WO2001059191A1 - High-strength polyester-amide fiber and process for producing the same - Google Patents

High-strength polyester-amide fiber and process for producing the same

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Publication number
WO2001059191A1
WO2001059191A1 PCT/JP2001/000792 JP0100792W WO0159191A1 WO 2001059191 A1 WO2001059191 A1 WO 2001059191A1 JP 0100792 W JP0100792 W JP 0100792W WO 0159191 A1 WO0159191 A1 WO 0159191A1
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WO
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Patent type
Prior art keywords
polyester
yarn
temperature
strength
stretching
Prior art date
Application number
PCT/JP2001/000792
Other languages
French (fr)
Japanese (ja)
Inventor
Yasuhiro Tada
Masayuki Hino
Toshiya Mizuno
Original Assignee
Kureha Kagaku Kogyo K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/82Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides

Abstract

A high-strength polyester-amide fiber made of a polyester-amide copolymer, characterized in that in dynamic viscoelastometry the fiber has a main dispersion peak at a temperature higher by at least 10°C than the temperature of the main dispersion peak of a nonoriented object made of the polyester-amide copolymer; and a process for producing high-strength polyester-amide fibers which comprises a series of steps of spinning a melt of a polyester-amide copolymer and immediately solidifying the resultant filament by cooling in an inert cooling medium having a temperature of 20°C or lower to thereby obtain a noncrystalline unstretched yarn, heightening the crystallinity of the unstretched yarn to 10 to 30 wt.%, and stretching the resultant unstretched yarn having a crystallinity of 10 to 30 wt.% in one or more steps so as to result in an overall stretch ratio of 4.5 or higher.

Description

Specification high strength polyester amides fiber and its production method art

The present invention relates to a high strength polyester amide fibers, more particularly, higher linear tensile strength, have a moderate elongation, relates to a high strength Polje Suteruamido fiber and a manufacturing method thereof showing the biodegradability. High strength polyester Ruamido fiber of the present invention is suitable for fishing and fishing nets, use as industrial materials, such as agricultural net. BACKGROUND

In recent years, the development of friendly textiles in the global environment with a biodegradable, such as biodegradable and photodegradable has been strongly desired. In general, fishing line, fishing nets, the etc. agricultural net, workability, strength, durability, and is formed from synthetic fibers such as excellent polyamide mono filament to heat resistance. Such conventional synthetic textiles, since no degradable under natural environment, for example, or spilled fishing line and nets, when or is left, straining force pulling the pollution problems such as severe marine pollution.

Many natural fibers, although biodegradable, fishing line, fishing net, process is not performed to issue a high performance such as high strength required for industrial materials such as agricultural net Bok. Also, natural fibers lack the workability required for mass production. For this, some of the aliphatic polyester, marine and river are known to undergo microbial degradation by adherent bacteria distributed, yet conventional spinning techniques and equipment have been developed for synthetic resins since it is a child process to fibers by utilizing the application to biodegradable fibers it has been studied.

For example, Japanese Laid-2-2 0 3 7 2 9 discloses, fishing line formed from an aliphatic polyester having a property of being gradually decomposed in the natural environment have been proposed. However, the publication, the specific description of the spinning techniques are rather name not be shown embodiment. Moreover, the publication, the fishing line that is formed from an aliphatic polyester Le, there are cases that undergo hydrolysis by moisture in air, also, since after use gradually strength decreases, in-out all the disposable It has been described as being.

JP 5 - The 5 9 6 1 1 JP, mono filament comprising poly force caprolactone has been proposed. The examples of this publication, poly force Puroraku tons (melting point = 6 0) melt spinning at 2 1 0 ° C, 1 at 5 ° in an aqueous solution of C after cooling, immediately 4 5 C in a warm water draw ratio five times exceed seven times less than perform stretching in the first stage, then performs all draw ratio in the second stage so that the 8 more than double stretched by 1 0 0 ° C in an oven, Furthermore, more to relaxation heat treatment, it is described that to obtain a high strength poly force caprolactone monofilament. However, the poly force caprolactone monofilaments, the heat resistance is insufficient, and the strength is remarkably reduced under high temperature conditions.

Thus, fibers made of aliphatic polyesters, although having biodegradability, are closed or a mechanical strength insufficient, disadvantages such as poor heat resistance. On the other hand, polyamide fibers, mechanical strength, heat resistance, although excellent in such workability, does not have biodegradability. Therefore, while improving the physical properties of aliphatic polyesters, in order to impart biodegradability to the polyamide, poly ester amide copolymer have been developed and have also been studied applications as a biodegradable fiber. 'For example, JP 5 4 - The 1 2 0 7 2 7 discloses a high molecular weight aliphatic Po Riesuteru and aliphatic polyamide, in an inert gas, the presence of a catalyst such as acetic anhydride zinc, by heating to their melting point or higher temperatures, and to perform the ester primary amide exchange reaction, to produce a polyester § bromide copolymer low molecular weight polyester blocks and low molecular weight polyamide blocks are bonded to a number alternately, this it is disclosed that the by melt-spinning a biodegradable fiber. However, the publication was spun by using the polyester amide copolymer, not shown specific examples the fiber.

JP 7 - The 1 7 3 7 1 6 JP, monofilament and a manufacturing method thereof comprising a polylactone amide copolymer comprising a polyamide units and polylactone units is disclosed. The publication, a polylactone amide copolymer melt spun, 6 0 ° C or less (preferably 2 6~6 0 ° C) was cooled and solidified in an inert liquid, stretching under 4 times exceeded 7 times perform first-stage stretching at a magnification, then Monofirame cement manufacturing method of stretching at a draw ratio of the total draw ratio is 7 times or more is described. Specifically, in the embodiment of the publication, port Rirakuton'ami the de copolymer melt spun at 2 0 0 ° C, 3 5 ° after cooling in warm water and C, immediately 8 0 ° C warm water bath in stretch ratio 4. performs extension Shin the first stage in five-fold, after relaxing heat treatment in warm water of 9 0 ° C, the total draw ratio at 1 2 0 ° C dry heat bath 9. 0 times become so perform stretching of the second stage, to be et al, performed relaxation heat treatment in a dry heat bath 1 0 0 ° C, it has been shown to be producing Monofuira placement of high strength.

