CN1890413A

CN1890413A - Polybenzazole fiber and article comprising the same

Info

Publication number: CN1890413A
Application number: CN 200480036797
Authority: CN
Inventors: 雾山晃平; 村濑浩贵; 阿部幸浩
Original assignee: Toyo Textile Co Ltd
Current assignee: Toyobo Co Ltd; Toyo Textile Co Ltd
Priority date: 2003-12-11
Filing date: 2004-12-09
Publication date: 2007-01-03
Also published as: JP2005171416A

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

Polybenzazole fiber reaches by its article that constitute

Technical field

Present patent application respectively to Japan's patent application 2003-412681 number, with 2003-424648 number, with 2003-424649 number, with 2003-424650 number, with 2003-424651, with 2003-424652 number, with 2003-424653, with 2003-424654 number, advocate priority with 2003-424655 number, by reference in this, with its entire combination in this specification.

The present invention relates at fabric, compile in the back manufacturing procedure of thing, braid, rope, flexible cord etc., even yarn is damaged and produces knot group (kink band) afterwards on yarn, under hot and humid degree, also have poly-indoles (Poly benzazole) fiber of excellent durability and contain it and article such as article, the especially textile strand, rubber armature, fiber reinforced composite material, braided fabric, knifeproof material or the bullet-proof vest that form, rope, canvas.

Background technology

As fiber with high strength, high-fire resistance, the known polybenzazole fiber that polybenzoxazoles (polybenzoxazole) or polybenzothiozole (poly benzothiazole) is arranged or constitute by these copolymer (copolymer).

Usually, polybenzazole fiber obtains by the following method: from spinning head extrude contain above-mentioned polymer (polymer) or copolymer and sour solvent spinning solution (dope) afterwards, being impregnated in the coagulability fluid (mixed liquor of water or water and inorganic acid) solidifies it, and then after thereby most solvent is removed in cleaning up hill and dale in washing is bathed, water-soluble liquid bath through inorganic base, after residual acid neutralizes with not being extracted in the yarn, carry out drying.

Polybenzazole fiber because mechanical property excellence such as intensity and heat resistance are also very high, therefore is used in various uses, but wishes in recent years further to improve performance.Especially, when processing the article that contain polybenzazole fiber and form, wish polybenzazole fiber strongly, in the back manufacturing procedure of for example fabric, volume thing, braid, rope, flexible cord etc., produce after the knot group on yarn even yarn is damaged, under hot and humid degree, also have excellent durability, promptly, even be exposed to high temperature and high humility following time for a long time, also can keep intensity fully.

For example, known have a textile strand that has used polybenzazole fiber.Yet, wish further to improve the performance of the textile strand that has used polybenzazole fiber, wish polybenzazole fiber strongly, especially in the back manufacturing procedure of fabric, volume thing, braid, rope, flexible cord etc., produce after the knot group on yarn even yarn is damaged, under hot and humid degree, also have excellent durability, promptly, even be exposed to high temperature and high humility following time for a long time, also can keep intensity fully.

Also have, in the past, be directed to the fiber that makes as rubber armatures such as tire, flexible pipe and belts, based on nylon fiber, polyester fiber, glass fibre and iron and steel fiber.In recent years, be the aromatic polyamide fibre of representative with Kevlar (kevlar) with high strength, high elasticity rate, be used as various rubber armatures.Even compare with this aromatic polyamide fibre, also have higher strength, elastic rate, and the also excellent polybenzazole fiber of heat resistance, DIMENSIONAL STABILITY, just noticeable as the rubber armature.Therefore, in rubber goods, materials and equipments field, organic fiber in the past is abundant inadequately on performance, is studying as requiring the more reinforcement of high strength, the high-fire resistance purposes aspect use of the polybenzazole fiber of fiber for this reason.

Yet, wish that strongly rubber strengthens the polybenzazole fiber of usefulness, especially this rubber intensive aspect is applied movingly when tired, can keep intensity fully when forming the environment of high temperature and high humility in the rubber.

In the past, as fiber reinforced composite material, used glass fibre always, but turned to purpose, the material that recently, develop, practicability is used carbon fiber or aromatic polyamides (aramid) fiber with high strength, light weight.But,, have poor, the crisp problem of impact although carbon fiber mechanical property aspect is very excellent.On the other hand, aramid fibre, although show better performance aspect resistance to impact, because its spring rate is lower than carbon fiber, so stiffening effect is less.Therefore, by the fiber reinforced composite material that polybenzazole fiber constitutes, resistance to impact, spring rate are all excellent, and show the stiffening effect above carbon fiber, therefore just are being expected for down centurial fiber reinforced composite material.

Yet expectation further improves the performance of the fiber reinforced composite material that contains polybenzazole fiber, and wishes the fiber reinforced composite material that is made of polybenzazole fiber strongly, is exposed to high temperature and high humility following time especially for a long time can keep intensity fully.

Also have, polybenzazole fiber such as above-mentioned is because therefore mechanical property excellences such as intensity, spring rate also are used the fiber structure of making to constitute protective materials, protection dress material and industrial goods, materials and equipments.Yet expectation further improves the performance of the braided fabric that contains polybenzazole fiber, and wishes the fabric that is made of polybenzazole fiber strongly, is exposed to hot and humid degree following time especially for a long time can keep intensity fully.

In the past,, used aramid fibre as knifeproof material or bullet-proof vest always, but recently, the material that develop, practicability has been used high-strength polyethylene fiber.But, used the knifeproof material or the bullet-proof vest of aramid fibre, need a large amount of fibers in order to show desired barrier propterty, cause weight to become heavy, thickness thickening thus, thus wear uncomfortable, can not a direct puncture.On the other hand, for knifeproof material that has used high-strength polyethylene fiber or bullet-proof vest,, fail to reduce thickness owing to proportion is less although reduced weight.Therefore, knifeproof material or bullet-proof vest by polybenzazole fiber constitutes show the barrier propterty above aramid fibre, high-strength polyethylene fiber, therefore are expected for the following centurial knifeproof material or the bullet-proof vest of light weight and thinner thickness.

Yet expectation further improves the performance of the knifeproof material or the bullet-proof vest that contain polybenzazole fiber, and wishes the knifeproof material or the bullet-proof vest that are made of polybenzazole fiber strongly, is exposed to high temperature and high humility following time especially for a long time can keep intensity fully.

Also have, polybenzazole fiber such as above-mentioned, because mechanical property excellences such as intensity, and heat resistance is also very high, therefore is widely used in gradually with in the rope purposes that needs necessary strength or mar proof headed by the yacht rope (yacht rope).But,, therefore be subjected to the destruction of the machinery in the rope manufacturing process easily owing to the molecular chain structure that polybenzazole fiber has very high orientation.Therefore, wish polybenzazole fiber strongly, in the back manufacturing procedure of rope, flexible cord etc., on yarn, produce after the knot group even yarn is damaged, under hot and humid degree, also has excellent durability, that is,, also can keep intensity fully even be exposed to high temperature and high humility following time for a long time.

Also have, also be widely used in the canvas that contains polybenzazole fiber.Especially for the employed balloon sail of yacht contest, pursue high tension resistance or tensile strength, even also can not be out of shape so that the shape of design is subjected to the influence of wind.For this reason, in recent years, the fabric or the scrim (scrim) that will be made of high-strength high-elasticity rate fiber are clipped in 2 as be that the canvas of laminating molding between the film of representative is just forming main flow with polyester (Polyester).In addition, also in the method for exploitation by three-dimensional integrated shaping manufacturing balloon sail, said canvas in this specification just is meant to comprise this three-dimensional integrated formed products., used in the product of those technology, using has para-aramid (para-aramid) fiber or carbon fiber in the past.Carbon fiber is compared with the para-aramid fiber, and expectation improves the performance of the high balloon sail of tensile elasticity rate, but then, has the weak problem of the curved fatigability of not folding.For this reason, develop the balloon sail that contains polybenzazole fiber, and in the yacht contest of countries in the world, obtained good result.

Yet expectation further improves the performance of the balloon sail that contains polybenzazole fiber, and wishes the canvas that is made of polybenzazole fiber strongly, is exposed to high temperature and high humility following time especially for a long time can keep intensity fully.

