CN85100423A - Poly-adipoyl with high dimensional stability and high antifatigue is diamines (polyamide six or six) fiber and preparation method thereof - Google Patents
Poly-adipoyl with high dimensional stability and high antifatigue is diamines (polyamide six or six) fiber and preparation method thereof Download PDFInfo
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- CN85100423A CN85100423A CN85100423.7A CN85100423A CN85100423A CN 85100423 A CN85100423 A CN 85100423A CN 85100423 A CN85100423 A CN 85100423A CN 85100423 A CN85100423 A CN 85100423A
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Abstract
Poly-adipoyl diamines fiber has formyl relative viscosity 50～150; Tensile strength is 7.5g/d at least; Middle elongation is not more than 8% under 5.3g/d stress; Extension at break and middle elongation difference are under 5.3g/d stress at least 6%; Be not more than 5% under 160 ℃ of dry heat conditions of shrinkage factor, elongation is 12～20%; Dimensional stability is not more than 13%; Crystal orientation degree at least 0.85 is not more than 0.92; The perfect index at least 60% of crystal.The poly-adipoyl of its preparation fusion is diamines; Extrude from spinnerets, cooling extruded thing also solidifies; 1,000～6, the long yarn of coiling gained under the 000m/min coiling speed; Be not more than this filament yarn of hot-drawn under the draw speed of 100m/min.
Description
Background of invention
(1) scope of invention
The present invention relates to poly fibre (polyamide 66) and preparation method thereof.Especially, it relates to polyhexamethylene adipamide (polyamide 66) fiber with high dimensional stability and high antifatigue and preparation method thereof, and this fiber adopts makes tyre cord, conveyer belt or suchlike rubber stiffener.
(2) description of previous technology
Because poly fibre has splendid tensile strength, toughness, heat resistance, dyeability and staining property, it is widely used as being industrial materials, indoor bedding material, clothing fiber and the like.Especially, because it has splendid tensile strength, toughness, fatigue resistance and to the adhesivity of rubber, it is widely used as a kind of fiber into ratch tire cord.
Recently, even aspect tyre cord, also earnestly hope and reach energy-saving effect, and require to develop the tire that can reduce automobile fuel consumption, for this reason, the tyreman exhausts effort, has less resistance to rolling and the lighter tire of weight to provide.Therefore, wish to have chemical-fibres filaments yarn, in order to produce tyre cord with higher dimensional stability and higher tensile strength.The durability of improving tire is necessary, and this is not only in order to obtain economic effect by life of tire, and is in order to improve security, from this viewpoint, wishes to have the chemical-fibres filaments yarn with high fatigue resistance.
Nylon 66(polyamide 66) fiber surpasses nylon 6 aspect heat resistance and dimensional stability, and also surpasses polyethylene terephthalate (polyester) fiber aspect heat resistance, and especially heat resistance under high humidity and anti-amine decomposability are all the more so.Yet the shortcoming of nylon 66 fiber is that this fiber is inferior to pet fiber aspect dimensional stability.For this reason, in the occasion of radial ply tire, requiring has preferable dimensional stability, thereby mainly uses steel wire, pet fiber and artificial fibre.Because steel wire and artificial fibre are being low aspect the tensile strength of per unit weight,, consequently improved the weight and the cost of tire so must improve the amount of the used cord of each tire.Pet fiber is aspect heat resistance, especially be inferior aspect the heat resistance under high humidity, therefore, pet fiber just is restricted at truck or doughnut and in the application aspect the high high-speed tire of operating temperature.In this case, the dimensional stability with regard to an urgent demand improvement nylon 66 keeps its excellent characteristic, for example high tensile strength, high heat resistance and high fatigue resistance simultaneously again.
In " Japanese unexamined patent publication " NO53-58032, revealed a kind of in order to the dimensional stability of improvement plyester filament yarn yarn and the method for fatigue resistance.In the method, mainly the polyester of being made up of the polyethylene terephthalate carries out melt spinning under heavily stressed, and the filament yarn that does not stretch that produces like this has a quite high birefringence, and its value is 9 * 10
-3To 70 * 10
-3, and then carry out hot-stretch.Adopt the coiling speed of the speed of 1000 * 2000 meters of per minutes as coiling undrawn filament yarn.Above-mentioned do not authorize patent publications promulgation after, done various investigation improve dimensional stability and fatigue resistance so that the chemical-fibres filaments yarn by high melt spinning stretches.With regard to poly fibre, " Japanese unexamined patent publication " NO58-60012 has revealed a method, comprising: polyhexamethylene adipamide is carried out melt spinning; Filament yarn to spinning is reeled with the coiling speed that is higher than 2,000 meters of per minutes; Then filament yarn is stretched.Yet if by improving the degree of orientation that spinning speed improves filament yarn, tensility will variation so.In the polyhexamethylene adipamide with very high crystallization velocity, this trend is particularly evident.Therefore, the shortcoming of polyhexamethylene adipamide is, spinning speed is high more, and then the tensile strength and the elongation of the stretched filament yarn of gained are just low more.The inherent function of tyre cord has been a humidification, if the tensile strength of tyre cord and elongation reduce, then must need to increase the amount of filament yarn used in the tire, consequently certainly will increase the weight of tire and improve manufacturing cost.
Abstract of invention
Therefore, main purpose of the present invention is to give poly fibre with good tensile strength, elongation, dimensional stability and fatigue resistance.
Other purpose advantages of the present invention can be seen from following introduction apparently.
According to a basic demand of the present invention, a kind of poly fibre is provided, be characterized in: (1) formic acid relative viscosity is 50～150; (2) tensile strength is at least the 7.5g/d(gram/dawn); (3) be the 5.3g/d(gram/dawn at stress) condition under, middle elongation is not more than 8%; (4) be the 5.3g/d(gram/dawn at stress) condition under, the difference between extension at break (%) and the middle elongation (%) is at least 6%; And (5) under 160 ℃ dry heat condition, and shrinkage factor is not more than 5%.