Incidentally, in the production of textiles, such as monofilaments from polyamides such as nylon, polyamide melt spun and quenched as undrawn yarn, which quickly by stretching the unstretched yarn. This is to suppress crystallization of the undrawn yarn by quenching a order to orient reasonably molecular chains during stretching. Molecular chains stretched during stretching results in orientation and crystallization, oriented in both the crystal portion and the amorphous portion is fixed, exhibit excellent mechanical strength.

However, the polyester amide copolymer, the application of such spinning and rolling Shinho, flame is frame to obtain a fiber mechanical strength is sufficiently improved. That is, the polyamide segments of the polyesteramide copolymer, chain length To reduce the biodegradability of the copolymer are designed to short Kunar so. Thus, polyester amide copolymer is less crystalline, oriented crystallization even or bought difficulty occurs as compared to polyamide homopolymers, or crystallization speed is slow. Therefore, to that stretched amorphous unstretched yarn obtained by rapid cooling, can not be sufficiently fix the orientation of the amorphous portions, the mechanical strength is not sufficiently improved.

Further, in order to achieve both biodegradability and mechanical strength, the polyester amide copolymer obtained by shortening design a chain length of the polyamide segments of the undrawn amorphous, subsequently, the undrawn yarn 5 0 ° If you'll stretching at a relatively high temperature conditions, such as exceeding C, fusing is likely to occur, and child satisfactorily stretching is difficult.

By adjusting the cooling and solidification conditions such as the cooling temperature of the undrawn yarn, the method of crystallizing a part of, or could not obtain sufficient crystallinity, it is difficult to precisely control the degree of crystallinity . Further, in order to achieve both biodegradability and mechanical strength, the polyester Ruamido copolymer shortened design a chain length of the polyamide segments melt spinning, and relatively cold 却固 reduction in coolant adjusted to a high temperature crystal even if an attempt to perform a reduction, because spun yarn is close to still molten state, such as a resistance of the resistor and the roll of the cooling medium, deformed by or elongation or meandering. Was melt spun yarn is staying for a predetermined time in air even if an attempt is sintered crystallized, if thread diameter is relatively large monofilament, cooling efficiency is extremely poor, it is impractical. Moreover, not uniform yarn diameter thread near the molten state is deformed in the flight.

Thus, polyether Suteruamido copolymer obtained by copolymerizing an aliphatic polyester and polyamide has been expected as a resin having both the toughness of biodegradable and polyamide aliphatic polyester, in the conventional manufacturing method, excellent balance between biodegradability and mechanical strength, it has been difficult to produce a polyesteramide fibers sufficiently high strength. Disclosure of the Invention

An object of the present invention, the linear tensile strength significantly higher, has a moderate elongation, to provide a high strength polyester Ami de fiber and a manufacturing method thereof showing the biodegradability.

The present inventors have made intensive studies to achieve the above object, found by Rukoto adjusting the main dispersion peak temperature in a dynamic viscoelasticity measurement of the polyether Suteruami de fibers, that the straight tensile strength can significantly improve It was. High strength polyester amides fiber of the present invention, a polyester amide copolymer melt spun and immediately 2 0 ° C or less, preferably 1 5 ° C or less, more rather preferably is 1 0 ° C or less inert cooling medium It cooled and solidified substantially obtain an undrawn yarn of the amorphous and in the medium, after increasing the crystallinity of the undrawn yarn 1 0-3 0% by weight, the total draw ratio 4.5 times or more, can preferably also one stage such that at least five times that produced by multi-stage stretching. To enhance the crystallinity of the undrawn yarn 1 0-3 0% by weight, there is a method to advance the well crystallized, such as by standing for 24 hours the undrawn yarn for example at room temperature.

In the stretching step, enlargement single stage or multi-stage rolling so that the total draw ratio undrawn crystallinity 1 0-3 0% by weight at a temperature 2 0 ~ 1 2 O t is four. Five times or more, the time, preferably 5 0~ 1 2 0 ° C, more preferably by placement of at least one drawing stage stretching in the stretching ratio 1.3 times in 7 0 to 1 1 0 ° C, a particularly good the results can be obtained. Further, the drawn yarn by drawing the undrawn yarn substantially non-crystalline, the crystallinity of the drawn yarn was increased to 1 0-3 0% by weight, by a method of one-stage or multi-stage stretching, the high it is possible to obtain the strength polyester amide fibers. The present invention has been completed based on these findings.

According to the present invention, there is provided a fiber comprising a polyester amide copolymer, the main dispersion peak temperature in a dynamic viscoelasticity measurement of the fibers, than the main dispersion peak temperature of the unoriented consisting of the polyesteramide copolymer high strength polyesteramide fiber characterized 1 0 ° C or more higher Ikoto is provided.

Further, according to the present invention, a polyester amide copolymer melt spinning method of producing a polyester Ami de fibers drawing the undrawn yarn obtained smell Te,

(1) a polyester amide copolymer melt spun immediately temperature 2 nonzero obtaining an undrawn yarn was cooled and solidified in an inert cooling medium noncrystalline under,

(2) yet-step of increasing the crystallinity of the drawn yarn into a 0-30% by weight and,

(3) a step of one-stage or multi-stage stretching as undrawn yarn total draw ratio of crystallinity 1 0-3 0% by weight is over 4.5 more than double

High strength polyester amides method for producing a fiber which comprises a series of steps consisting of are provided.

Furthermore, according to the present invention, a polyester amide copolymer melt spinning method of producing a polyester Ami de fibers drawing the undrawn yarn obtained smell Te,

(I) a polyester amide copolymer melt spun, to obtain an amorphous unstretched yarn was immediately cooled and solidified at a temperature 2 in the following inert cooling medium step,

(II) the undrawn yarn stretched at a temperature one 1 0 ° C~ 5 0 ° C ratio: 1. step to extend more than 3 times drawn yarn,

(III) the step of increasing the crystallinity of the drawn yarn to 1 0 to 30% by weight and,

(IV) step of the total draw ratio drawn yarn of crystallinity 1 0-3 0% by weight is more one-stage or multi-stage stretching in such a way that 4.5 or more times

High strength polyester amides method for producing a fiber which comprises a series of steps consisting of are provided. BEST MODE FOR CARRYING OUT THE INVENTION

1. Polyester amide copolymer

Polyester Ami de copolymer used in the present invention is a polymer having a polyamide bromide units and polyester units in the molecular chain. The proportion of each unit is preferably a polyamide units 5-8 0 mol%, more preferably from 2 0-7 0 mol%, particularly preferably 3 0-6 0 mol%, corresponding to these, a polyester unit is preferably 2 0-9 5 mol%, more preferably 3 0-8 0 mol%, particularly preferably 4 0-7 0 mol%. If the proportion of polyamide mi de unit is too small poor mechanical strength, when it is excessively large, biodegradable is impaired.