Summary of the invention

The present invention is conceived to above-mentioned thing and realizes, produces after the knot group on yarn even its purpose is to provide yarn to be damaged, and is exposed to the polybenzazole fiber that only causes also under high temperature and the high humility that less intensity reduces for a long time.

Also have, another object of the present invention is to provide the article that contain this polybenzazole fiber and form, especially article such as textile strand, braided fabric, rubber armature, fiber reinforced composite material, rope, canvas, knifeproof material or bullet-proof vest.

That is, the present invention adopts following structure.

1, a kind of polybenzazole fiber is characterized in that,

By the value of the strength retention (%) of (a/b) * 100 definition more than or equal to 80%, wherein, a: twist so that reach twist factor 30 back placements 30 seconds by the S turn, separate the twisting count that is twisted to twist factor 6 by the S turn afterwards, afterwards after handling 240 hours under the environment of 80 ℃ of relative humidity 80%, the intensity of at room temperature taking out and measuring [cN/dtex];

B: twist so that reach twist factor 30 back placements 30 seconds by the S turn, separate the intensity of measuring behind the twisting count that is twisted to twist factor 6 [cN/dtex] by the S turn afterwards.

2, according to above-mentioned 1 described polybenzazole fiber, it is characterized in that,

The average diameter D of single thread is 5～22 μ m, and the mean intensity of the long 100mm of fiber of mensuration is more than or equal to 4.5GPa.

3, according to above-mentioned 1 described polybenzazole fiber, it is characterized in that,

Coefficient of variation CV (standard deviation/mean value) when spreading all over the long 500mm of fiber at interval and measure the diameter of single thread with 10mm is smaller or equal to 0.08.

4, according to above-mentioned 1 described polybenzazole fiber, it is characterized in that,

The residual inorganic base and the stoichiometric proportion of inorganic acid are 0.8～1.4: 1 in the fiber.

5, according to above-mentioned 1 described polybenzazole fiber, it is characterized in that,

Contain heat decomposition temperature in the fiber more than or equal to 200 ℃ and be dissolved in the organic pigment of inorganic acid and form.

6, according to above-mentioned 5 described polybenzazole fibers, it is characterized in that,

The containing ratio of organic pigment is 2～8 quality %.

7, a kind of textile strand is characterized in that,

At least a portion is used each described polybenzazole fiber in above-mentioned 1～6 and is formed.

8, a kind of rubber is strengthened using flexible cord, it is characterized in that,

9, a kind of composite is characterized in that,

10, a kind of braided fabric is characterized in that,

11, a kind of knifeproof material is characterized in that,

12, a kind of bullet-proof vest is characterized in that,

13, a kind of high strength fibre rope is characterized in that,

14, a kind of canvas is characterized in that,

Present inventors find following situation, until having finished invention.

What (1) contain specified quantitative in fiber has heat decomposition temperature more than or equal to 200 ℃ high-fire resistance, and be dissolved in the organic pigment in the inorganic acid, have in preferred its molecular structure-material of N=base and/or NH-base, especially purple cyclic ketones and/or perylene kinds, phthalocyanines, quinoline a word used for translation ketone, then with yarn in do not contain above-mentioned organic pigment situation compare, on yarn, produce after the knot group even yarn is damaged, also can improve the durability under the hot and humid degree, be specially and to suppress to be exposed to for a long time caused intensity reduction under high temperature and the high humility significantly.

(2) in addition, the pH of the yarn inside of maintenance polybenzazole fiber is extremely important near 7, thus, on yarn, produce after the knot group even yarn is damaged, also can improve the durability under the hot and humid degree, be specially and to suppress to be exposed to for a long time caused intensity reduction under high temperature and the high humility significantly.

Description of drawings

Fig. 1 is the example that the resin that is used to make the composite that is made of polybenzazole fiber of the present invention contains bath unit and drawing-die (dies).

Among the figure, the A-fiber yarn; B-imports the angle; The C-nozzle diameter; D-parallel portion length; The E-drawing-die.

The specific embodiment

Below, the present invention is at length described.

Polybenzazole fiber of the present invention is meant the fiber that contains polybenzazole polymers and form.Poly-indoles (below, be also referred to as PBZ) polymer is meant, from by polybenzoxazoles (below, be also referred to as PBO), polybenzothiozole (below, be also referred to as PBT), and the group that constitutes of polybenzimidazoles (below, be also referred to as PBI) in the polymer more than a kind selected.

In the present invention, PBO is meant the polymer that contains oxazole (oxazole) ring that is incorporated into the aromatic series base, and this aromatic series base needn't be a phenyl ring.In addition, PBO also extensively contains, by poly-(to the two oxazoles of phenylene benzo) (poly (p-phenylenebenzobisoxazole)) or be incorporated into the polymer that the unit of a plurality of oxazole rings of aromatic series base constitutes.Same viewpoint also is applicable to PBT or PBI.

Also have, polybenzazole polymers of the present invention also comprises the mixture arbitrarily of PBO, PBT and PBI, based on the two or more block of PBO, PBT and PBI or atactic polymer etc.

The structural units that the PBZ polymer contains is preferably selected in the lyotropic liquid crystal polymer from inorganic acid, with specific concentrations formation liquid crystal.This polymer contains the monomer unit of structural formula (a)～(f) record and forms.

[changing 1]

Polybenzazole fiber can be from containing the spinning solution manufacturing of PBZ polymer.Suitable solvent as being used to modulate this spinning solution can exemplify the acid of the non-acidizing that can dissolve cresols (cresol) or its polymer.Example as the acid of suitable non-acidizing can exemplify the sulfuric acid of polyphosphoric acid, methanesulfonic acid and high concentration or these mixture.Wherein, polyphosphoric acid and methanesulfonic acid are more suitable, especially the polyphosphoric acid optimum.

Polymer concentration in the spinning solution is preferably at least about 7 quality %, more preferably at least 10 quality %, most preferably at least 14 quality %.Cmax is subjected to the qualification of the actual usability of the dissolubility of so-called polymer for example or spinning solution viscosity.Because of these boundary line factors, usually, polymer concentration is no more than 20 quality %.

In the present invention, suitable polymer blend or copolymer and spinning solution can be synthetic by known method.For example, can be with reference to the United States Patent (USP) the 4th of Wolfe, 533, the 4th, 772, No. 678 specifications of United States Patent (USP) (1988.9.22) of No. 693 specifications (1985.8.6), Sybert, the United States Patent (USP) the 4th of Harris, 847, the record of the 5th, 089, No. 591 specifications of United States Patent (USP) (1992.2.18) of No. 350 specifications (1989.7.11) or Gregory.

According to above-mentioned document, by in the acid solution of non-acidizing and dehydration property, under non-acidizing atmosphere and high-speed stirred and shear conditions, from about 60 ℃ to 230 ℃, make the suitable monomer reaction with stage ground or certain programming rate elevated temperature, thus it is synthesized.

Extrude the spinning solution of such acquisition from spinning head, in the space, elongate forming long filament.Suitable manufacture method is recorded in the 5th, 034, No. 250 specifications of previous described list of references or United States Patent (USP).Leave the spinning solution of spinning head, enter the space between spinning head and the rinse bath chamber.This space is commonly referred to as air gap, contains gases such as air, nitrogen, argon, helium, carbon dioxide usually, also can accommodate do not dissolve solvent and not with the liquid of spinning solution reaction.

Long filament after the spinning for fear of excessive extension, needs the part of cleaning and removing solvent.Then, further clean, and, remove most solvent by the neutralization of inorganic bases such as suitable NaOH, calcium hydroxide, potassium hydroxide.Here said cleaning is meant, makes the contact of fiber or long filament have intermiscibility with respect to the inorganic acid that is dissolved with polybenzazole polymers and do not become the liquid of solvent with respect to polybenzazole polymers, removes the disacidify solvent thus from spinning solution.As suitable cleaning liquid, for example can exemplify the mixture of water or water and sour solvent.Long filament preferably in residual inorganic acid concentration smaller or equal to 8000ppm, further preferably cleaning smaller or equal under the 5000ppm.Afterwards, long filament carries out drying, heat treatment as required, batches etc.