Preferred poly fibre has more following characteristic: (6) elongation is 12% to 20%; (7) dimensional stability is not more than 13%; (8) the crystal orientation degree is at least 0.85, but is not more than 0.92; (9) the perfect index of crystal (CPI) is at least 60%; And (10) are that 110 Hz(are conspicuous in frequency) time dynamic mechanically loss tangent (tan) that records peak temperature Tmax, can satisfy the following formula requirement:
100≤T max+4（9.5-DS）≤116
In the formula, DS is tensile strength (g/d).
According to another basic demand of the present invention, provide one in order to prepare the method for poly fibre, it comprises: making the formic acid relative viscosity is 50～150 polyhexamethylene adipamide fusion; Melt is extruded from a spinnerets; Make extrudate cooling and solidify thus, with the filament yarn of the coiling speed coiling gained of 1000 meters to 6,000 meters of per minutes; Be not higher than 100 meters draw speed with per minute then filament yarn is carried out hot-stretch.
The simple description that stretches
Fig. 1 is the schematic diagram of a typical melt spinning device, and this device is used for producing the unstretched filament yarn of polyhexamethylene adipamide according to the present invention;
Fig. 2 is a hot-stretch schematic representation of apparatus, is to be used for carrying out once step stretching;
Fig. 3 is a hot-stretch schematic representation of apparatus, is to be used for carrying out the stretching of two steps; And Fig. 4 is the profile of non-direct contact heater.
The preferred description of specializing
Polyhexamethylene adipamide used among the present invention mainly is made up of the repetitive of following chemical structural formula:
Also can use in the present invention the polyhexamethylene adipamide of modification, it is modification by incorporating by weight other moulding amide units of 10% into as the part of repetitive and in addition. With regard to regard to this moulding acid amides component of incorporating on a small quantity, can enumerate: such as decanedioic acid and these aliphatic dicarboxylic acids of dodecoic acid; Such as terephalic acid and these aromatic dicarboxylic acids of isophathalic acid; Such as these aliphatic diamines of decane diamines, such as its these aromatic diamines of xyxylene diamines, such as these omega-amino-carboxylic acids of EACA, and such as caprolactam and these aromatics lactams of lauryl lactam. In addition, also can use poly hexamethylene adipamide The admixture of hexamethylene diamine and 20% other polyamide (for example polycaprolactam or polyhexamethylene sebacamide) by weight.
In addition, in above-mentioned polyhexamethylene adipamide, also can incorporate conventional additives into, for example, such as Schweinfurt green, copper chloride, cupric iodide and these copper compounds of 2-mercaptobenzimidazole one copper complex, such as 2-mercaptobenzimidazole and four-[methyl-3-(3,5-two-tertiary butyl-4-hydroxyl-phenyl)-propionamido-]-these heat stabilizers of methane, such as manganese lactate and these light stabilizers of manganese hypophosphite, such as phosphoric acid, these thickeners of benzenephosphonic acid and sodium pyrophosphate, such as titanium dioxide and these delustering agents of kaolin, such as ethene-two-hard acid amides and these lubricants of calcium stearate, and plasticizer.
The formic acid relative viscosity of used polyhexamethylene adipamide should be 50 to 150 among the present invention, and this is necessary. Said " formic acid relative viscosity " this term refers to polymer dissolution in 90% formic acid in addition, concentration be 8.4%(by weight), the relative viscosity of formed solution when temperature is 25 ℃. If the formic acid relative viscosity is lower than 50, the fatigue resistance of so resulting poly fibre then is very inferior. If the formic acid relative viscosity surpasses 150, tensility then is low so, thereby can not obtain to have the initial chemical fibre filament yarn of sufficient intensity, and dimensional stability also is low. It is desirable to, the formic acid relative viscosity of polyhexamethylene adipamide should be 60 to 100.
Above-mentioned polymer after drying its water content is not more than 0.1%, adopt then a kind of extruder type spinning machine to carry out melt spinning, perhaps will enter a spinneret through being guided through a conduit by the molten polymer that the continuous polymerization effect obtains, polymer is able to direct fabrics whereby. In this spinning stage, preferably 270 ℃ to 320 ℃ of the temperature of melt. Extrudate is cooled off by cold air, and is solidified whereby, it is applied to finish again. The chemical-fibres filaments yarn is reeled by a takers-in, and then carries out the package of coiled one shaping type. Impose on after the finish, the chemical-fibres filaments yarn can be directly on bobbin-winding machine, and needn't make Use takers-in.
Winding speed should be 1,000 meter to 6,000 meters of per minute, and this is necessary. If winding speed is lower than 1,000 meter of per minute, the improvement of the fatigue resistance of the fiber of drawn and dimensional stability then is little so. If winding speed surpasses 6,000 meters of per minutes, the strength and elongation of the chemical-fibres filaments yarn of drawn then is low so. Preferably, winding speed should not be higher than 5,000 meters of per minutes.
With regard to poly fibre, if spinning speed is about about 600 meters to 4,000 meters of per minutes, the chemical-fibres filaments yarn through reeling will extend because of moisture absorption so, so normal the coiling just can not be carried out. Correspondingly, if winding speed is per minute 1,000 meter to 4,000 meters, so just should take so a kind of method: in this method, chemical-fibres filaments yarn through cooling carries out steam shaping, reel then, perhaps take so a kind of method: in this method, the filament yarn of spinning is reeled by takers-in, between takers-in and roller thereafter, stretch to be not more than 2.0 draw ratio then, and then reel.