The polyamide units, various known polyamides can be used. When the melting point is used excessively high polyamides, because it may result in thermal decomposition of the polyester segment during melt molding, a polyamide 6 (nylon 6), made of Polyamide 6 6 (nylon 6 6), or co these heavy the coalescence preferably les polyester units, from the viewpoint of biodegradability, although aliphatic Poriesu ether are preferably used, so long as they exhibit biodegradability, alicyclic polyesters or aromatic, such as xylylene-methyl adipate to polycyclo polyester Le etc., may be used in combination with either alone or aliphatic polyesters. The aliphatic polyesters, polybutylene adipate, polyethylene adipate Pies and polylactone is preferred.

Synthesis of the polyester amide copolymer is not particularly limited, for example, (1) a polyester by introducing the polyamide in the aliphatic polyester alternately number Ri by the Ami dough transesterification - process for the amide copolymer ( JP Akira 5 4 1 2 0 7 2 7 No.), (2) a polyamide-forming compound (e.g., .epsilon. force and caprolactam, etc.), dicarboxylic acid and the polyester diol (e.g., polylactone diol) and the reaction and; a polyester-forming compound (lactones such as dibasic acids and diols) - method of (Hei 7-1 7 3 7 1 6 JP), (3) a polyamide-forming compound (such as Chikarapu Rorakutamu e.g., epsilon) a method of reacting the like.

In the method (1), as the polyester, poly force Purorakuto down, polyethylene adipate, polybutylene adipate, and examples of the polyamide include nylon 6, nylon 6 6, nylon 6 9, Na Iron 6 1 0, nylon 6 1 2, nylon 1 1, nylon 1 2 can be mentioned up.

The polyamide-forming compounds, for example, .omega. Amino acid, omega - § amino valeric acid, .omega.-aminocaproic acid, .omega.-aminoenanthic acid, omega - Amino force prills acid, .omega. Amino base Rarugon acid, omega - aminoundecanoic acid, omega - Amino carbon number 4-1 2 Aminokarubon acids such dodecanoic acid; § one Puchirorakutamu, .epsilon. force caprolactam, E Nantes lactam, Capri Rorakutamu, lactam number 4-1 2 carbons, such as laurolactam; and and the like. Further, as the polyamide-forming compounds, mention may be made of nylon salt composed of a dicarboxylic acid and Amin, is the said dicarboxylic acids, succinic acid, Darutaru 'acid, adipic acid, pimelic acid, suberic acid, sebacic acid, Azerain acid, aliphatic dicarboxylic acid having a carbon number of 4-1 2 such as dodecanedioic acid; hydrogenated terephthalic acid, alicyclic dicarboxylic acids, such as hydrogenated isophthalic acid; terephthalic acid, isophthalic acid, aromatic dicarboxylic such as phthalic acid acid; and the like, also, examples of the Jiamin, tetramethylene Chirenjiamin, pentamethylene di § Min, hexamethylene diamine, heptamethylene di § Min, O Kuta methylene Asia Min, Nonamechirenji Amin, decamethylenedicarboxylic § Min, © down decamethylenedicarboxylic § Min, a Dodekame Chirenjiamin Carbon number 4-1 2 aliphatic Jiamin of; cycloheteroalkyl hexa Njiamin, Kisanjiamin alicyclic Jiamin such methylcyclohexane; aromatic, such as key Shirenjiamin Jiamin; and the like.

In the method (2), as the dicarboxylic acid, succinic acid, glutaryl Le acid, adipic acid, pimelic acid, suberic acid, sebacic acid, Azerain acid, aliphatic dicarboxylic acids such as dodecanedioic acid; hydrogenated terephthalic acid, alicyclic dicarboxylic acids such as hydrogenated isophthalic acid; terephthalic acid, isophthalic Le acids, full evening aromatic dicarboxylic acids such as Le acids; and the like.

In the method (2), the polyester diol, Porirakutonjio Ichiru average molecular weight 5 0 0-4 0 0 0 can be mentioned, with Dali call compound as a reaction initiator, a carbon number 3-1 It is either 2 of lactone et synthesis. The lactone, 3-propiolactone, / 3-Petit port lactone, .delta.-valerolactone, epsilon - force caprolactone, Enantorakuto down, caprylolactone, laurolactone, and the like.

In the method (3), Examples of the dibasic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, Azerain acid, dodecanedioic acid. Examples of the diol include ethylene glycol, 1, 3-propanediol , 1, 4-butanediol, 1, 5-pen evening Njioru, 1, hexanediol to 6, 2, 3 _ butanediol, 2, Kisanji ol to 5, 2 - methyl - 1, 4 _ butanediol, 3-methyl - 2, 4 one-pentanediol, 2-methyl-2, 4 one-pentanediol, 2-E Ji Lu methyl one 1, 3 - propanediol, 2, 3 - dimethyl-2, 3-butanediol and the like.

In the method (3), examples of the lactone, / 3-propiolactone, I3- butyrolactone, <5-valerolactone, epsilon - force caprolactone, E Na Ntorakuton, caprylolactone, such as lauroyl lactone. Other, glycolic acid, Gurikori de, lactic acid, 3- hydroxybutyric acid, beta - such as hydroxyvaleric acid can be mentioned as polyester forming compound.

Examples of the polyester amide copolymer, the mechanical strength and in terms of path lance biodegradable, nylon 6 Zeta polybutylene adipate base one preparative copolymer, Na Iron 6 6 Zeta polybutylene adipate copolymer, nylon 6 Zeta Poryechi Ren'aji Bae over preparative copolymer, nylon 6 6 / polyethylene adipate copolymer polymers, nylon 6 / poly force caprolactone copolymer, nylon 6 6 Zeta poly force caprolactone copolymers and the like are preferable.

The melting point of the polyester amide copolymer (T m) is preferably 9 0 ° C or more on, more preferably 1 0 0 ° C or more, in many cases, 9 0~ 1 8 0 ° approximately C. The melting point of the polyester Ami de copolymer (T m), using a differential scanning calorimeter, a crystal melting peak temperature when measured at a heating rate of 1 0 ° CZ minute, when a plurality of melting peaks appear the means large peak temperature of highest calorific value. If the melting point is too low, it not is sufficient heat resistance of the polyester amides textiles, decrease in strength under high temperature environment, tend to occur problems such as fusing by grinding Kosunetsu during use. On the other hand, if the melting point is too high, the melt spinning temperature is high, easy decomposed polyester segment Kunar.