As having heat decomposition temperature more than or equal to 200 ℃ high-fire resistance and be dissolved in organic pigment in the inorganic acid among the present invention, when can be polymerization or add in the polymer spun silk stock solution, still residue in the material in the fiber after the spinning.Can exemplify insoluble azo colour, condensed azo pigment, color lake, isoindoline ketone, same indoles, dioxazine, purple cyclic ketones (perinones) and/or perylene kinds, phthalocyanines, quinoline a word used for translation ketone etc. as concrete example.Wherein, have-material of N=base and/or NH-base more preferably purple cyclic ketones and/or perylene kinds, phthalocyanines, quinoline a word used for translation ketone in the also preferred molecule.

Can exemplify as purple cyclic ketones and/or perylene kinds, bisbenzimidazole [2,1-b:2 ', 1 ', i] benzo [1mn] [3,8] phenanthrolene-8,17-diketone, bisbenzimidazole [2,1-b:1 ', 2 '-j] benzo [1mn] [3,8] phenanthrolene-6, the 9-diketone, 2, and two (p-mehtoxybenzyl) anthracenes of 9-[2,1,9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, two (the p-ethoxybenzene methyl) anthracenes [2 of 9-, 1,9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, two (3, the 5-di mehtoxybenzyl) anthracenes [2,1 of 9-, 9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, two (p-methoxyphenyl) anthracenes of 9-[2,1,9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-and tetraketone, 2, two (p-ethoxyl phenenyl) anthracenes [2,1 of 9-, 9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, two (3, the 5-dimethyl phenyl) anthracenes of 9-[2,1,9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, the 9-dimethyl anthracene [2,1,9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-tetraketone, 2, two (the 4-phenyl azo phenyl) anthracenes [2,1 of 9-, 9-def:6,5,10-d ' e ' f '] two isoquinolin-1,3,8,10 (2H, 9H)-and tetraketone, 8,16-pyranthrene diketone etc.Also can and with the compound more than 1 or 2 of these purple cyclic ketones classes.

As phthalocyanine (phthalocyanines) class, as long as have phthalocyanine frame, then no matter have or not metal and the atomic species that is coordinated in its center.Concrete example as these compounds can exemplify, 29H, 31H-phthalocyanine salts (2-)-N29, N30, N31, N32 copper, 29H, 31H-phthalocyanine salts (2-)-N29, N30, N31, N32 iron, 29H, 31H-phthalocyanine salts-N29, N30, N31, the N32 cobalt, 29H, 31H-phthalocyanine salts (2-)-N29, N30, N31, N32 copper, oxo (29H, 31H-phthalocyanine salts (2-)-N29, N30, N31, N32), (SP-5-12) titanium etc.Also have, these phthalocyanine frames also can have sub stituents such as halogen atom more than 1, methyl, methoxyl group.Also can and with the compound more than 1 or 2 of these phthalocyanines.

Can exemplify as quinoline a word used for translation ketone, 5,12-dihydro-2,9-dimethyl quinoline also [2,3-b] acridine-7,14-diketone, 5,12-EEDQ also [2,3-b] acridine-7,14-diketone, 5,12-dihydro-2,9-dichloroquinoline be [2,3-b] acridine-7 also, the 14-diketone, 5,12-dihydro-2,9-dibromo quino [2,3-b] acridine-7,14-diketone etc.Also can and with the compound more than 1 or 2 of these quinoline a word used for translation ketones.

Also have, also can and use the compound more than 2 or 3 of perylene kinds, purple cyclic ketones class, phthalocyanines and quinoline a word used for translation ketone.

The method that contains these organic compounds in the yarn is not particularly limited, and the stage of polymer spun silk stock solution that can be when arbitrary stage of poly-indoles polymerization or polymerization finish is contained it.For example preferred, the method that simultaneously organic pigment is fed intake when the raw material of poly-indoles is fed intake, with the stage or programming rate elevated temperature and the method that makes any time point of its reaction add organic pigment arbitrarily, also have, when finishing, polymerisation in the reaction yarn, adds organic pigment, and the method that mixes.

The maximum feature of polybenzazole fiber of the present invention is that after twist factor 30 twisting, the strength retention after handling 240 hours under the environment of 80 ℃ of relative humidity 80% is more than or equal to 80%.That is, polybenzazole fiber of the present invention, by the value of the strength retention (%) of (a/b) * 100 definition more than or equal to 80%.

Wherein, a: twist so that reach twist factor 30 back and placed 30 seconds by the S turn, separate the twisting count that is twisted to twist factor 6 by the S turn afterwards, afterwards after handling 240 hours under the environment of 80 ℃ of relative humidity 80%, the intensity of at room temperature taking out and measuring [cN/dtex],

The strength retention of polybenzazole fiber of the present invention (%), preferred 80～100%, more preferably 82～100%, more preferably 84～100%, more preferably 85～100%, more preferably 80～99%, more preferably 80～98%, more preferably 84～98%.

Because polybenzazole fiber molecule self rigidity is higher, and strand interaction each other is less, therefore,,, produce knot group in vertical direction then with respect to the fiber axis direction if to the fibration bending stress.Although according to the kind of back processing, there is difference in the degree that knot takes place, needs only one and carries out the back processed, will produce knot group usually.Also have, even only yarn is twisted, as long as twisting count uprises and will produce knot group.Be exposed to for a long time under high temperature and the high humility if will produce the polybenzazole fiber of knot group, then compare, expose the intensity that causes and reduce the tendency that existence enlarges markedly with the situation of no knot.But, contain described organic pigment by making in the yarn after the spinning, even when producing knot group, also can improve the durability hot and humid degree under, that is, and the intensity reduction when reducing under hot and humid degree long-time the exposure.Thus, in the back manufacturing procedure of fabric, volume thing, braid, rope, flexible cord etc., on yarn, produce after the knot group, under hot and humid degree, also have excellent durability even yarn is damaged.Here said organic pigment, be as described have heat decomposition temperature more than or equal to 200 ℃ heat resistance and be dissolved in the material of inorganic acid, preferably have in its molecular structure-organic pigment of N=and/or NH-.The organic pigment of more preferably purple cyclic ketones and/or perylene kinds, phthalocyanines or quinoline a word used for translation ketone.

Above-mentioned polybenzazole fiber of the present invention wishes that the stoichiometric proportion (stoichiometry) of inorganic base and inorganic acid residual in the fiber is 0.8～1.4: 1.If inorganic base residual in the fiber is too little with respect to the stoichiometric proportion of inorganic acid, then because the pH of yarn inside becomes acidity terrifically, so the water decomposition that adds of PBZ molecule carries out easily, and intensity reduces easily.Compare with the situation of no knot, this tendency of polybenzazole fiber that knot has taken place is more remarkable, is exposed to the intensity reduction that causes under high temperature and the high humility for a long time thereby increase.On the other hand, if residual inorganic base is too big with respect to the stoichiometric proportion of inorganic acid in the fiber, then because the pH of yarn inside becomes alkalescence terrifically, so the water decomposition that adds of PBZ molecule carries out easily, and intensity reduces easily.Compare with the situation of no knot, this tendency of polybenzazole fiber that knot has taken place is more remarkable, is exposed to the intensity reduction that causes under high temperature and the high humility for a long time thereby increase.According to more than, the stoichiometric proportion of wishing inorganic base residual in the fiber and inorganic acid is 0.8～1.4: 1, more preferably 1.0～1.3: 1, and wish that arbitrary portion is all realized above-mentioned stoichiometric proportion in the fiber.Neutralization method as the inorganic base in cleaning can exemplify, directed oiling (guide oiling) mode, oil spout (showering) mode, dipping (dipping) mode etc., but be not special qualification.

Above-mentioned polybenzazole fiber of the present invention, the containing ratio of wishing the organic pigment described in the fiber are 2～8 quality %, more preferably 3～6 quality %.If containing ratio is low excessively, then reduce making the effect that contains organic pigment in the yarn and expect, that is, the durability on the yarn behind the generation knot group is specially the inhibition effect that is exposed to the intensity reduction that causes under high temperature and the high humility for a long time.On the other hand, if containing ratio is too high, the situation that then exists the increase that causes filament linear-density or fiber number inequality, the yarn intensity at initial stage to reduce.Containing ratio also can not reduce because of organic pigment becomes the early strength that defective causes fiber in fiber, and the spinnability during spinning is also fine, and can be kept the good operability of no cracked ends in the scope of 2～8 quality %.Be speculated as this pigment dissolved that is based on interpolation in inorganic acid, therefore also be dissolved in the polymer spun silk stock solution, but the present invention be not limited to this investigation.