If winding speed surpasses per minute 4,500 meters, winding tension will improve so, and because the contraction of chemical-fibres filaments yarn, paper bobbin can not take out from up-coiler, perhaps swells in this part of the bobbin end face of the approaching yarn of having reeled of limit yarn meeting, if winding speed surpasses per minute 5,000 meter, so this trend is particularly evident.In this occasion, be necessary to take a kind of like this method: in this method, the filament yarn of spinning is reeled by work beam, so yarn just can relax 18% between work beam and roller thereafter, and then reels.
In the method for the invention, preferably, before the stretching operation, the birefringence of the unstretched polyhexamethylene adipamide filament yarn of high orientation is 20 * 10
-3To 50 * 10
-3If this birefringence is less than 20 * 10
-3, the improvement of the fatigue resistance of the fiber of drawn and dimensional stability then is little so.If this birefringence surpasses 50 * 10
-3, the intensity that shows is not enough, yet, can adopt drawing process by the present invention's design.Particularly it is desirable to, above-mentioned birefringence should be 25 * 10
-3To 45 * 10
-3
When the unstretched filament yarn with big fiber number (for example tyre cord) was stretched, adopting per minute on general draw roll in the end was the draw speed of hundreds of rice to several kms.Improve draw speed and can cause boosting productivity, and recently, owing to adopt direct spinning stretching technology, draw speed has been brought up to the degree of several kms of per minute.Yet, our result of study, have found that: when high directed not stretched chemical-fibres filaments yarn is stretched, draw speed is for the influence that physical characteristic produced of the chemical-fibres filaments yarn of drawn, and the influence that is produced when stretching more than the unstretched chemical-fibres filaments yarn for low orientation is much serious.In order to obtain fiber of the presently claimed invention, be necessary to accomplish: the draw speed on last draw roll should not be higher than 100 meters of per minutes, if draw speed surpasses this critical value, intensity that fiber showed that is obtained and elongation then are not enough so, and its fatigue resistance and dimensional stability also descend.Particularly it is desirable to, draw speed should not be higher than 50 meters of per minutes.
If draw speed is too low,, can't produce what defective, but productivity ratio is restricted widely with regard to the physical characteristic of fiber.Therefore, from practical perspective, draw speed should be 2 meters of per minutes at least.
In the present invention, promptly can adopt single-stage to stretch, also can adopt multistage stretching (comprising secondary at least).Recently, in the production of the high tenacity chemical-fibres filaments yarn of using for tyre cord, adopted multistage stretching, to obtain the chemical-fibres filaments yarn of high tenacity.According to technology of the present invention, by the chemical-fibres filaments yarn that adopts single-stage to stretch and to obtain to have enough toughness, fatigue resistance and dimensional stability.If adopt single-stage to stretch, equipment just can be simplified, and can reach energy-saving effect.
With regard to draw roll device used among the present invention, what deserves to be mentioned is: the Nelson that comprises two pairs of active type driven vollers rolls plainly-packed putting; Comprise the stretching device of several active type driven vollers and several free roller combinations, and comprise 5 drum apparatus to 9 active type driven vollers, this drum apparatus is generally used for short fibre yarn or mono filament yarn.
Preferably before draw roll, arrange a feeding roller so that on filament yarn to be stretched, apply a tension force, and preferably between feeding roller and draw roll, give filament yarn with one less than 5% extension.Certainly, also can adopt such method: in the method, can arrange three grades or more multistage draw roll, and can between first order draw roll and second level draw roll, obtain one and be lower than 5% extension.
First order draw roll preferably reaches mirror finish, the second level and thereafter what draw roll preferably have one and be not more than the bright finished surface of 10S or the surface of unglazed (hair side) fineness, in addition, the surface of bright finished surface and unglazed frosted finish can alternately be arranged in the second level and thereafter on what the draw roll.The Nelson drum apparatus or comprise several active type driven vollers and the situation of the drum apparatus of several free roller combination under, the chemical-fibres filaments yarn is wound onto and reaches 2 circles on the draw roll to 7 circles.On bright finished roller, the number of turns may be little, and on the roller of unglazed frosted finish, along with the increase of roughness, the number of turns also improves thereupon.Can adopt the number of turns, but in this occasion, the length of roller will increase, thereby this technology just seems not conform to and lets it pass economically greater than 7 circles.
In general, draw roll should maintain under the temperature conditions that is higher than room temperature.In being used for to high conventional process directed, that unstretched chemical-fibres filaments yarn stretches, NO58-60012 revealed as " Japanese unexamined patent publication ", first draw roll maintains 80 ℃ to 150 ℃, and second draw roll maintains 160 ℃ to 240 ℃.Certainly, in the present invention, also can adopt these temperature for these draw rolls, but in the present invention,, still can finish the stretching operation reposefully even draw roll maintains room temperature, and not having any fault, its condition is the heater that needs to use a chemical-fibres filaments yarn.Therefore, equipment can be simplified, and can reach energy-saving effect.
In desirable technology of the present invention, the heater of chemical-fibres filaments yarn is arranged between the draw roll, to reach the purpose of hot-stretch.The heater of chemical-fibres filaments yarn can be a contact, also can be contactless.With regard to the contact heating, the temperature of heater should be 180 ℃ to 260 ℃; With regard to contactless heating, the temperature of heater should be 200 ℃ to 280 ℃.