The relative viscosity of the polyester amide copolymer is preferably from 1. 0 or more, more preferably 1.3 or more, in many cases, it is from 1.0 to 3.0. The relative viscosity of the polyester amide copolymer, hexa full O b isopropanoyl Nord (HFIP) as a solvent to a concentration 0. 4 g / d 1 (polymer 0 to the solvent 1 0 0 m 1. 4 g ratio of the polymer solution in dissolution), in an atmosphere of temperature 1 0 ° C, a value measured using an Ubbelohde viscometer. If the relative viscosity is too low, the degree of polymerization (or molecular weight) is too low, it is difficult to obtain a fiber excellent in mechanical strength, too high, it tends to occur diameter spots and strength mottled fibers, uniform it is difficult to obtain a fiber physical properties.

2. Process for producing a polyester amide fibers

In the present invention, by using a polyester amide copolymer, to produce a polyesteramide fiber by the following production process. Polyesteramides textiles is usually a monofilament, optionally, it may be Maruchifirame cement.

That is, the method of producing a polyester amide fibers of the present invention, melt spinning the Poriesu Teruamido copolymer, is a method for producing a polyether Suteruamido fibers drawing the undrawn yarn obtained, which by a series of steps below line.

(1) a polyester amide copolymer melt spun immediately temperature 2 0 ° C or less to obtain a noncrystalline undrawn yarn was cooled and solidified in an inert cooling medium under

(2) yet-step of increasing the crystallinity of the drawn yarn into a 0-30% by weight and,

(3) a step of undrawn yarn total draw ratio of crystallinity 1 0-3 0% by weight to 1 stage or multi-stage stretching in such a way that the 4.5 more than double.

Wherein in the step (1), a polyester amide copolymer melt spun and immediately 2 0 ° C or less, the cooling preferably 1 5 ° C or less, more preferably in a 1 0 ° C or less inert cooling medium It solidified to Ru obtain an undrawn yarn of substantially amorphous. Spinning temperature for melt spinning is usually about 1 00-200 ° C, the spinning take-up speed, if the monofilament, usually from l to 50 m / min extent, in the case of a multi-filament, usually, it is a 20~ 1, 0 0 0 m / min.

When the temperature of the cooling medium is too high, there is a call partial crystallization in unstretched yarn occurs, but it is difficult to uniformly and precisely control the degree of crystallinity, shed information, sufficient mechanical strength it is difficult to obtain a polyester amide fibers having. Further, when the temperature of the cooling medium is too high, then the undrawn yarn is deformed, it is difficult to mold the uniform fiber. The lower limit temperature of the cooling medium, depending on the type of the cooling medium is preferably about 0 ° C. As the cooling medium, e.g., water, glycerol, polyester Ami de copolymers such as ethylene glycol inert liquid compounds and mixtures thereof. Among these, water is preferred. In this step (1), 5% crystallinity is preferably less, more preferably 3% or less, obtained often 0% substantially amorphous unstretched yarn.

In the step (2), substantially the crystallinity of the undrawn amorphous 1 0-3 0% by weight, preferably increased to a range of 1 2 to 2 8% by weight. To enhance the crystallinity of the undrawn yarn, methods 1 0 min undrawn yarn obtained in step (1) in an atmosphere of 1 0 to 8 0 ° C placing 72 hours and the like. In general, a longer enough processing time ambient temperature is low, by shortening the higher processing time, it is preferable to adjust the degree of crystallinity desired range. To do this binding crystallization process, winding the undrawn yarn of substantially amorphous obtained in step (1) for example in a roll, with the wound up, an atmosphere adjusted to a predetermined temperature condition how to stand predetermined time is preferable. To precisely control the crystallinity of the undrawn yarn, the undrawn yarn was wound, in an atmosphere adjusted to a predetermined temperature in the range of 1 0 to 3 5 ° C, usually 5-7 2 hours , preferably about 1 0 to 30 hours, a method of standing is desirable.

By adopting such a method, generally have low crystallinity, can be strictly controlled as the crystallinity of the undrawn yarn crystallization rate consists of slow polyester amide copolymer has a desired range . When the crystallinity of the undrawn yarn is too low, the orientation of the amorphous portion be sufficiently secured scratches, to obtain a fiber excellent in strength it becomes difficult at the time of stretching. On the other hand, when the sintering crystallization degree of the undrawn yarn is too high, lowered strength voids occurs during the stretching, in some cases, it may be cut in the middle stretch.

In the step (3), the undrawn yarn total draw ratio of crystallinity 1 0-3 0% by weight makes a one-stage or multi-stage stretching in such a way that 4.5 times or more. Hereinafter sometimes referred to as the step and the crystal stretching step. The stretching temperature is preferably 2 0~ 1 2 0 ° C, the upper limit is adjusted so as not to exceed the melting point of the polyester Ami de copolymer using (Tm). Adjustment of the stretching temperature is carried out using a dry hot gas or liquid heating medium was adjusted to a predetermined temperature.

In the present invention, is carried out stretched in one stage or two or more stages, where, preferably extending extension temperature 5 0-1 2 0 ° C, and more preferably adjusted to 7 0-1 1 0, the placing the drawing stage of stretching at 1.3 times or more of the draw ratio in stretching temperature is particularly desirable in obtaining a high-strength fibers. Stretching at this temperature is preferably carried out in dry hot body. By the child placed the drawing stage, elevated in moderate range crystallinity of the drawn fiber, at the same time, it is possible to increase the orientation of the crystal portion and the amorphous portion (crystal orientation) as well, as a result, machine it is possible to obtain an excellent fiber 械的 strength.

Stretching in the stretching step, when the one-stage stretching, for example, Ru can be accomplished by a method of stretching one stage draw ratio for 5-7 times at a stretching temperature of 7 0~ 1 1 0 ° C. In the case of multi-stage stretching, if I 1 is disposed a drawing stage at least three times the draw ratio in the temperature range of the other stretching, for example, 2 5, such as ° C 5 0 less than ° C it may be carried out at a temperature. Stretching in the stretching step can be carried out in one stage or multiple stages, the stretching ratio is 1.3 times or more, it is preferably 1 2 times or less.