Above-mentioned polybenzazole fiber of the present invention, the average diameter D of preferred single thread is 5～22 μ m, more preferably 10～20 μ m.

Also have, preferably the mean intensity of measuring with the long 100mm of fiber is more than or equal to 4.5GPa, more preferably 5.0～8.0GPa.

And then polybenzazole fiber of the present invention as above-mentioned, wishes to contain in the fiber organic pigment.Therefore, require the fiber footpath inequality of fiber is managed fully.Polybenzazole fiber of the present invention, the coefficient of variation CV (standard deviation/mean value) when wishing to spread all over the diameter of the long 500mm mensuration of fiber single thread at interval with 10mm be smaller or equal to 0.08, is more preferably less than to equal 0.06.If the coefficient of variation is excessive, stress takes place then thin part easily concentrates, thereby ruptures easily.

Polybenzazole fiber of the present invention owing to have the durability of the excellence under hot and humid degree, therefore, as following, is suitable for the use of various article.Especially, polybenzazole fiber of the present invention can be applicable to article such as textile strand, rubber armature, fiber reinforced composite material, braided fabric, knifeproof material or bullet-proof vest, rope, canvas aptly.

Polybenzazole fiber of the present invention can make aptly as textile strand; especially, be used to constitute protective materials or the protection dress material that is used in the necessary high strength of needs, high heat-resisting fire-entry suit, heat-resisting clothes, uniforms for worker etc. and be used in the textile strand of fiber structure that the necessary high strength of needs, high heat-resisting conveyance material, fender, lining are protected the industrial goods, materials and equipments of material etc.

Textile strand of the present invention also comprises the composite spinning yarn of fiber blend with other.Fiber as other can exemplify, natural fabric, organic fiber, metal fibre, inorfil, mineral fibres etc.Also have, be not particularly limited, both can use the continuous blending method of general opening or cleaning, also can make it form core sheath structure for the method or the mode of blending.

Polybenzazole fiber of the present invention also can make as rubber reinforcement materials such as tire, belt, flexible pipes aptly.

Be used in rubber of the present invention and strengthen polybenzazole fiber,, can use ring doubling frame etc. to give unidirectional twisting or doublet cord twisting from improving the viewpoint of fatigue durability with flexible cord.At this moment, twist factor (K) can be 10～100.

Also have,, can implement corona treatment or Cement Composite Treated by Plasma etc. the surface of above-mentioned polybenzazole fiber in order to improve the caking property with rubber.In addition, also can give polybenzazole fiber and can or implement the compound of the fiber surface reaction of corona treatment etc. with fiber surface.Also have,, also can implement impregnation process polybenzazole fiber in order to improve the caking property with rubber.As this treatment fluid, can use following separately or be used in combination: (A) aqueous dispersions of epoxy resin; (B) aqueous dispersions of blocked isocyanate (blockedisocyanate); (C) aqueous dispersions of latex; (D) resorcin formaldehyde resin-latex (RFL) mixed liquor is generally handled by the multistage more than a section or two sections, but also can be used other method.

Polybenzazole fiber of the present invention also can use aptly and make composite.By the composite that polybenzazole fiber of the present invention constitutes, can be any mode of unidirectional reinforcement, plan isotropism (pseudoisotropic) lamination, fabric laminate.Also have,, can use any resin of interchangeable heat plastic resins such as senior engineering plastics such as thermosetting resins such as epoxy resin, phenolic resin, PPS, PEEK or PE, PP, polyamide etc. as matrix (matrix) resin.

Polybenzazole fiber of the present invention can make aptly as braided fabric; especially, be used to constitute protective materials or the protection dress material that is used in the necessary high strength of needs, high heat-resisting fire-entry suit, heat-resisting clothes, uniforms for worker etc. and be used in the braided fabric of fiber structure that the necessary high strength of needs, high heat-resisting conveyance material, fender, lining are protected the industrial goods, materials and equipments of material etc.

Braided fabric of the present invention also can comprise the composite braided thing of mixed with fibers with other.Fiber as other can exemplify, natural fabric, organic fiber, metal fibre, inorfil, mineral fibres etc.In addition, be not particularly limited, can adopt for fabric to interweave or bilayer is knitted or lip ends (lip stop) etc. for the method for mixing, for compile thing can adopt hand over compile or double-deckly compile, also have in addition circular knit, plain stitch, through volume, La Sheer warp knitting fabrics etc.In addition, the fibre bundle for constituting braided fabric also is not particularly limited, and can use monofilament, multifilament, twist yarn and twisted yarn, cladded yarn, textile strand, crush cutting (stretch broken) textile strand, heart sheath structure yarn, braid etc.

Polybenzazole fiber of the present invention also can make aptly as knifeproof materials such as vest, gloves and use.Knifeproof material of the present invention is made of the laminate of the fabric that polybenzazole fiber constitutes.As the tissue of fabric, can use flat tissue, twill-weave, in addition, also can use any of the employed tissue of common fabric.If preferred flat tissue, the twill-weave etc. used are difficult for noticeable tissue, then can show high anti-sword performance.

The degree of knitting of the employed polybenzazole fiber of knifeproof material of the present invention smaller or equal to 600dtex, as if the low degree of knitting that is preferably smaller or equal to 300dtex, then obtains high anti-sword performance easily.Also have, the textile density of the employed fabric of knifeproof material of the present invention is preferably greater than and equals 30/25mm, more preferably greater than equaling 50/25mm.When density is hanged down, exist because of yarn moves to cause easily to obtain the situation of anti-sword performance fully.In addition, the order of fabric is paid to be preferably greater than and is equaled 100g/m ², and then if more than or equal to 150g/m ², then more can bring into play excellent anti-sword performance.Also have, also can or contain part or all that is dipped in fabric used in the present invention resinous coat.Knifeproof material of the present invention is the laminate of this fabric, but also can be used by the state that high-intensity sewing thread makes fabric each other into one.

Polybenzazole fiber of the present invention also can make aptly as bullet-proof vest and use.Bullet-proof vest of the present invention is made of the laminate of the fabric that polybenzazole fiber constitutes.As the tissue of fabric, can use flat tissue, twill-weave, in addition, any of the common employed tissue of fabric.If preferred flat tissue, the twill-weave etc. used are difficult for noticeable tissue, then can show high anti-sword performance.The degree of knitting of the employed polybenzazole fiber of bullet-proof vest of the present invention is preferably smaller or equal to 1100dtex, if more preferably smaller or equal to the low degree of knitting of 600dtex, then obtain high ballistic performance easily.Also have, the textile density of the employed fabric of bullet-proof vest of the present invention is preferably smaller or equal to 40/25mm.In addition, the order of fabric is paid preferably smaller or equal to 200g/m ²If, and then 150g/m ², then more can bring into play excellent ballistic performance.Bullet-proof vest of the present invention is the laminate of this fabric, but also can be used by the state that high-intensity sewing thread makes fabric each other into one.

Polybenzazole fiber of the present invention also can make as canvas aptly.Canvas of the present invention can be with for example polyethylene fiber, para-aramid fiber, Wholly aromatic polyester fiber or carbon fiber etc., and other the high strength fibre use that combines.For canvas, on the direction of complexity, strengthen by fiber.In the present invention, the axial durability of the fiber of polybenzazole fiber importantly promptly, is improved the strength retention that is exposed to high temperature and high humility following time for a long time.

(embodiment)

Below, adopt example that the present invention is described particularly.The present invention is not subjected to the restriction of following embodiment certainly, can suitably apply change certainly in the scope of aim described later before can being suitable for, and these all are contained in the technical scope of the present invention.

