yarns, and the durability was evaluated under high temperature and high humidity. The rate was 76%.

[0171] In addition, after twisting the obtained six polybenzazole fibers in a Z direction with a twist of 32 TZ10 cm, the two were combined and a twist of 32 TZ1 Ocm was applied in the S direction to produce a raw. I got the code. Next, the raw code was subjected to two-step dip processing to create a dip code. The first stage dipping solution was an aqueous dispersion of epoxy resin, the processing temperature was 240 ° C, the second stage dipping solution was RFL solution, and the processing temperature was 235 ° C. Dip obtained The durability of the cord under high temperature and high humidity was 78%.

[0172] In addition, a twisted yarn having a thickness of 3000 denier was obtained by twisting the obtained 12 polybenzasol fibers while applying 80 twists per lm. Eight hammered ropes were manufactured by braiding eight of the obtained ply-twisted yarns using an ordinary device. The durability of the obtained rope under high temperature and humidity was evaluated, and as a result, the strength retention was 78%.

[0173] Also, a staple fiber with a cut length of 5 lmm was manufactured from the obtained polybenzazole fiber, the twist factor was set to 3.5, a 20ZlNe spun yarn was manufactured with a cotton count, and the two yarns were twisted. To obtain a twin yarn of 20Z2Ne.

Using the obtained twin yarn, a 2Z1 twill fabric was manufactured with a driving number of 68 Z inches in the warp direction and 60 Z inches in the weft direction. The tensile strength in the vertical direction of the obtained woven fabric was 4270N Z3cm. Subsequently, the durability of the obtained woven fabric under high temperature and high humidity was evaluated. As a result, the strength retention was 72%.

Using the spun yarn 20ZlNe obtained above, a circular knitted fabric having a length of 68 inches in the warp direction and a length of 29 inches in the weft direction was produced. The obtained circular knitted fabric had a tensile strength in the vertical direction of 15 to 90 NZ5 cm. The durability of the obtained circular knitted fabric under high temperature and high humidity was evaluated, and the strength retention was 70%.

[0174] Using the obtained polybenzazole fiber yarn, a plain woven fabric was produced using a Levia loom with a vertical number of 60 Z inches in each direction. The weight of the obtained woven fabric was 134 gZm ² . The tensile strength in the warp direction was 5780NZ3cm. When the durability of the obtained woven fabric under high temperature and high humidity was evaluated, the strength retention was 73%.

[0175] Further, the obtained four polybenzazole fibers were combined so as not to be twisted to obtain a total denier of 1,000. Using the obtained yarn, a composite material was obtained by the method for producing a composite material sample described above. The fiber content in the obtained composite material was 0.30 by volume fraction. The durability of the obtained composite material under high temperature and high humidity was evaluated. As a result, the strength retention was 73%.

[0176] From the obtained polybenzazole fiber, a staple fiber having a cut length of 5 lmm was produced, a twist coefficient was set to 3.5, and a spun yarn of 20Ne was produced with a cotton count. The resulting spinning The tensile strength of the yarn was 9.3 cNZdtex. The strength retention of the obtained spun yarn after a durability test under high temperature and high humidity was 75%.

[0177] Further, the obtained two polybenzazole fibers were combined so as not to be twisted, and a yarn having a thickness of 555 dtex was obtained. Using the obtained yarn, a plain weave was manufactured using a Levia loom with a number of 30-inch z-inches in each of the vertical and horizontal directions. The weight of the obtained woven fabric was 133 gZm ² . The tensile strength in the warp direction was 5540NZ3cm. When the durability of the obtained woven fabric under high temperature and high humidity was evaluated, the strength retention was 71%.

[0178] Tables 1 to 3 summarize the above results. As is clear from these tables, the polybenzazole fiber of each example and the article comprising the same have better durability at high temperature and high humidity than the comparative example.

[0179] [Table 1]

〕〕〔〔 table 1

Polybenzazole fiber

In fiber In fiber In fiber In fiber Na / P Type of pigment at high temperature and high humidity Initial strength CV