Total draw ratio is 4.5 times or more, preferably 5 times or more, its upper limit is about 1 5 times. When the total draw ratio is too low, it is impossible to obtain a sufficient mechanical strength. After the stretching step, at a constant length or relaxed state, it may be heat-treated at the thermal melting point (T m) or lower.

Further, in the present invention, by the following steps, it is possible to manufacture a high-strength polyester amides fiber excellent in balance between biodegradability and mechanical strength. (I) a polyester amide copolymer melt spun immediately temperature 2 0 ° C following steps solidified by cooling to obtain a noncrystalline undrawn yarn in an inert cooling medium,

(II) unstretched drawn yarn at a temperature one 1 0 ° C~5 0 ° C ratio: 1. step to extend more than 3 times drawn yarn,

(III) the step of increasing the crystallinity of the drawn yarn to 1 0 to 30% by weight and,

(IV) a step of further 1-stage or multi-stage stretching as the total draw ratio of the drawn yarn of crystallinity 1 0-30 wt% is 4.5 times or more.

In the step (I), the spinning temperature for melt spinning is usually 1 00~ 2 0 0 ° about C, spinning take-up speed is usually l to 5 0 m / min extent der is, cooling temperature of the medium is preferably 1 5 ° C, more preferably at most 1 0 ° C. In the step ([pi), the stretching temperature is preferably 0 to 4 0 ° C, and more preferably 1 0 to 3 5 ° C, the stretching ratio is preferably 2 times or more, more preferably 3 times or more There, in many cases, it is possible to obtain good results in 4-1 0 times. In this step (II), when increasing the draw ratio, in 1 0 to 3 5 ° C about the stretching temperature, it is desirable to perform a multi-stage extending Shin about 2-5 times.

Wherein step (II) is an amorphous stretching step of stretching the unstretched yarn of substantially non-crystalline. Drawn yarn obtained in step (II) is, the crystallinity of 1 0-3 0 by weight%, preferably increased to a range of 1 2 to 28% by weight. To increase the crystallinity of the drawn yarn, a method of placing 7 2 hours for 10 minutes the drawn yarn in an atmosphere of 1 0 to 80 ° C and the like. To do this crystallization process, winding the drawn yarn obtained we are in step ② for example, a roll, in a state where the wound, is preferably predetermined time stand how to atmosphere adjusted to a predetermined temperature condition . To precisely control the crystallinity of the drawn yarn, a drawn yarn wound, in an atmosphere adjusted to a predetermined temperature in the range of 1 0~ 3 5 ° C, usually for 5-7 2 hours, preferred properly 1 0 about 30 hours, a method of standing is desirable.

After the drawn yarn in an amorphous state, the crystallinity of the drawn yarn increased to the range of 1 0 to 3 0 wt%, then by arranging the stretching step (IV), sufficient mechanical strength of it is possible to increase. In step (IV), the total draw ratio of the drawn yarn of crystallinity 1 0-3 0% by weight makes a one-stage or multi-stage stretching in such a way that 4.5 times or more. The stretching temperature is preferably 2 0~ 1 20 ° C, adjustment of the stretching temperature is carried out using a dry hot gas or liquid heating medium was adjusted to a predetermined temperature. In the stretching step (IV), preferably the stretching temperature 5 0~ 1 2 0 ° C, adjusted to a more preferred rather is 7 0~ 1 1 0 ° C, 1. more than three times stretched at the stretched temperature magnification in placing the stretching step of stretching, particularly desirable arbitrariness in obtaining high strength fibers. Other stretching conditions are the same as those of the aforementioned methods.

3. polyesteramides fibers polyesteramides fibers present invention, the main dispersion peak temperature that put the dynamic viscoelasticity measurement of the fibers, the main dispersion peak temperature than 10 ° C non-oriented composed of the polyester amide copolymer or higher, preferably higher than 1 2 ° C. That the primary dispersion peak temperature of the drawn fiber is higher than 1 0 ° C in comparison to non-oriented material shows that amorphous molecular chains are highly tensioned restrained. In other words, extending Shin is effectively carried out, as a result, not only the molecular chains of the crystalline portion of the fiber, the molecular chain of the amorphous portion also indicates that the highly oriented. The upper limit of the temperature difference between the primary dispersion peak temperature is about 1 7 ° C, a 1 5 ° about C often. Polyesteramides fibers of the present invention, crystallinity of the fiber (wt%) of A and the long period (A) B as measured by small-angle X-ray scattering, the formula (I)

5≤ (AXB) / 100≤ 30 (I)

It is preferable that satisfies the relationship.

The long period B is measured by the degree of crystallinity A and small-angle X-ray scattering, and more preferred details, formula (II)

1 0≤ (AXB) / 100≤ 25 (II)

Satisfies the relationship, particularly preferably the formula (III)

1 5≤ (AXB) / 1 00≤ 20 (III)

To satisfy the relationship.

The product of the long period B is measured by the degree of crystallinity A and small-angle X-ray scattering, which corresponds to the thickness of the crystal produced by the crystallization of the polyamide Mi de segment. (AX B) / 1 0 0 fibers such that less than 5, since the communication chain length of the polyamide segment is short, have low crystallinity, sufficiently polyamide units introduced into the molecular chain to improve the machine 械的 strength there is a possibility that does not contribute. On the other hand, fibers such as (AXB) / 1 0 0 is 2 5 exceeded, because the chain length of the polyamide segments is too long, there is a possibility that biodegradability is impaired.

Crystal orientation of the polyester amide fibers of the present invention is preferably 90% or more, more preferably 9 to 3% or more. The upper limit of the degree of crystal orientation is about 9 8%. By high degree of crystal orientation of the fibers, it has excellent mechanical strength.

Such polyester Ami de fibers, the can be obtained by the manufacturing method, and it has a moderate elongation and excellent linearity tensile strength.

That is, polyesteramides fiber of the present invention can then enhance the crystallinity of the amorphous unstretched yarn made of polyester amide copolymer in 1 0-3 0% by weight, obtained by stretching. Further, polyesteramides textiles of the present invention, stretching the amorphous unstretched yarn made of polyester amide copolymer, then increased the crystallinity of the drawn yarn obtained in 1 0-3 0% after, it is possible Tokuraru extends to further.