Under the contact heating state,, just can not finish sufficient stretching if the temperature of heater block is lower than 180 ℃; And if the temperature of heater block is higher than 260 ℃, then can cause the broken end of chemical-fibres filaments yarn owing to fusion.Under contactless heating state,, just can not finish sufficient stretching if the temperature of heater block is lower than 200 ℃; And if the temperature of heater is to be higher than 280 ℃, then can cause the broken end of chemical-fibres filaments yarn owing to fusion.Usually, often utilize the heater of hot plate as the chemical-fibres filaments yarn, in conventional process, the temperature maintenance of hot plate is at 180～220 ℃.For example, in the method that " Japanese unexamined patent publication " № 58-60012 is revealed, be to adopt from 150 ℃ to 210 ℃ the temperature in the scope.Equally, in the present invention, if under the occasion of contact heating, can adopt 180～230 ℃ temperature; Under the occasion of contactless heating, can adopt 200～240 ℃ temperature.Yet,,, preferably adopt higher temperature for the heater of chemical-fibres filaments yarn in order to obtain a kind of have higher strength and elongation and higher dimensional stability.Just, under contact heating occasion, preferentially select 230～255 ℃ temperature for use; And under the occasion of contactless heating, preferentially select 240～275 ℃ temperature for use.If the temperature of the heater of contact chemical-fibres filaments yarn raises, by being coated in that finishing agent on the chemical-fibres filaments yarn is derived and the tarry matters that comes will promptly be deposited on the heater of chemical-fibres filaments yarn.Therefore, correspondingly had better adopt contactless heating.
A concrete device of preferentially selecting for use of the inventive method is existing by being described it with reference to the accompanying drawings.Fig. 1 illustrates the melt spinning step.Fig. 2 illustrates the stretching step of once step stretching method.Fig. 3 illustrates the stretching step of two step extensions.Certainly, scope of the present invention is not subjected to the limitation of illustrational concrete device in the accompanying drawings.
With reference to Fig. 1; fusion polyhexamethylene adipamide (polyamide 66) is extruded from a spinnerets with many meticulous spinneret orifices (or head, cap) 1, and by a protective atmosphere (this protective atmosphere is maintained under the temperature of being adjusted by the heating drying cylinder 2 that is configured under the spinnerets).Then, extrudate is cooled off with the cold air that constant rate of speed blows out from a cold air chamber 3, thereby and must solidify, then, by steam 4 setting that are blown into the steam conditioning device.Apply a kind of finishing agent for shaping chemical fibre gauze by an oiling roller 6.The chemical-fibres filaments yarn that is shaped is reeled by work beam 7, and makes it the do not stretch package 9 of chemical-fibres filaments yarn pattern of coiled by bobbin winder 8.
The package 9 of the chemical-fibres filaments yarn pattern that do not stretch of coiled supplies to a stretching heat-treating machine as employed initial chemical fibre filament yarn in the stretching step as shown in Figure 2 like this.From the chemical-fibres filaments yarn package that do not stretch be fed to a feeding roller 10 from the loose chemical-fibres filaments yarn of reeling condition, and between feeding roller 10 and first draw roll (drawing rollers) 11, give of the extension of chemical-fibres filaments yarn with a few percent.The heater 12 of a chemical-fibres filaments yarn is to be arranged between first draw roll 11 and second draw roll 13, the chemical-fibres filaments yarn then carries out hot-stretch between first draw roll 11 and second draw roll 13, and then stretched the package 14 of chemical-fibres filaments yarn pattern of coiled.
In addition, the do not stretch package 9 of chemical-fibres filaments yarn pattern is fed to a stretching heat-treating machine equally as the initial chemical fibre filament yarn that uses in the stretching step as shown in Figure 3.From the package 9 of the chemical-fibres filaments yarn pattern that do not stretch be fed to a feeding roller 10 from the loose chemical-fibres filaments yarn of reeling condition, and between the feeding roller 10 and first draw roll 11, give of the extension of chemical-fibres filaments yarn with a few percent.The heater 12 of a chemical-fibres filaments yarn is to be arranged between first draw roll 11 and second draw roll 13, and the heater 15 of another chemical-fibres filaments yarn is arranged is between second draw roll 13 and the 3rd draw roll 16 that is arranged.The chemical-fibres filaments yarn carried out for two steps and has stretched between first draw roll and second draw roll and second draw roll and the 3rd draw roll, chemical-fibres filaments yarn stretched the package 14 of chemical-fibres filaments yarn pattern of coiled more then.In concrete device shown in Figure 3, the chemical-fibres filaments yarn can be heat-treated with the relaxation rate up to 15% between second draw roll and the 3rd draw roll.Figure 4 shows that the profile of a contactless heater.When the chemical-fibres filaments yarn by one by heater 17 and thermal insulation part 19 round chemical-fibres filaments yarn groove 18 time, the chemical-fibres filaments yarn is heated.
Polyhexamethylene adipamide (polyamide 66) fiber according to method for preparing has following properties: (1) formic acid relative viscosity is 50～150; (2) tensile strength is at least the 7.5g/d(gram/dawn), be generally the 7.5g/d(gram/dawn) to the 10.5g/d(gram/dawn); (3) at the 5.3g/d(gram/dawn) under the stress, middle elongation is no more than 8%, is about 6% to 8% usually; (4) poor between extension at break (%) and the middle elongation (%) is at the 5.3g/d(gram/dawn) under the stress, be at least 6%, be generally 6% to about 10%; (5) under 160 ℃ of dry heat conditions, shrinkage factor is no more than 5%, is generally about 2% to 5%.Preferably, this fiber and have following characteristic; (6) dimensional stability is not more than 13%; (7) elongation is 12% to 20%; (8) perfect index (CPT) bottom line of crystal is 60%, is generally 60% to about 80%; (9) the crystal orientation degree is at least 0.85, but is not more than 0.92; (10) peak temperature (Tmax) of dynamic mechanically loss tangent (tan δ), conspicuous at 110 Hz() when measuring under the frequency, can satisfy the requirement of following formula:
100≤T max+4（9.5-D S）≤116
DS represents tensile strength (g/d) in the formula.