(twisting method of long filament)

With JIS-L1013 is standard, uses twist tester, clamps (grips) and is made as 50cm at interval, based on the ordinance load that obtains from following calculating formula, to twist tester sample is installed, and twists so that reach twist factor 30.In addition, twisting is made as the S turn.Place after 30 seconds, separate the twisting count that is twisted to twist factor 6, obtain the sample of the twist factor 6 of S turn thus by the S turn.In addition, the calculating formula of the ordinance load (a) during twisting, and the relational expression of twist factor (K) and twisting count (Tw) be shown in following.

a＝(1/10)DK＝0.124×Tw×D ^1/2

A: ordinance load (g)

Tw: twisting count (return/inch)

D: long filament degree of knitting (Dtex)

(the Evaluation of Durability method under high temperature and the high humility)

For the Evaluation of Durability under high temperature and the high humility, estimate with respect to the conservation rate of the tensile strength before handling by the tensile strength after high temperature and the high humility keeping processing.

Under the state on the resin bobbin of diameter 10cm, after the keeping of high temperature and high humility is handled in Constant Temperature and Humidity Chambers, taken out sample in sample (state of the twist factor 6 of the S turn) circumvolution that will carry out twisting by above-mentioned twisting method.The tensile strength measured value of implementing tension test under the room temperature and obtaining is made as a (cN/dtex), with implement under the room temperature by above-mentioned twisting method carried out twisting sample (state of the twist factor 6 of S turn) tension test and the measured value of the tensile strength that obtains is made as b (cN/dtex), and remove a by b and multiply by 100 and tried to achieve strength retention.In addition, handle for the keeping under the hot and humid degree, use big and the system Humidic Chamber 1G43M of science society, complete shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.The mensuration of tensile strength is standard with JIS-L1013, and (Shimadzu Seisakusho Ltd.'s system, pattern AG-50KNG) measures by cupping machine.

(the residual phosphorus concentration in the long filament, the evaluation method of na concn)

Residual phosphorus concentration in the long filament after the wet type decomposition samples, is tried to achieve by the colorimetric analysis of molybdenum blue method.Residual sodium concentration in the long filament behind carbonization, calcining, sour dissolved samples, makes 1.2N-HCl solution, is tried to achieve by the atom light absorption method.

(assay method in fiber footpath)

The mensuration in fiber footpath can by method of optics, and any of the method for machinery as micrometer all can carry out.Consider method of optics such as preferred scanning electronic microscope (SEM) or laser type measuring outside diameter device from the aspect of the simplicity of measuring operation.Also have,, need to measure a plurality of single thread in order to react the integral body picture of total fiber.At first, need measure a plurality of single thread as much as possible, measure 5% of whole long filament numbers at least, more preferably measure 7% of whole long filament numbers.For the meticulous change of polybenzazole fiber,, therefore the yarn length direction is also needed to measure enough numbers because the change of yarn length direction is more greater than the situation of the change between long filament.Therefore, on the yarn length direction, measure at least more than or equal to 500mm, more preferably measure more than or equal to 750mm, even the measuring interval of this moment at interval greatly also should be smaller or equal to 25mm, be more preferably less than and equals 12mm.If measuring interval is long, leaked from measuring point in the fiber of taper portion footpath in the middle of then might making, but if consider actual alteration mode, and when then adopting the measuring interval less than 5mm, the diameter variation amount is very little.From relevant viewpoint, in the present invention, adopted the method that spreads all over the long 500mm actual measurement of fiber single thread diameter with 10mm at interval.Use scanning electronic microscope (SEM), measure the single thread diameter down for 5000 times, calculate its mean value and the standard deviation that is assumed to regular distribution, and calculated the coefficient of variation (CV) by the formula shown in following in multiplying power.In addition, use the latex pearl of known diameter in advance, carry out the multiplying power revisal of scanning electronic microscope after, implemented mensuration.

The mean value [μ m] of the standard deviation of CV=single thread diameter [μ m]/single thread diameter

(high temperature of canvas sample and the Evaluation of Durability method under the high humility)

For the high temperature of canvas sample and the Evaluation of Durability under the high humility, after in Constant Temperature and Humidity Chambers, sample being carried out the keeping of high temperature and high humility and handles, in standard state (temperature: 20 ± 2 ℃, relative humidity: take out in the laboratory 65 ± 2%), and implemented tension test with interior at 30 minutes, the tensile strength after being handled by high temperature and high humility keeping is then estimated with respect to the conservation rate of the tensile strength before handling.Handle for the keeping under the hot and humid degree, use big and the system Humidic Chamber 1G43M of science society, complete shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.The mensuration of tensile strength is standard with JIS-L1096, by cupping machine (Shimadzu Seisakusho Ltd.'s system, pattern AG-50KNG), the sample of specimen width 2.5cm is measured.

(rubber is strengthened with the high temperature of flexible cord or composite sample and the Evaluation of Durability method under the high humility)

Strengthen with the high temperature of flexible cord or composite sample and the Evaluation of Durability under the high humility for rubber, after in Constant Temperature and Humidity Chambers, sample being carried out the keeping of high temperature and high humility and handles, in standard state (temperature: 20 ± 2 ℃, relative humidity: take out in the laboratory 65 ± 2%), and implemented tension test with interior at 30 minutes, the tensile strength after being handled by high temperature and high humility keeping is then estimated with respect to the conservation rate of the tensile strength before handling.Handle for the keeping under the hot and humid degree, use big and the system Humidic Chamber 1G43M of science society, complete shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.The mensuration of tensile strength is standard with JIS-L1013, and (Shimadzu Seisakusho Ltd.'s system, pattern AG-50KNG) measures by cupping machine.

(high temperature of high strength fibre rope and the Evaluation of Durability method under the high humility)

Under the situation that does not apply above-mentioned twisting processing, implemented the Evaluation of Durability of high strength fibre rope.Evaluation for the reduction of the intensity under high temperature and the high humility, after in Constant Temperature and Humidity Chambers, carrying out high temperature and high humility keeping processing, in standard state (temperature: 20 ± 2 ℃, relative humidity: take out in the laboratory 65 ± 2%), and implemented tension test with interior at 30 minutes, estimate with respect to the strength retention of the intensity before handling by the intensity after handling then.In addition, for the keeping under hot and humid degree test, use big and the system Humidic Chamber 1G43M of science society, complete shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.Strength retention is by measuring the tensile strength before and after the keeping of hot and humid degree, is removed the tensile strength after the hot and humid degree keeping test and be multiply by 100 by the tensile strength before the hot and humid degree keeping test then and obtain.

(high temperature of braided fabric sample and the Evaluation of Durability method under the high humility)

For the high temperature of braided fabric sample and the Evaluation of Durability under the high humility, after in Constant Temperature and Humidity Chambers, sample being carried out the keeping of high temperature and high humility and handles, in standard state (temperature: 20 ± 2 ℃, relative humidity: take out in the laboratory 65 ± 2%), and implemented tension test with interior at 30 minutes, the tensile strength after being handled by high temperature and high humility keeping is then estimated with respect to the conservation rate of the tensile strength before handling.Handle for the keeping under the hot and humid degree, use big and the system Humidic Chamber 1G43M of science society, complete shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.The mensuration of the tensile strength of fabric is standard with JIS-L1096, in addition, compiles the mensuration of the tensile strength of thing, is standard with JIS-L1018, and (Shimadzu Seisakusho Ltd.'s system, pattern AG-50KNG) measures by cupping machine.

(preparation method of composite sample)

Batch fiber yarn not make its turn by level, after making the surface of its stainless steel rounding post that alternatively contacts 5 Φ 100mm then and opening fibre, contact has 1/4 curved punching block of the circle of radius 50mm, on the direction of advance of the fiber yarn that moves, inlet portion at curved punching block is provided with slit, and extrusion resin coated with resin on fiber, the fiber yarn that keeps tension force is moved on this curved surface and give and cut off opposing, thus impregnation resin.Afterwards, make impregnation the fiber yarn of resin through having the drawing-die of introduction part and spray nozzle part, obtained shaft-like composite after the cooling.Fig. 1 represents that resin contains an example of bath unit and drawing-die.As resin, use the Network ラレ of Co., Ltd. system ethylene-vinyl alcohol (ethylene vinyl alcohol) copolymer " エバ one Le (registration mark) " (105B), as drawing-die, use the drawing-die that imports 30 ° at angle, nozzle diameter Φ 0.6mm, parallel portion length 0.5mm.