Straight tensile strength of the polyester amide fibers of the present invention is usually, 3 0 0 MP a or more, preferably 3 5 OMP a higher, more preferably 3 8 0 MP a or more, particularly preferably 40 OMP a more. Straight tensile strength is often of the order of 3 8 0~70 0MP a. Elongation of the polyester Ami de fibers of the present invention is usually 1 0% or more, preferably 1 to 5% or more in the case of Many is about 1 0-50%.

Polyesteramides fibers of the present invention, it is desirable biodegradability is good. Polyesteramides fibers of the present invention, when removed from the buried 6 months in the soil, or the fibers have lost their shape, or decreased to 50% or less compared to the previous value of the linear tensile strength of fill since there can be biodegradability is assessed as good. The diameter of the polyester § Mid fiber of the present invention, in the case of monofilaments, usually 5 0-4 is about 0 0 O m, when the multifilament is usually 1~ 5 0 ΠΙ. Polyesteramides fibers of the present invention may optionally contain pigments, dyes, antioxidants, ultraviolet absorbers, may contain various additives such as a plasticizer. Example

Examples and Comparative Examples below, will be explained more specifically the present invention. Measurement methods, such as physical properties are as follows.

(1) main dispersion peak temperature

After standing the sample in an atmosphere of 2 3 ° C, 5 0% RH (relative humidity) for 24 hours, using a dynamic viscoelasticity measuring apparatus RS A manufactured by Rheometrics, Ji jack distance 2 0 mm , at a measuring frequency 1 0 Hz, - 1 0 was heated to 1 2 0 ° C from 0 ° C at a heating rate of 2 ° CZ min, the temperature was measured dispersion curve of the loss tangent tan <5. The temperature at which the temperature dispersion curve exhibits a maximum as a main dispersion peak temperature (° C).

(2) the degree of crystallinity

Using Perkin Elmer one company made of a differential scanning calorimeter DSC 7, a sample of about 1 Omg set in a measurement cell, in a nitrogen gas atmosphere, from 3 0 ° C at 1 0 ° C / min heating rate 2 0 0 was heated to ° C was measured DSC curve. Calculated melting Entarupi ΔΗ crystals from the DSC curve (J / g), it was calculated crystallinity from the following equation (wt%).

Crystallinity = (ΔΗΖΔΗ.) XI 00

Here, ΔΗ. = 1 90. 88 (J / g)

(3) long period measured by small-angle X-ray scattering

Align the extending direction of the fibers, length 2 0 mm, aligned with the wide strips 4 mm, were prepared samples which were fixed in Xia cyanoacrylate based adhesive. Incident X-rays in a direction perpendicular to the extending direction of the fibers of the sample this. As X-ray generator manufactured by Rigaku Corporation at a low evening with flex RU- 2 0 0 B, a C u K line through the N i filter one 4 0 k V- 2 0 OmA is X-ray source. Using an imaging plate (Fuji Photo Film Co., Ltd. BAS- SR 1 2 7), sample one imaging plate distance 5 0 Omm, exposed at the exposure time of between 24 hours, using a Rigaku Co. R- AX ISDS 3 Te, it was to create a scattering angle intensity distribution curve on the meridian. It was determined long period (A) from the peak angle of the scattering angle intensity distribution curve.

(4) degree of orientation measured by wide angle X-ray scattering

Align the extending direction of the fibers, length 20 mm, aligned with the wide strips 4 mm, were prepared samples which were fixed in Xia cyanoacrylate based adhesive. Incident X-rays in a direction perpendicular to the extending direction of the fibers of the sample this. Using Rigaku Corporation rotor flex RU-20 0 B as X-ray generator, a C u K shed line through the N i filters one 3 0 k V- 1 0 0mA and the X-ray source. Imaging plate using (manufactured by Fuji Photo Film Co., Ltd. BAS- SR 1 2 7), the sample - imaging plate distance 6 Omm, exposed with an exposure time 2 0 min, using a Rigaku Co. R- AX ISDS 3, poly amide 6 alpha-type crystal (20 0) azimuth of diffraction from surface (0 angle) intensity distribution curve was created. This from the triangular intensity distribution curve, the orientation of the fiber sample as described in the first 8 1 pair one di guidance revised third edition of the X-ray diffraction of the issue Rigaku Denki Co., Ltd. (issue 1 98 5 June 3 0, 2008) according to the measuring method each time, equatorial two points on the line (beta corners 9 0 ° and 2 7 0 °) half-value width W i (in degrees) sum .SIGMA.W i (in degrees) from the orientation degree by the following equation for (% ) was determined.

The degree of orientation = [(36 0 -ΣW i) / 360] X 100

(5) linear tensile strength

After the sample was allowed to stand for 2 3 ° C, 5 0% RH of temperature and humidity controlled room with a 24-hour, with Toyo pole dough in manufactured Tensilon UTM- 3 in the same chamber, initial sample length (chuck distance) 3 300 mm, subjected to tensile test at a crosshead speed of 30 0 mm fraction, seeking breaking stress (MP a), was the measured value and the straight line tensile strength (MP a).

(6) biodegradable production (biodegradability)

The sample was removed from the filling 6 months in the soil, where the fibers of the sample which has dropped to 50% less than the value before or have lost their shape, or the linear tensile strength fill, microbial degradation sex was evaluated as good.

[Example 1]

Polyester amide copolymer [B ayer Co. B AK 1 0 9 5: nylon 6 / polybutylene adipate = 5 0 5 0 (mol%); mp (T m) 1 2 5 ° C, relative viscosity 1.47 ] supplies to 3 0 mm phi single screw extruder, melted at the end of the extruder temperature 140 ° C, extruded from a spinning nozzle with a diameter of 1. 5 mm, which is adjusted to a temperature 140 ° C, immediately temperature adjusted to 5 ° C was cooled in a water bath, and taken off at a take-up speed of 3mZ min to obtain an undrawn yarn of a diameter of 740 m. Winding the undrawn yarn on the roll, it was left at room temperature overnight (2 5 ° C). The crystallinity of the undrawn yarn after standing was 1 4.7% by weight. The undrawn yarn having enhanced the crystallinity, was stretched to the stretching ratio of 5 in the dry heat path is adjusted to a temperature 8 0 ° C, drawn fibers: was obtained (monofilament diameter 1 6 5 zxm) .

On the other hand, the fiber for 5 minutes thermally pressed at 1 40 ° C and formed into a press sheet having a thickness of 2 50 m, and a non-oriented material specimen of the polyester amide copolymer. The primary dispersion peak temperature of the non-oriented material samples, - was 1 1 ° C.