The formic acid relative viscosity be 25 ℃ for a measured relative viscosity of polymer solution, the compound method of this polymer solution be with concentration be 8.4%(by weight) polymer dissolution in 90% formic acid.Each tensile strength, elongation and middle elongation all utilize an automatic recording type tester [S-100 type, provide by Tianjin, island company (shimazu Corp)] measure, the length of selecting the chemical-fibres filaments yarn during measurement for use is 25cm(centimetre), if ball speed is the 30cm/min(cm per minute), record-paper speed is the 60cm/min(cm per minute), the amount of twist of sample chemical-fibres filaments yarn is every meter twisting count of 80T/m(), the damping in advance 24 hours in the humiture conditioning chamber that keeps 20 ℃ of temperature and 65% relative temperature of sample chemical-fibres filaments yarn.The shrinkage factor (constriction coefficient) of sample chemical-fibres filaments yarn is measured at dry heat condition, the damping in advance 24 hours in the humiture conditioning chamber that keeps 20 ℃ of temperature and 65% relative humidity of sample chemical-fibres filaments yarn, the sample chemical-fibres filaments yarn of continuing to employ 1.0 meters [being equivalent in load (initial load) record under the condition of every DENIER sample chemical-fibres filaments yarn 1/20 gram], and it was remained in 160 ℃ the air drying cabinet free shrink 30 minutes at one, in above-mentioned humiture conditioning chamber, make sample chemical-fibres filaments yarn damping 4 hours again, and as the same load of initial load under the length of working sample chemical-fibres filaments yarn.
Dimensional stability (DIMENSIONAL STABILITY) is by 5.3g/d(per dawn gram number) down in the middle of extend and 160 ℃ dry heat condition under the shrinkage factor sum express.
The crystal orientation degree is by using the Cu Ka ray in the wide-angle X-ray scattering instrument [(Rigaku Denki) provides by electric corporation of science] to measure, and from along equatorial line (1,0,0) in H ° of the intensity distributions half breadth of debye ring, calculated according to following fraction:
fc＝ (180°-H°)/(180°)
The mensuration of the perfect index of crystal is for the Cu Ka that helps use in the wide-angle X-ray scattering instrument [(Rigaku Denki) provides by electric corporation of science]
αRay, and from the intercrystalline of crystal face (1,0,0) and crystal face [(0,1,0)+(1,1,0)] every d(100) intercrystalline is every d[(010)+(110)], calculate according to following formula:
(d（100）/d[（010）+（110）]-1)/0.189 ×100（%）
Temperature T max is the peak temperature of dynamic mechanically loss tangent (tam δ), be the Wei Bailong vibration gauge DDV-IIC(Vibron DDV-IIC that provides by by Japan one Baldwin company (To Yo Baldwin)), be that 110 Hz(are conspicuous in frequency) and programming rate be to measure in 3 ℃/minute the dry air.
Though polyhexamethylene adipamide of the present invention (polyamide 66) fiber is at the 5.3g/d(gram/dawn) constant stress under have low elongation (under the 5.3g/d stress in the middle of elongation) and high rigidity, the shrinkage factor of fiber is low.Correspondingly, fiber of the present invention has high dimensional stability.In addition, although fiber of the present invention has low middle elongation, extension at break is high, and energy to failure is big.The crystal orientation degree of fiber of the present invention is not different with habitual chemical fibre silk in fact, but the perfect index of the crystal of fiber of the present invention is high, and amorphous area (amorphous region) is loose, and can move easily.A factor of indication amorphous area mobility is peak temperature Tmax, and it is upheld by fiber and is changed, and for this reason, peak temperature should be revised according to tensile strength, so that understand the mobility of fiber inherence.Correction is every g/d(gram/dawn) 4 ℃ of tensile strengths.
Fiber of the present invention is at aspects such as dimensional stability, fatigue resistance, tensile strength and elongations, all than comparatively good by the performance of the habitual chemical-fibres filaments yarn of the chemical-fibres filaments yarn drawn gained that do not stretch that is spun at a high speed to the thousands of meters speed at the hundreds of rice of per minute.
For this reason, this fiber can be used for doing tyre cord or conveyer belt.
The present invention will consult following example now and be described in detail, and these examples and not meaning that limit the scope of the invention.
The performance of having handled cord is without every meter twisting count of 80T/m() twisting, under situation, measure as the initial chemical fibre filament yarn performance of mensuration.In the occasion of initial chemical fibre filament yarn, middle elongation is at the 5.3g/d(gram/dawn) measure down; But in the occasion of handling cord, middle elongation is at the 2.65g/d(gram/dawn) measure down.Fatigue resistance is by measuring under following condition according to the method for the 3.2.2.1 A joint of the L-1017 of Japanese Industrial Standards (J I S) because of special pipe fatigue test (Goodyear tube fat ique test).
Cast:
Internal diameter: the 12.5mm(millimeter)
External diameter: the 26mm(millimeter)
Length: the 230mm(millimeter)
Bent angle: 90 °
The interior pressure: 3.5kg/cm
2The G(kilograms per centimeter
2Gauge pressure)
Revolution: 850rpm(rev/min)
The fatigue strength test is carried out under these conditions, and records the required time of tracheal rupture.