(high temperature of textile strand and the Evaluation of Durability method under the high humility)

Under the situation that does not apply above-mentioned twisting processing, implemented the Evaluation of Durability of textile strand.With the textile strand circumvolution under the state of resin bobbin, in Constant Temperature and Humidity Chambers sample is carried out the keeping of high temperature and high humility and handle the back and take out, the tensile strength measured value of not implementing the textile strand that hot and humid degree keeping handles that obtains by implementing tension test under the room temperature is then removed the tensile strength measured value of implementing tension test under the room temperature and obtaining and be multiply by 100 and tried to achieve strength retention.In addition, handle for the keeping under the hot and humid degree, identical with the situation of long filament before the cutting, use big and the system HumidicChamber 1G43M of science society, fully shading is not so that allow light enter in the Constant Temperature and Humidity Chambers, and implemented 240 hours processing under 80 ℃, the condition of relative humidity 80%.The mensuration of tensile strength is standard with JIS-L1095, and (Shimadzu Seisakusho Ltd.'s system, pattern AG-50KNG) measures the yarn of the long 200mm of yarn by cupping machine.

(embodiment 1)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, has reacted 25 hours, 5 hours, 20 hours.In the intrinsic viscosity that the 2.0kg that obtains is measured by 30 ℃ methanesulfonic acid solution is poly-(two oxazoles to the phenylene benzo) (poly (p-phenylenebenzobisoxazole)) spinning solution of 29dL/g, add 14.8g intellectual circle (threne) and mix.

Afterwards, directly become under 11.5 μ m, the condition at 1.5 dawn, spin at the single thread long filament.Under 175 ℃ of temperature of spinning, after extruding spinning stoste and make long filament from the nozzle of aperture 0.18mm, hole count 166, bring together in position, be impregnated in the 1st rinse bath that disposes in the mode of making multifilament, and solidify.Air gap place between spinning jet nozzle and the 1st rinse bath is provided with quenching chamber, so that can elongate long filament with more uniform temperature.Hardening heat is made as 65 ℃.Afterwards, be washed to residual phosphorus concentration in the polybenzazole fiber, do not carry out drying and directly long filament has been batched on the resin bobbin smaller or equal to 5000ppm.In addition, coiling speed was made as 200m/ minute.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the polybenzazole fiber of said method acquisition, the result of na concn, and phosphorus concentration is 4600ppm, and na concn is 3600ppm, and the Na/P mol ratio is 1.05.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 86%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 87%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 89%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 87%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, make the textile strand of 20/1Ne, 2 of doubling twistings and obtained the doublet cord of 20/2Ne by cotton number by the polybenzazole fiber that obtains.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4220N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1660N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5850N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.29.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.3cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 84%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5600N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

(embodiment 2)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, has reacted 25 hours, 5 hours, 20 hours.In the intrinsic viscosity that the 2.0kg that obtains is measured by 30 ℃ methanesulfonic acid solution is poly-(two oxazoles to the phenylene benzo) spinning solution of 30dL/g, add the 14.8g copper phthalocyanine and mix.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 120 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the polybenzazole fiber of said method acquisition, the result of na concn, and phosphorus concentration is 4500ppm, and na concn is 2400ppm, and the Na/P mol ratio is 0.72.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 83%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 82%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 85%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 85%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4250N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1710N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 80%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 134g/m ²The tensile strength of vertical yarn direction is 5890N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 80%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 14.8cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 81%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5580N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 80%.

(embodiment 3)

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the polybenzazole fiber of said method acquisition, the result of na concn, and phosphorus concentration is 4400ppm, and na concn is 3600ppm, and the Na/P mol ratio is 1.10.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 88%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 90%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 91%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 90%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4250N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 87%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1670N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5800N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 87%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.8cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 85%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5620N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

(embodiment 4)

Afterwards, directly become under 11.5 μ m, the condition at 1.5 dawn (denier), spin at the single thread long filament.Under 175 ℃ of temperature of spinning, after extruding spinning stoste and make long filament from the nozzle of aperture 0.18mm, hole count 166, bring together in position, be impregnated in the 1st rinse bath that disposes in the mode of making multifilament, and solidify.Air gap place between spinning jet nozzle and the 1st rinse bath is provided with quenching chamber, so that can elongate long filament with more uniform temperature.Hardening heat is made as 65 ℃.Afterwards, be washed to residual phosphorus concentration in the polybenzazole fiber, do not carry out drying and directly long filament has been batched on the resin bobbin smaller or equal to 5000ppm.In addition, coiling speed was made as 200m/ minute.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 3 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the polybenzazole fiber of said method acquisition, the result of na concn, and phosphorus concentration is 4700ppm, and na concn is 5400ppm, and the Na/P mol ratio is 1.55.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 86%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 87%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 88%.

Also have,, make the staple (staple fiber) of coupe 51mm, be set at twist factor 3.5, make the textile strand of 20/1Ne, 2 of doubling twistings and obtained the doublet cord of 20/2Ne by cotton number by the polybenzazole fiber that obtains.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4190N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1660N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5700N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.1cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 84%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5550N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

(embodiment 5)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, has reacted 25 hours, 5 hours, 20 hours.In the intrinsic viscosity that the 2.0kg that obtains is measured by 30 ℃ methanesulfonic acid solution is poly-(two oxazoles to the phenylene benzo) spinning solution of 30dL/g, add the 4.4g copper phthalocyanine and mix.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4500ppm, and na concn is 4000ppm, and the Na/P mol ratio is 1.20.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 81%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 83%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 81%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4300N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1740N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 133g/m ²The tensile strength of vertical yarn direction is 5920N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 80%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.29.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 79%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 14.5cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 80%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 133g/m ²The tensile strength of vertical yarn direction is 5690N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 79%.

(embodiment 6)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, has reacted 25 hours, 5 hours, 20 hours.In the intrinsic viscosity that the 2.0kg that obtains is measured by 30 ℃ methanesulfonic acid solution is poly-(two oxazoles to the phenylene benzo) spinning solution of 30dL/g, add the 32.5g copper phthalocyanine and mix.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4400ppm, and na concn is 3400ppm, and the Na/P mol ratio is 1.04.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 87%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 89%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4010N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 87%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1590N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 138g/m ²The tensile strength of vertical yarn direction is 5610N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.31.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.5cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 85%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 138g/m ²The tensile strength of vertical yarn direction is 5280N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

(embodiment 7)

Under nitrogen current, in 2165.5g 122% polyphosphoric acid, add 334.5g 4,6-diamino-resorcinol dihydrochloride, 252.7g terephthalic acids, and after stirring 1 hour under 60 ℃, slowly heating up makes them respectively under 120 ℃, 135 ℃, 150 ℃, has reacted 4 hours, 20 hours, 5 hours.And then, after in this oligomer spinning solution, being added in the dispersion liquid that has added 5.6g terephthalic acids and 19.5g copper phthalocyanine in the 74.4g116% polyphosphoric acid, reacted 5 hours, 10 hours down at 170 ℃, 200 ℃ respectively, having obtained by the intrinsic viscosity that 30 ℃ methanesulfonic acid solution is measured is poly-(to the two oxazoles of phenylene benzo) spinning solution of 29dL/g.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 120 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4600ppm, and na concn is 2400ppm, and the Na/P mol ratio is 0.70.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 84%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 81%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 86%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 86%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4240N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1690N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5820N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.29.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 81%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.0cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 83%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5500N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 80%.

(embodiment 8)

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4900ppm, and na concn is 4200ppm, and the Na/P mol ratio is 1.15.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 89%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 88%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 92%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4210N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 88%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5780N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 89%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 16.0cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 86%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5480N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

(embodiment 9)

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 3 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4800ppm, and na concn is 5600ppm, and the Na/P mol ratio is 1.57.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 84%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4150N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1670N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5790N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 82%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.0cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 84%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5560N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

(embodiment 10)

Under nitrogen current, in 2165.5g 122% polyphosphoric acid, add 334.5g 4,6-diamino-resorcinol dihydrochloride, 252.7g terephthalic acids, and after stirring 1 hour under 60 ℃, slowly heating up makes them respectively under 120 ℃, 135 ℃, 150 ℃, has reacted 4 hours, 20 hours, 5 hours.And then, after in this oligomer spinning solution, being added in the dispersion liquid that has added 5.6g terephthalic acids and 5.6g copper phthalocyanine in the 74.4g116% polyphosphoric acid, reacted 5 hours, 10 hours down at 170 ℃, 200 ℃ respectively, having obtained by the intrinsic viscosity that 30 ℃ methanesulfonic acid solution is measured is poly-(to the two oxazoles of phenylene benzo) spinning solution of 30dL/g.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4500ppm, and na concn is 3800ppm, and the Na/P mol ratio is 1.14.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 82%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 82%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 84%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4380N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1760N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 6040N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 81%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 78%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 14.6cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 81%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 134g/m ²The tensile strength of vertical yarn direction is 5770N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 78%.