Example 2-3]

In Example 1, it was changed to 6 times the draw ratio of the undrawn yarn from 5-fold (Example 2) or 7-fold (Example 3), to give a drawn fiber and, respectively, in Examples 1 and same as It was.

[Example 4]

In Example 1, by dividing the stretching process into two stages, the first stage was stretched 5 times 4. 45 ° C, then stretched 1.3 3 times the second stage at 7 5 ° C, the total the stretching magnification except that a 6-fold, to produce the drawn fiber in the same manner as in example 1.

[Comparative Example 1-3]

In Example 1, was changed to double the draw ratio of the undrawn yarn from 5-fold (Comparative Example 1) or 3 times (Comparative Example 2) or 4 times (Comparative Example 3), respectively in Example 1 to obtain a drawn fiber in the same manner.

[Comparative Example 4]

Is supplied to the polyester amide copolymer (B ayer Co. B AK 1 0 9 5) a 3 0 mm phi single screw extruder, and melted at the end of the extruder temperature 1 40 C, was adjusted to a temperature 140 ° C extruded from a spinning nozzle having a diameter of 1. 5 mm, immediately cooled in regulated water bath to a temperature 5 ° C, taking pull in take-up speed 1 OMZ min to obtain an undrawn yarn of a diameter of 740 m. Without winding the undrawn yarn immediately temperature 2 5 ° dry heat bath which is adjusted to C, and then stretched in the stretching ratio 3.5 times, stretching the fiber: the (monofilament diameter 1 9 7 ^ m) Obtained.

[Comparative Example 5-6]

In Comparative Example 4, except for changing the 5-fold 4. draw ratio of the undrawn yarn 3. 5-fold (ratio Comparative Examples 5) or 5.5-fold (Comparative Example 6), similarly to each of Comparative Example 4 to obtain a drawn fiber in to.

[Comparative Example 7]

In Comparative Example 4, divided stretching process in three stages, was stretched 5 times 4. 1 stage at 2 5 ° C, then stretched in the second stage to 44 times 1. 2 5 ° C, further continued the 3-stage had stretched 1.1 5 times 2 5 ° C, except that stretched the entire draw ratio 7.5 times, to produce the drawn fiber in the same manner as in Comparative example 4.

[Example 5]

Drawn fibers obtained in Comparative Example 7: (monofilament total stretching ratio = 7.5 times) was allowed to stand at room temperature overnight. The crystallinity of the drawn fibers after standing is 26. was 2 wt%. The drawn fibers with increased crystallization degree was stretched 6 times 1. Temperature 8 0 ° C, it was 12 times the total draw ratio.

[Comparative Example 8]

Supplies nylon 6 (homopolymer) to 3 Ommc /) single-screw extruder, and melted at the end of the extruder temperature 2 6 0 ° C, the spinning temperature 2 60 ° C adjusted to diameter 1. 5 mm extruded from the nozzle, and immediately cooled in regulated water bath to a temperature 5 ° C, and taken off at a take-up speed 1 0 mZ min to obtain an undrawn yarn of a diameter of 7 4 0 m. Without winding the undrawn yarn immediately at a temperature of 8 5 ° regulated in dry heat path C, the stretching ratio 3. Was stretched 8 times, then the temperature 9 5 ° regulated dry heat bath to C . in 1 it was stretched 4 seven times, the total draw ratio was 5 6 fold extending Shin fibers: was obtained (monofilament diameter 1 5 6 u rn)..

Stretching conditions employed in these Examples and Comparative Examples are shown in Table 1 shows the results of measurement of physical properties in Table 2.

table 1

(Footnote) Example 5: drawn fiber obtained in Comparative Example 7 (total draw ratio = 7.5 times) after crystallization treatment was stretched

Table 2 Structure Parameters drawn fibers mechanical strength ± 曰

曰曰 main dispersion peak temperature crystallinity long period AXB King 77 straight tensile strength elongation at orientation AB / 100

Non-oriented products as the solution of

Difference (%) (° C) (in) (wt.%) (A) (MPa) (96) Comparative Example 1 85.9 -10.1 0.9 17.3 80.2 13.9 good 168.6 266 Comparative Example 2 90.3 -4.0 7.0 15.7 80.6 12.7 251.9 120 Comparative Example 3 92.9 -1.8 9.2 21.2 82.9 17.6 good 290.1 ​​58 Example 1 93.4 0.1 11.1 22.2 84.1 18.7 good 392.0 47 Example 2 93.9 1.1 12.1 L. On. 0 io. L good

Example 3 94.1 2.0 13.0 23.3 82.9 19.3 good 520.4 24 Example 4 94.4 3.0 14.0 20.1 83.3 16.7 Good 502.7 21 Example 5 95.0 3.0 14.0 22.1 83.0 18.3 good 614.5 19

88.8 -9.8 1.2 27.9 74.5 20.8 good 145.0 163 91.3 -9.8 1.2 13.7 73.9 10.1 good 199.9 81 91.5 -9.7 1.3 23.0 73.3 16.9 good 253.8 66 93.9 -8.7 2.3 26.2 79.9 20.9 good 369.5 49

94.3 34.0 103.0 35.0 poor

Industrial Applicability

According to the present invention, the linear tensile strength is high, has a moderate elongation, high strength polyester amides fiber and a manufacturing method thereof showing the biodegradability is provided. High strength polyester amides fiber of the present invention can be suitably applied to fishing line or a fishing net, use as industrial materials, such as agricultural net.