Example 1
The aqueous solution of 50% hexamethylene adipamide diamines is with 2000 parts constant rate of speed feed per hour, and is condensed to 70% in a thickener.In first reactor, in 1.5 hours time, make temperature rise to 250 ℃ from 220 ℃, and the reaction vessel internal pressure remain on the 17.51kg/cm(kilograms per centimeter).Secondly, in second reaction vessel, pressure is returned to atmospheric pressure when temperature is elevated to 280 ℃.Water vapour is separated in vapour one liquid/gas separator, and polymerisation in polymeric kettle in 280 ℃ of temperature and 350mm Hg(millimetres of mercury) carried out 15 minutes under the pressure.Reactant mixture is directed to a spinneret, by a conduit, is spun into silk from a spinnerets [having 624 diameters is the 0.27mm(millimeter) pore] in 298 ℃.The formic acid relative viscosity of extrudate is 65.And then, extrudate is cooled, and uses steam treatment, is coated on the chemical-fibres filaments yarn to finish a kind of then, and the chemical-fibres filaments yarn is wound onto with on the work beam that rotates under the coiling speed shown in the table 1, and bobbin package under the speed same as coiling speed.Then, the chemical-fibres filaments yarn of La Shening does not uphold 1% being maintained at the feeding roller under the room temperature and being maintained between first draw roll under the room temperature, then stretches by the draw ratio shown in the table 1 being maintained at first draw roll under the room temperature and being maintained between second draw roll under the room temperature.One maintain 238 ℃ and length be the 250mm(millimeter) hot plate be configured between first draw roll and second draw roll.Draw speed be 15m/min(rice/minute) as the peripheral speed of second draw roll.This draw ratio is a maximal draw ratio, under this draw ratio, for the time 15 minutes no chemical-fibres filaments yarn breakages produce.The performance of the chemical-fibres filaments yarn that gained has stretched is shown in table 1.
32.0T/10cm(first twist per 10 centimetres of twisting counts) gives the 1890d(DENIER of gained like this) initial chemical fibre filament yarn.After two the chemical-fibres filaments yarn of twisting is pooled capital like this, again at the per 10 centimetres of twisting counts of 32.0T/10cm() add under the twisting count and twist to form former cord.By the Computreator of Rall Co., Ltd. (Ritzlar Co) now in using, former cord easily stands the impregnation process with resorcinol one formalin latex, in first district in 160 ℃ and 2.0kg/cord(kilogram/cord) tension force 140 seconds when be down, in second district in 230 ℃ with 3.8kg/cord(kilogram/cord) when under the tension force being 40 seconds and 230 ℃ with 2.6kg/cord(kilogram/cord) 40 seconds when under the tension force being.The gluing dosage that applies is 4.5%.The treated physical property of crossing cord is shown in table 2.
As can be seen, spinning speed be higher than 1000m/min n(rice/minute), the perfect index of crystal improves, and peak temperature Tmax reduces, then just can obtain good dimensional stability and fatigue resistance, obviously, spinning speed is high more, can improve dimensional stability and fatigue resistance more.
Example 2
Prepare not the chemical-fibres filaments yarn that stretches by the same mode described in example 1, just spinning speed change to 1500m/min(rice/minute) or 3000m/min(rice/minute).Then, the chemical-fibres filaments yarn that does not stretch is according to stretching at the drawing process described in the example 1 with under the draw speed shown in table 3 and the table 4.According to the same quadrat method described in example 1, be prepared into the cord of having handled from the chemical-fibres filaments yarn that has stretched of gained like this.Gained the results are shown in table 3 to table 6.
As can be seen, if draw speed surpass 100m/min(rice/minute), then reductions such as the perfect index of crystal, tensile strength, elongation, dimensional stability and fatigue resistance.
Comparative example 1
Prepare not the chemical-fibres filaments yarn that stretches by the same mode described in example 1, just spinning speed change to 1500m/min(rice/minute) or 3000m/min(rice/minute).The chemical-fibres filaments yarn of La Shening is not wound onto on the first Nelson cylinder, and second to the 4th Nelson cylinder that leads continuously, and there circumference rotary speed little by little increases, so that the hot-stretch setting divided for three steps carried out.The chemical-fibres filaments yarn that gained has stretched with 1500m/min(rice/minute) the package of speed coiled.First to fourth Nelson cylinder is made up of G1 to G4 the special roll dies of dagger-axe platform respectively.The Ge Taite godet roller correspondingly remains on 80 ℃ of room temperatures, 220 ℃ and 230 ℃ to G1 to G4.It is 1.01 to the peripheral speed between G2 and the G1 than G2/G1 that dagger-axe closes special godet roller; The Ge Taite godet roller is variable to the peripheral speed between G3 and the G2 than G3/G2; The Ge Taite godet roller is 1.6 to the peripheral speed between G4 and the G3 than G4/G3; Coiling speed and Ge Taite godet roller are 0.95 to the ratio of G4.Stretched chemical-fibres filaments yarn is handled the cord of having handled to obtain by the same manner described in the example 1.Its gained result as table 3 to shown in the table 6.
As can be seen, the perfect index of crystal, tensile strength, dimensional stability and fatigue resistance relatively poor than gained in the example 2 all.
Example 3
With employed 1500m/min n(rice in example 2/minute) the chemical-fibres filaments yarn that does not stretch that obtains of spinning speed, stretch by the same manner described in the example 1 again, what just the temperature of heater was as shown in table 7 changes like that to some extent.The chemical-fibres filaments yarn that has stretched from gained is prepared into the cord of having handled by the same manner described in the example 1.It the results are shown in the table 8.
As can be seen, when draft temperature raise, tensility was improved, and the perfect exponential sum dimensional stability of crystal improves.
Example 4
With employed 1500m/min n(rice in example 2/minute) the chemical-fibres filaments yarn that spinning speed was obtained does not stretch, stretch according to the drawing process described in the example 1 again.It has in its surface the chemical-fibres filaments yarn groove 18 that forms heater 17(, and by one around thermal insulation part 19 give heat insulation, be configured in as shown in Figure 4) between first draw roll and second draw roll.The length of this heater is the 500mm(millimeter), the chemical-fibres filaments yarn is carried by the chemical-fibres filaments yarn groove of heater, so that the chemical-fibres filaments yarn does not contact with heater.The temperature of heater is by adjusting shown in the table 9.The chemical-fibres filaments stretched from gained is prepared into treated cord by the same manner described in the example 1.It the results are shown in the table 10
As can be seen, under the situation of contactless heating, temperature can be enhanced, and the improvement of tensility then can be compared with the contact heating.