(embodiment 11)

Under nitrogen current, in 2165.5g 122% polyphosphoric acid, add 334.5g 4,6-diamino-resorcinol dihydrochloride, 252.7g terephthalic acids, and after stirring 1 hour under 60 ℃, slowly heating up makes them respectively under 120 ℃, 135 ℃, 150 ℃, has reacted 4 hours, 20 hours, 5 hours.And then, after in this oligomer spinning solution, being added in the dispersion liquid that has added 5.6g terephthalic acids and 41.1g copper phthalocyanine in the 74.4g116% polyphosphoric acid, reacted 5 hours, 10 hours down at 170 ℃, 200 ℃ respectively, having obtained by the intrinsic viscosity that 30 ℃ methanesulfonic acid solution is measured is poly-(to the two oxazoles of phenylene benzo) spinning solution of 28dL/g.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4800ppm, and na concn is 3900ppm, and the Na/P mol ratio is 1.09.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 88%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 89%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 3990N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1560N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 138g/m ²The tensile strength of vertical yarn direction is 5590N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 86%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.29.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 85%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 15.3cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 85%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 137g/m ²The tensile strength of vertical yarn direction is 5310N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

(embodiment 12)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 19.2g quinoline a word used for translation ketone, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, reacted 25 hours, 5 hours, 20 hours, having obtained by the intrinsic viscosity that 30 ℃ methanesulfonic acid solution is measured is poly-(to the two oxazoles of phenylene benzo) spinning solution of 24dL/g.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4900ppm, and na concn is 3900ppm, and the Na/P mol ratio is 1.07.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 85%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 83%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 84%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4120N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 84%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1610N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 83%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 136g/m ²The tensile strength of vertical yarn direction is 5830N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 81%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 135g/m ²The tensile strength of vertical yarn direction is 5500N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 82%.

(comparative example 1)

Under nitrogen current, under 60 ℃, with 334.5g 4,6-diamino-resorcinol dihydrochloride, 260.8g terephthalic acids, 2078.2g 122% polyphosphoric acid stirred after 1 hour, slowly heating up makes them respectively under 135 ℃, 150 ℃, 170 ℃, reacted 25 hours, 5 hours, 20 hours, having obtained by the intrinsic viscosity that 30 ℃ methanesulfonic acid solution is measured is poly-(to the two oxazoles of phenylene benzo) spinning solution of 30dL/g.

With 10 seconds of yarn that 1%NaOH aqueous solution neutralization is batched, washed for 15 seconds afterwards after, dry 4 hours down at 80 ℃.Mensuration is by the residual phosphorus concentration in the fiber of the silk of said method acquisition, the result of na concn, and phosphorus concentration is 4400ppm, and na concn is 4000ppm, and the Na/P mol ratio is 1.22.

By the result of the durability under said method evaluation high temperature and the high humility, strength retention is 77%.

The polybenzazole fiber of 6 acquisitions is not twisted and doubling, make the yarn at total dawn 1500, and made average 1 inch scrim that all inserts 5 these yarns on longitudinal direction and transverse direction.The scrim that obtains is clipped between 2 extension polyester films of 12 microns of thickness having smeared the polyamine esters sticker, solidifies drying and made canvas.The canvas sanction that obtains is the size of width 2.5cm, length 50cm, to comprise 5 reinforcing fibre yarns, estimates the result of the durability under high temperature and the high humility thus, strength retention is 76%.

Also have, to the polybenzazole fiber of 6 acquisitions, the turn that an edge Z direction applies 32T/10cm is on one side behind the doubling twisting, applies the turn of 32T/10cm with its 2 on plying and along the S direction, obtained natural flexible cord thus.Then, natural flexible cord is implemented two stage impregnation process, made dipping flexible cord (dip cord).The impregnation process liquid of phase I is the aqueous dispersions of epoxy resin, and treatment temperature is made as 240 ℃, and the impregnation process liquid of second stage is RFL liquid, and treatment temperature is made as 235 ℃.The high temperature and the durability under the high humility of the dipping flexible cord that obtains are 78%.

Also have, to the polybenzazole fiber of 12 acquisitions, while apply average 1m80 time turn doubling twisting, having obtained thickness is the also twist yarn at 3000 dawn.Adopt common device to 8 acquisitions and after twist yarn organizes into groups, made the rope of 8 knotting structures.The result of the durability under the hot and humid degree of the rope that evaluation obtains, strength retention is 78%.

The doublet cord that use to obtain has been made 2/1 TWILL CLOTH with 60 pieces/inch the radical that beats up on 68 pieces/inch, transverse direction on the longitudinal direction.The tensile strength of the longitudinal direction of the fabric that obtains is 4270N/3cm.Then, estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 72%.

And then, use the textile strand 20/1Ne of above-mentioned acquisition, made on the longitudinal direction the round fabric of 29 order/inches on 68 order/inches, the transverse direction.The tensile strength of the longitudinal direction of the round fabric that obtains is 1610N/5cm.Then, estimate the high temperature of the round fabric that obtains and the result of the durability under the high humility, strength retention is 70%.

Also have, use the polybenzazole fiber yarn that obtains, and use Rapier looms to be 60 pieces/inch the radical that beats up and made flat fabric with longitudinal and transverse all directions.The weight of the fabric that obtains is 134g/m ²The tensile strength of vertical yarn direction is 5780N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 73%.

Also have,, do not apply turn and pool capital and obtained the yarn at total dawn 1000 polybenzazole fiber of 4 acquisitions.The yarn that use to obtain, the preparation method of the composite sample by above-mentioned record has obtained composite.Fiber containing ratio in the composite that obtains is a percentage by volume 0.30.Also have, estimate the high temperature of the composite that obtains and the result of the durability under the high humility, strength retention is 73%.

Also have,, make the staple of coupe 51mm, be set at twist factor 3.5, made the textile strand of 20Ne by cotton number by the polybenzazole fiber that obtains.The tensile strength of the textile strand that obtains is 9.3cN/dtex.Also have, the strength retention after the long duration test under the high temperature of the textile strand of acquisition wets more is 75%.

Also have,, do not apply turn and pool capital and obtained the yarn of thickness 555dtex the polybenzazole fiber of 2 acquisitions.The yarn that use to obtain, and use Rapier looms to be 30 pieces/inch the radical that beats up with longitudinal and transverse all directions and made flat fabric.The weight of the fabric that obtains is 133g/m ²The tensile strength of vertical yarn direction is 5540N/3cm.Estimate the high temperature of the fabric that obtains and the result of the durability under the high humility, strength retention is 71%.

Above result is summarized in table 1～table 3.From these tables as can be known, compare the polybenzazole fiber of each embodiment and good by its article high temperature that constitutes and the durability under the high humility with comparative example.