Claims

The scope of the claims
1. A fiber comprising the polyester amide copolymer, the main dispersion peak temperature in the dynamic viscoelasticity measurement of the fibers, 1 0 than the main dispersion peak temperature of the unoriented consisting of the polyesteramide copolymer polymer ° C high strength polyester amide fibers to feature high that more.
2. crystallinity of the fiber (wt%) A and the long period (A) B as measured by small-angle X-ray scattering, the formula (I)
5≤ (AXB) / 100≤ 30 (I)
High strength polyester amides fiber according to claim 1, wherein satisfying the relationship.
3. Polyester Ami de copolymers, polyamide units 5-8 0 mol% and the polyester unit 2 0-9 5 mol% and high strength polyester amides fiber according to claim 1, wherein the polyester amide copolymer consisting of.
4. polyesteramide copolymer, high-strength polyester amides fiber according to claim 1, wherein a polyester amide copolymer having a melting point of 9 0~ 1 8 0 ° C.
5. polyesteramide copolymer, 1.0 to 3.0 of the high-strength Poriesu Teruamido fiber according to claim 1, wherein the polyester Ami de copolymer have a relative viscosity.
6. polyesteramide copolymer, nylon 6 / polybutylene adipate Pies copolymer, nylon 66 Z polybutylene adipate copolymer, Na Iron 6 Z polyethylene adipate copolymer, nylon 6 6 / Poryechi Ren'ajipeto copolymer , nylon 6 / poly force caprolactone copolymer or nylon 6 6 Roh high strength polyester amides fiber of claim 1 wherein the polycaprolactone copolymer.
7. Polyester Ami de co Contact Keru main dispersion peak temperature in a dynamic viscoelasticity measurement of fibers made of polymer, the polyesteramide copolymer comprising a polymer dividend 1 0~ 1 7 ° C than the main dispersion peak temperature of Mukobutsu high intensity Po Li esteramide fiber high claim 1.
8. High strength polyesteramide fiber according to claim 1, wherein the linear tensile strength is 3 80~ 7 0 0 MP a.
9. High strength polyesters § ¾ Boku繊 of claim 1, wherein the elongation is 1 0-5 0%.
After increasing the 1 0. of polyester amide copolymer amorphous undrawn crystallinity in 1 0-3 0% by weight, high strength according to claim 1, wherein the drawn yarn obtained by drawing polyester amide fiber.
1 1. stretching the amorphous unstretched yarn made of polyester amide copolymer, then after having increased the crystallinity of the drawn yarn obtained in 1 0-3 0% by weight, and extends to the al high strength polyester amides fiber according to claim 1, wherein the drawn yarn obtained.
1 2. High strength polyesteramide fiber of claim 1 wherein the biodegradable.
1 3. melting polyester amide copolymer spun, in the manufacturing method of the polyester amide fiber drawing the undrawn yarn obtained,
(1) a polyester amide copolymer melt spun immediately temperature 20 ° C or more to obtain the amorphous unstretched yarn was cooled and solidified in an inert cooling medium under
(2) yet-step increase the crystallinity of the drawn yarn to 1 0 to 30 wt%, 'and
(3) Crystallinity 1 0-3 0-fold, the amount% of undrawn yarn total draw ratio 4. step of one-stage or multi-stage stretching in such a way that more than five times
Process for producing a high strength polyester amide fibers, characterized in that it comprises a series of steps consisting of.
14. In step (2), by placing 7 2 hours for 10 minutes the undrawn yarn in an atmosphere of 1 0 to 8 0 ° C, the crystallinity of the undrawn yarn 1 0-30 wt% the method according to claim 1 3, wherein the increase in.
1 5. In step (3), crystallinity of 1 0-3 0% by weight of undrawn yarn temperature 2 0 to 1 2 0 ° 1 stage so that the total draw ratio becomes 4.5 times or more in C also multistage stretched, this time, the temperature 5 0-1 2 0 manufacturing how of claims 1 to 3, wherein disposing at least one drawing stage of stretching in the stretching ratio 1.3 times or more ° C shall in.
1 6. melt spinning the polyester amide copolymer, the process for producing a polyester amide fiber drawing the undrawn yarn obtained,
(I) a polyester amide copolymer melt spun immediately Temperature 20 ° C The following process was cooled and solidified to obtain a non-crystalline undrawn yarn in an inert cooling medium,
(II) the undrawn yarn temperature - 1 0 ° C~5 0 ° C at a draw ratio 1. step of the drawn yarn was stretched to more than three times,
(ΙΠ) step to increase the crystallinity of the drawn yarn 10 to 30% by weight and,
(IV) a step of further 1-stage or multi-stage stretching as the total draw ratio of the drawn yarn of crystallinity 1 0-3 0% by weight is 4.5 times or more
High strength polyesters Ami de method for producing a fiber which comprises a series of steps consisting of.
1 7. In step (II), The method according to claim 1 6, wherein the stretching in draw ratio from 1.3 to 10 times the undrawn yarn at a temperature 2 0 ° C over 5 0 ° less than C.
1 8. In step (III), by placing 7 2 hours for 10 minutes the drawn yarn in an atmosphere of 1 · 0~ 80 ° C, 1 0~ 3 0 by weight of the crystallinity of the drawn yarn the method according to claim 1 6, wherein the increase in%.
1 9. In step (IV), further 1 Dhamma as total draw ratio drawn yarn of crystallinity 1 0-3 0% by weight at a temperature 2 0 to 1 2 0 ° C is 4.5 times or more others multistage stretching, time, temperature 5 0~ 1 2 0 ° C at a draw ratio 1. the process according to claim 1 6, wherein disposing at least one drawing stage of stretching at least three times.
PCT/JP2001/000792 2000-02-10 2001-02-05 High-strength polyester-amide fiber and process for producing the same WO2001059191A1 (en)

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CN103757739A (en) * 2013-12-31 2014-04-30 马海燕 Biodegradable polymer monofilament and production method thereof
CN103911002A (en) * 2014-03-14 2014-07-09 江苏华洋尼龙有限公司 Novel nanometer polyamide 66 resin
CN103952794B (en) * 2014-04-10 2016-07-06 中国石油化工股份有限公司 A polyamide ester parallel type conjugated fiber composite

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JPS54120727A (en) * 1978-03-09 1979-09-19 Agency Of Ind Science & Technol Biodegradable fiber
JPH07173716A (en) * 1993-10-28 1995-07-11 Toray Ind Inc High-strength biodegradable polylactoneamide monofilament and production thereof
US5446109A (en) * 1993-02-23 1995-08-29 Teijin Limited Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same
US5644020A (en) * 1993-08-12 1997-07-01 Bayer Aktiengesellschaft Thermoplastically processible and biodegradable aliphatic polyesteramides

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS54120727A (en) * 1978-03-09 1979-09-19 Agency Of Ind Science & Technol Biodegradable fiber
US5446109A (en) * 1993-02-23 1995-08-29 Teijin Limited Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same
US5644020A (en) * 1993-08-12 1997-07-01 Bayer Aktiengesellschaft Thermoplastically processible and biodegradable aliphatic polyesteramides
JPH07173716A (en) * 1993-10-28 1995-07-11 Toray Ind Inc High-strength biodegradable polylactoneamide monofilament and production thereof

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