Example 5
Small pieces with formic acid relative viscosity polyhexamethylene adipamide as shown in table 11, after being melted in an extruder, melt is the 0.25mm(millimeter from having 624 diameters) spinnerets of pore carries out spinning in 305 ℃.Making long filament and twist yarn is the 150mm(millimeter by a length that is heated to 350 ℃) the heating drying cylinder, then through cooling with use steam treatment.Then, to be coated on the chemical-fibres filaments yarn to finish, the chemical-fibres filaments yarn be wound onto with 1400m/min(rice/minute) on the work beam of speed rotation, and then with the same speed of coiling speed under the coiled package, secondly, the chemical-fibres filaments yarn of La Shening does not reach 1% being maintained at the feeding roller under the room temperature and being maintained to uphold between first draw roll under 105 ℃ of temperature.The chemical-fibres filaments yarn is at first draw roll be maintained between second draw roll of 220 ℃ of temperature and stretch by the draw ratio shown in the table 11 then.Contact hot plate heater holding temperature is at 240 ℃, and its length is the 250mm(millimeter), be configured between first draw roll and second draw roll.Draw speed be 12m/min(rice/minute).The gained performance of elongate filaments yarn is shown in table 11.Be prepared into treated cord from the yarn of elongate filaments of gained like this by the same manner described in the example 1.It the results are shown in table 12.
As can be seen, along with the raising of viscosity, fatigue resistance has improvement, but when 80～90 formic acid relative viscosity, the tensile strength of being reached is in fact saturated.
Example 2 relatively
The chemical-fibres filaments yarn that does not stretch for preparing in example 5 rolls letter by first Nelson and batches, and is directed to first to fourth Nelson cylinder continuously, and there circumference rotary speed increases gradually, and the heat setting branch three that consequently stretches goes on foot to be finished.The chemical-fibres filaments yarn with 1500m/min(rice/minute) package of speed coiled.First to fourth Nelson cylinder is made up of G1 to G4 the Ge Taite godet roller respectively.The Ge Taite godet roller correspondingly maintains room temperature, 80 ℃, 220 ℃ and 230 ℃ to G1 and G4.The Ge Taite godet roller is 1.01 to the peripheral speed between G2 and the G1 than G2/G1.The Ge Taite godet roller is variable to the peripheral speed between G3 and the G2 than G3/G2.The Ge Taite godet roller is 1.6 to the peripheral speed between G4 and the G3 than G3/G2; Coiling speed and Ge Taite godet roller are 0.95 to the ratio of the peripheral speed of G4.Gained has been stretching in the chemical-fibres filaments yarn and has handled by the same manner described in the example 1, so that the cord that acquisition had been handled.It the results are shown in table 13 and the table 14.
As can be seen, tensile strength, the perfect index of crystal, dimensional stability and fatigue resistance are all relatively poor than what obtained in example 5.
Example 6
The employed chemical-fibres filaments yarn that does not stretch in example 3 is in the feeding roller of keeping room temperature with keep to uphold between first draw roll of 90 ℃ of temperature and reach 1%.Then, at first draw roll with keep that the draw ratio with 2.0 stretches between second draw roll of 200 ℃ of temperature.Then, the filament yarn that has stretched is at second draw roll with maintain that the draw ratio with 1.6 stretches coiled package then further between the 3rd draw roll of 200 ℃ of temperature.It is the 250mm(millimeter that temperature remains on 235 ℃ length) contact hot plate heater be configured between first draw roll and second draw roll, it is the 250mm(millimeter that another temperature remains on 245 ℃ length) contact hot plate heater be configured between second draw roll and the 3rd draw roll.Draw speed be 20m/min(rice/minute).It is the 9.4g/d(gram/dawn that the chemical-fibres filaments yarn that has stretched of gained has tensile strength), elongation is 16.0%, middle elongation is 7.5%, the shrinkage factor under dry heat condition be 4.4% and dimensional stability be 11.1%.The chemical-fibres filaments yarn that has stretched carries out impregnation process according to the same mode described in example 1, to obtain a kind of cord of having handled, it has tensile strength is the 8.0g/d(gram/dawn), elongation is 20.2%, middle elongation is 8.2%, shrinkage factor under dry heat condition is 3.5%, dimensional stability be 11.7% and solid special (G Y) fatigue life be 980 minutes.
The background of specification 11 inventions is left out
2 (1) scopes of invention are left out
The description of 7 (2) previous technologies is left out
2 18 1000 * 2,000 1000 to 2000
38 abstracts of invention are left out
The 46 simple descriptions that stretch are left out
The 4 12 preferred descriptions of specializing are left out
6 20 18% 10%
10 11 leak 5 adds numbering 5
In the 11 8 concrete devices among the embodiment
Claims (20)
1, a kind of high strength polyhexamethylene adipamide (polyamide 66) fiber have the formic acid relative viscosity be 50～150 and tensile strength be at least 7.5g/d (gram/dawn), this fiber has been characterised in that: elongation is to be not more than 8% under 5.3g/d (restraining for the 7 dawn) condition at stress in the middle of (1); (2) extension at break (%) and middle elongation (%) is poor, is to be at least 6% under 5.3g (gram/dawn) condition at stress; (3) shrinkage factor is not more than 5% under 160 ℃ of dry heat conditions.
2, as described in the claim 1, this polyhexamethylene adipamide (polyamide 66) elongation of fiber is in 12～20% scopes.
3, as described in claim 1 or the claim 2, the formic acid relative viscosity of this polyhexamethylene adipamide (polyamide 66) fiber is in 60～100 scopes.
4, as claim 1 as described in claim 3 arbitrary, another characteristics of this polyhexamethylene adipamide (polyamide 66) fiber are to have the perfect index of crystal to be at least 60%.
5, as claim 1 as described in arbitrary claim of claim 4, the another characteristics of this polyhexamethylene adipamide (polyamide 66) fiber are to have the crystal orientation degree to be at least 0.85, but are not more than 0.92.