[table 1]

	The kind of pigment	Polybenzazole fiber
		Polybenzazole fiber							Pigment containing ratio in the fiber	Early strength	CV	Phosphorus concentration in the fiber	Na concn in the fiber	The Na/P mol ratio	Evaluation of Durability result under high temperature and the high humility
		％	GPa	-	ppm	ppm	-	％	Pigment containing ratio in the fiber	Early strength	CV	Phosphorus concentration in the fiber	Na concn in the fiber	The Na/P mol ratio
		％	GPa	-	ppm	ppm	-	％	Embodiment 1	The intellectual circle	5.0	5.8	0.047	4600	3600	1.05	86
Embodiment 2	Copper phthalocyanine	5.0	5.9	0.036	4500	2400	0.72	83	Embodiment 1	The intellectual circle	5.0	5.8	0.047	4600	3600	1.05	86
Embodiment 2	Copper phthalocyanine	5.0	5.9	0.036	4500	2400	0.72	83	Embodiment 3	Copper phthalocyanine	5.0	5.9	0.034	4400	3600	1.10	88
Embodiment 4	Copper phthalocyanine	5.0	5.8	0.040	4700	5400	1.55	86	Embodiment 3	Copper phthalocyanine	5.0	5.9	0.034	4400	3600	1.10	88
Embodiment 4	Copper phthalocyanine	5.0	5.8	0.040	4700	5400	1.55	86	Embodiment 5	Copper phthalocyanine	1.5	6.0	0.047	4500	4000	1.20	81
Embodiment 6	Copper phthalocyanine	10	5.6	0.062	4400	3400	1.04	87	Embodiment 5	Copper phthalocyanine	1.5	6.0	0.047	4500	4000	1.20	81
Embodiment 6	Copper phthalocyanine	10	5.6	0.062	4400	3400	1.04	87	Embodiment 7	Copper phthalocyanine	5.0	5.9	0.057	4600	2400	0.70	84
Embodiment 8	Copper phthalocyanine	5.0	5.8	0.043	4900	4200	1.15	89	Embodiment 7	Copper phthalocyanine	5.0	5.9	0.057	4600	2400	0.70	84
Embodiment 8	Copper phthalocyanine	5.0	5.8	0.043	4900	4200	1.15	89	Embodiment 9	Copper phthalocyanine	5.0	5.8	0.039	4800	5600	1.57	86
Embodiment 10	Copper phthalocyanine	1.5	6.1	0.031	4500	3800	1.14	82	Embodiment 9	Copper phthalocyanine	5.0	5.8	0.039	4800	5600	1.57	86
Embodiment 10	Copper phthalocyanine	1.5	6.1	0.031	4500	3800	1.14	82	Embodiment 11	Copper phthalocyanine	10	5.5	0.059	4800	3900	1.09	87
Embodiment 12	Quinoline a word used for translation ketone	5.0	5.7	0.039	4900	3900	1.07	85	Embodiment 11	Copper phthalocyanine	10	5.5	0.059	4800	3900	1.09	87
Embodiment 12	Quinoline a word used for translation ketone	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]

	Canvas	The dipping flexible cord	The polybenzazole fiber rope	Polybenzazole fiber fabric (TWILL CLOTH)		Polybenzazole fiber is compiled thing (round volume thing)		Polybenzazole fiber fabric (flat fabric, knifeproof material purposes)
	Canvas	The dipping flexible cord	The polybenzazole fiber rope	Polybenzazole fiber fabric (TWILL CLOTH)		Polybenzazole fiber is compiled thing (round volume thing)					Durability	Durability	Durability	The fabric rerum natura	Durability	Compile the thing rerum natura	Durability	The fabric rerum natura	Order is paid	Durability
	％	％	％	N/3cm	％	N/5cm	％	N/3cm	g/m ²	％	Durability	Durability	Durability	The fabric rerum natura	Durability	Compile the thing rerum natura	Durability	The fabric rerum natura	Order is paid	Durability
	％	％	％	N/3cm	％	N/5cm	％	N/3cm	g/m ²	％	Embodiment 1	87	89	87	4220	86	1660	85	5850	135	84
Embodiment 2	82	85	85	4250	82	1710	80	5890	134	82	Embodiment 1	87	89	87	4220	86	1660	85	5850	135	84
Embodiment 2	82	85	85	4250	82	1710	80	5890	134	82	Embodiment 3	90	91	90	4250	87	1670	85	5800	136	86
Embodiment 4	86	87	88	4190	84	1660	83	5700	135	83	Embodiment 3	90	91	90	4250	87	1670	85	5800	136	86
Embodiment 4	86	87	88	4190	84	1660	83	5700	135	83	Embodiment 5	82	83	81	4300	83	1740	83	5920	133	80
Embodiment 6	89	85	88	4010	87	1590	85	5610	138	86	Embodiment 5	82	83	81	4300	83	1740	83	5920	133	80
Embodiment 6	89	85	88	4010	87	1590	85	5610	138	86	Embodiment 7	81	86	86	4240	83	1690	82	5820	136	82
Embodiment 8	88	91	92	4210	88	1660	85	5780	135	86	Embodiment 7	81	86	86	4240	83	1690	82	5820	136	82
Embodiment 8	88	91	92	4210	88	1660	85	5780	135	86	Embodiment 9	84	86	88	4150	85	1670	83	5790	136	82
Embodiment 10	81	82	84	4380	82	1760	83	6040	135	81	Embodiment 9	84	86	88	4150	85	1670	83	5790	136	82
Embodiment 10	81	82	84	4380	82	1760	83	6040	135	81	Embodiment 11	87	88	89	3990	86	1560	85	5590	138	86
Embodiment 12	83	84	87	4120	84	1610	83	5830	136	81	Embodiment 11	87	88	89	3990	86	1560	85	5590	138	86
Embodiment 12	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]

	Composite		The polybenzazole fiber textiles		Polybenzazole fiber fabric (flat fabric, bullet-proof vest purposes)
	Composite		The polybenzazole fiber textiles					Fiber containing ratio in the composite	Durability	Early strength	Durability	The fabric rerum natura	Order is paid	Durability
	Volume fraction	％	cN/dtex	％	N/3cm	g/m ²	％	Fiber containing ratio in the composite	Durability	Early strength	Durability	The fabric rerum natura	Order is paid	Durability
	Volume fraction	％	cN/dtex	％	N/3cm	g/m ²	％	Embodiment 1	0.29	82	15.3	84	5600	135	83
Embodiment 2	0.30	80	14.8	81	5580	136	80	Embodiment 1	0.29	82	15.3	84	5600	135	83
Embodiment 2	0.30	80	14.8	81	5580	136	80	Embodiment 3	0.30	87	15.8	85	5620	135	85
Embodiment 4	0.30	83	15.1	84	5550	136	82	Embodiment 3	0.30	87	15.8	85	5620	135	85
Embodiment 4	0.30	83	15.1	84	5550	136	82	Embodiment 5	0.29	79	14.5	80	5690	133	79
Embodiment 6	0.31	85	15.5	85	5280	138	84	Embodiment 5	0.29	79	14.5	80	5690	133	79
Embodiment 6	0.31	85	15.5	85	5280	138	84	Embodiment 7	0.29	81	15	83	5500	135	80
Embodiment 8	0.30	89	16	86	5480	136	84	Embodiment 7	0.29	81	15	83	5500	135	80
Embodiment 8	0.30	89	16	86	5480	136	84	Embodiment 9	0.30	82	15	84	5560	135	82
Embodiment 10	0.30	78	14.6	81	5770	134	78	Embodiment 9	0.30	82	15	84	5560	135	82
Embodiment 10	0.30	78	14.6	81	5770	134	78	Embodiment 11	0.29	85	15.3	85	5310	137	84
Embodiment 12	0.30	82	15	84	5500	135	82	Embodiment 11	0.29	85	15.3	85	5310	137	84
Embodiment 12	0.30	82	15	84	5500	135	82	Comparative example 1	0.30	73	9.3	75	5540	133	61

(industrial utilizability)

According to the present invention, produce after the knot group even can provide on the yarn, be exposed to high temperature and high humility following time for a long time, also can fully keep the polybenzazole fiber of intensity.Therefore, by using this fiber, can improve the purposes that is processed as fabric, compiles thing, braid, rope, flexible cord etc., promptly, cable, electric wire or fiber optics isostension element, stretching materials such as rope, the shock-resistant parts of using such as the material of anti-the bullet, anti-wound parts such as gloves, the practicality of rubber armatures such as belt, tire, sole, rope, flexible pipe etc.

Claims

1, a kind of polybenzazole fiber is characterized in that,

By the value of the strength retention (%) of (a/b) * 100 definition more than or equal to 80%,

2, polybenzazole fiber according to claim 1 is characterized in that,

The average diameter D of single thread is 5～22 μ m, and the mean intensity when measuring with the long 100mm of fiber is more than or equal to 4.5GPa.

3, polybenzazole fiber according to claim 1 is characterized in that,

4, polybenzazole fiber according to claim 1 is characterized in that,

5, polybenzazole fiber according to claim 1 is characterized in that,

6, polybenzazole fiber according to claim 5 is characterized in that,