Pigment content First

Phosphorus concentration Na; Degree Molar ratio Durability evaluation result

% GPa-Ppm ppm-% Example 1 Slen 5.0 5.8 0.047 4600 3600 1.05 86 Example 2 Copper phthalocyanine 5.0 5.9 0.036 4500 2400 0.72 83 Example 3 Copper phthalocyanine 5.0 5.9 0.034 4400 3600 1.10 88 Example 4 Copper phthalocyanine 5.0 5.8 0.040 4700 5400 1.55 86 Example 5 Copper phthalocyanine 1.5 6.0 0.047 4500 4000 1.20 81 Example 6 Copper phthalocyanine 10 5.6 0.062 4400 3400 1.04 87 Example 7 Copper phthalocyanine 5.0 5.9 0.057 4600 2400 0.70 34 Example 8 Copper phthalocyanine 5.0 5.8 0.043 4900 4200 1.15 89 Example 9 Copper phthalocyanine 5.0 5.8 0.039 4800 5600 1.57 86 Example 10 Copper phthalocyanine 1.5 6.1 0.031 4500 3800 1.14 82 Example 1 1 鋇 phthalocyanine 10 5.5 0.059 4800 3900 1.09 87 Example 1 2 Quinacridone 5.0 5.7 0.039 4900 3900 1.07 85 Comparative Example 1-0 6.3 0.028 4400 4000 1.22 77

Table 2

Cell cloth Dip cord Polybenzazole Polybenzazole fiber woven Polybenzazole fiber woven Polybenzazole fiber woven Weave rope (Twill woven) (Round silk) (Plain woven fabric, blade-proof material) Durability Durability Durability Properties Textile properties Durability 11 things te Durability Textile properties

NZ3cm N / 5cm N / 3cm g / rri ¾ Example 1 87 89 87 4220 86 1660 85 5850 135 84 Example 2 82 85 85 4250 82 17) 0 80 5890 134 82 Example 3 90 91 90 4250 87 1670 85 5800 136 86 Example 4 86 87 88 4190 84 1660 83 5700 135 83 Example 5 82 83 84 4300 83 1740 83 5920 133 80 Example 6 89 85 SS 4010 87 1590 85 5610 138 86 Example 81 86 86 4240 83 1690 82 5820 136 82 Example 8 88 91 92 4210 88 1660 85 5780 135 86 Example 9 84 86 88 4150 85 1670 83 5790 136 82 Example 1 0 81 82 84 43B0 82 1760 83 6040 135 81 Example 1 1 87 88 89 3990 86 1560 85 5590 138 86 Example 1 2 83 84 87 4120 84 1610 83 5830 136 81 Comparative example 1 76 78 78 4270 72 1590 70 5780 134 73

[Table 3]

Industrial applicability

According to the present invention, there is provided a polybenzazole fiber which can maintain sufficient strength even when exposed to high temperature and high humidity for a long time after a kink band occurs in the yarn. Can be provided. Therefore, by using the fiber, it is processed into a woven fabric, a knitted fabric, a braid, a rope, a cord, etc. It is possible to enhance the practicality of impact-resistant members such as wood, cut-resistant members such as gloves, and rubber reinforcing materials such as belts, tires, shoe soles, ropes, hoses, and the like.

Claims

The scope of the claims

[I] A polybenzazole fiber characterized in that the strength retention (%) defined by (a / b) X 100 is 80% or more.

[2] Average strength force of a single yarn measured at a average diameter D of 5-22 μm and a fiber length of 100 mm 4.5 G

2. The polybenzazole fiber according to claim 1, wherein the fiber is Pa or more.

[3] Coefficient of variation CV when measuring the diameter of single yarn at 10 mm intervals over a fiber length of 500 mm

2. The polybenzazole fiber according to claim 1, wherein (standard deviation Z average) is 0.08 or less.

[4] The polybenzazole fiber according to claim 1, wherein the stoichiometric ratio of the inorganic base and the mineral acid remaining in the fiber is 0.8-1.4: 1.

[5] The polybenzazole fiber according to claim 1, wherein the fiber contains an organic pigment soluble in a mineral acid having a thermal decomposition temperature of 200 ° C or higher.

6. The polybenzazole fiber according to claim 5, wherein the content of the organic pigment is 2 to 8% by mass.

[7] A spun yarn comprising at least a part of the polybenzazole fiber according to claim 16.

[8] A rubber reinforcing cord comprising the polybenzazole fiber according to any one of claims 1 to 6 in at least a part thereof.

[9] A composite material comprising at least a part of the polybenzazole fiber according to claim 16.

[10] A woven or knitted fabric characterized by using at least a part of the polybenzazole fiber according to any one of claims 1 to 6.

[II] at least a part of the polybenzazole fiber according to any one of claims 1 to 6; A blade-proof material characterized by becoming.

[12] A bulletproof vest comprising at least a part of the polybenzazole fiber according to claim 16.

[13] A high-strength fiber rope obtained by using at least a part of the polybenzazole fiber according to claim 16.

[14] A sail cloth comprising at least a part of the polybenzazole fiber according to claim 16.