6, as claim 1 as described in arbitrary claim of claim 5, characteristics again of this polyhexamethylene adipamide (polyamide 66) are the peak temperature Tmax with dynamic mechanically loss tangent (tan), when conspicuous at 110Hz() when measuring under the frequency, can satisfy the requirement of following formula:
100≤Tmax+4（9.5-DS）≤116
DS represents tensile strength (g/d) in the formula.
7, one for preparing the method for polyhexamethylene adipamide (polyamide 66), and it comprises: it is 50～150 polyhexamethylene adipamide (polyamide 66) that fusion has the formic acid relative viscosity; From a spinnerets melt extrusion; Cooling extruded thing also solidifies thus; 1000～6000m/min(rice/minute) coiling speed under the chemical-fibres filaments yarn of coiling gained; Then be not more than 100m/min(rice/minute) draw speed under this chemical-fibres filaments yarn of hot-stretch.
8, according to the method for claim 7, wherein the formic acid relative viscosity of polyhexamethylene adipamide (polyamide 66) is in 60～100 scopes.
9, according to the method for claim 7 or claim 8, wherein hot-stretch is to heat by the contact that realizes the chemical-fibres filaments yarn in a stretching-machine to finish, and this stretching-machine comprises the heater of a contact chemical-fibres filaments yarn that is configured between first draw roll and second draw roll.
10, according to the method for claim 9, wherein the heater of chemical-fibres filaments yarn is that the temperature that keeps is 180～260 ℃.
11, according to the method for claim 9, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 230～255 ℃.
12, according to the method for claim 7 or claim 8, wherein hot-stretch is to finish by the contactless heating that realizes the chemical-fibres filaments yarn in a stretching-machine, and this stretching-machine comprises a heater that is configured in a chemical-fibres filaments yarn between first draw roll and second draw roll.
13, according to the method for claim 12, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 200～280 ℃.
14, according to the method for claim 12, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 240～275 ℃.
15, according to the method for claim 7 or claim 8, wherein hot-stretch is to heat by the contact that realizes the chemical-fibres filaments yarn in a stretching-machine to finish, and this stretching-machine comprises two heaters that are configured in the contact chemical-fibres filaments yarn between first draw roll, second draw roll, the 3rd draw roll and the draw roll thereafter at least.
16, according to the method for claim 15, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 180～260 ℃.
17, according to the method for claim 15, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 230～255 ℃.
18, according to the method for claim 7 or claim 8, wherein hot-stretch is to finish by the contactless heating that realizes the chemical-fibres filaments yarn in a stretching-machine, and this stretching-machine comprises two heaters that are configured in (contactless) chemical-fibres filaments yarn between first draw roll, second draw roll, the 3rd draw roll and the draw roll thereafter at least.
19, according to the method for claim 18, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 200～280 ℃.
20, according to the method for claim 18, wherein the heater of chemical-fibres filaments yarn is that to remain on temperature be 240～275 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100423 CN1013384B (en) | 1983-10-20 | 1985-04-01 | Polyamide 66 fibre of high form-stability and good fatigue resistance and its preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19517083A JPS6088115A (en) | 1983-10-20 | 1983-10-20 | Manufacture of polyhexamethylene adipamide fiber |
| CN 85100423 CN1013384B (en) | 1983-10-20 | 1985-04-01 | Polyamide 66 fibre of high form-stability and good fatigue resistance and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100423A true CN85100423A (en) | 1987-01-10 |
| CN1013384B CN1013384B (en) | 1991-07-31 |
Family
ID=25741310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85100423 Expired CN1013384B (en) | 1983-10-20 | 1985-04-01 | Polyamide 66 fibre of high form-stability and good fatigue resistance and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013384B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064725C (en) * | 1995-02-09 | 2001-04-18 | 罗纳-普朗克·维斯科苏希公司 | Polyamide-66-monofilaments for precision fabrics |
| US20170253997A1 (en) * | 2014-10-15 | 2017-09-07 | Invista North America S.A R.L. | High tenacity or high load bearing nylon fibers and yarns and fabrics thereof |
| CN109837627A (en) * | 2019-02-15 | 2019-06-04 | 南通纺织丝绸产业技术研究院 | One-step method nano fibre yarn Enhancement Method and a kind of hydrophilic chemical & blended fabric |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619503B (en) * | 2009-07-27 | 2011-04-27 | 神马实业股份有限公司 | High-strength ultra-low thermal contraction nylon 66 fiber and production method thereof |
-
1985
- 1985-04-01 CN CN 85100423 patent/CN1013384B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064725C (en) * | 1995-02-09 | 2001-04-18 | 罗纳-普朗克·维斯科苏希公司 | Polyamide-66-monofilaments for precision fabrics |
| US20170253997A1 (en) * | 2014-10-15 | 2017-09-07 | Invista North America S.A R.L. | High tenacity or high load bearing nylon fibers and yarns and fabrics thereof |
| CN111485294A (en) * | 2014-10-15 | 2020-08-04 | 英威达纺织（英国）有限公司 | High-tenacity or high-load-bearing nylon fiber and yarn and fabric thereof |
| CN111485294B (en) * | 2014-10-15 | 2023-03-31 | 英威达纺织（英国）有限公司 | High-tenacity or high-load-bearing nylon fiber and yarn and fabric thereof |
| CN109837627A (en) * | 2019-02-15 | 2019-06-04 | 南通纺织丝绸产业技术研究院 | One-step method nano fibre yarn Enhancement Method and a kind of hydrophilic chemical & blended fabric |
| CN109837627B (en) * | 2019-02-15 | 2021-11-12 | 南通纺织丝绸产业技术研究院 | One-step method for reinforcing nanofiber yarn and hydrophilic chemical fiber fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1013384B (en) | 1991-07-31 |
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