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 Download PDFInfo
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- 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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- copolymer
- fiber
- polyesteramide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
Definitions
- the present invention relates to a high-strength polyesteramide fiber, and more particularly, to a high-strength polyesteramide fiber having high linear tensile strength, appropriate elongation, and showing biodegradability, and a method for producing the same.
- the high-strength polyesteramide fibers of the present invention are suitable for use as industrial materials such as fishing lines, fishing nets, and agricultural nets. Background art
- fishing lines, fishing nets, agricultural nets, and the like are formed from synthetic fibers such as polyamide monofilament, which have excellent workability, strength, durability, and heat resistance. Since such conventional synthetic fibers do not have degradability in the natural environment, for example, if fishing lines or fishing nets flow out or are left alone, they cause serious pollution problems such as marine pollution.
- Natural fibers have biodegradability, but cannot provide high performance such as high strength required for industrial materials such as fishing line, fishing net, and agricultural net. Natural fibers also lack the processability required for mass production. In contrast, certain aliphatic polyesters are known to undergo microbial degradation by adherent bacteria distributed in the oceans and rivers, and spinning technologies and equipment that have been developed for conventional synthetic resins. Since it can be processed into fibers using, it is being studied for application to biodegradable fibers.
- Japanese Patent Application Laid-Open No. H5-596111 proposes a monofilament made of polyprolactone.
- the first-stage stretching is performed at a stretching ratio of more than 5 times and less than 7 times, and then the second-stage stretching is performed in an oven at 100 ° C so that the total stretching ratio is 8 times or more.
- a high-strength polyforced prolactone monofilament was obtained by relaxation heat treatment.
- this polyforce prolactone monofilament has insufficient heat resistance, and its strength is significantly reduced under high temperature conditions.
- the fiber made of the aliphatic polyester has biodegradability, but has drawbacks such as insufficient mechanical strength and poor heat resistance.
- polyamide fibers are excellent in mechanical strength, heat resistance, workability, etc., but do not have biodegradability. Therefore, in order to improve the physical properties of the aliphatic polyester and to impart biodegradability to the polyamide, a polyester amide copolymer has been developed, and its application as a biodegradable fiber is being studied. 'For example, Japanese Patent Application Laid-Open No.
- 54-127727 discloses that a high-molecular-weight aliphatic polyester and an aliphatic polyamide are produced in an inert gas in the presence of a catalyst such as anhydrous zinc acetate. By heating to a temperature higher than their melting point, an ester-amide transesterification reaction is carried out, and a polyester resin in which a large number of low molecular weight polyester blocks and low molecular weight polyamide blocks are alternately bonded. It is disclosed that a mid copolymer is produced and melt spun to produce a biodegradable fiber. However, the publication does not show a specific example in which the polyester amide copolymer is spun into fibers.
- Japanese Patent Application Laid-Open No. 7-173713 discloses a monofilament comprising a polylactone amide copolymer comprising a polyamide unit and a polylactone unit, and a method for producing the same.
- a polylactone amide copolymer is melt-spun, solidified by cooling in an inert liquid at 60 ° C or less (preferably 26 to 60 ° C), and stretched by more than 4 times and less than 7 times. It describes a method for producing a monofilament in which a first-stage stretching is carried out at a draw ratio, and then a draw ratio at which a total draw ratio is 7 times or more is obtained.
- the polylactone amide copolymer is melt-spun at 200 ° C., cooled in 35 ° C. hot water, and immediately placed in a 80 ° C. hot water bath. After stretching the first stage at 4.5 times the stretching magnification, performing a relaxing heat treatment in warm water at 90 ° C, and then stretching the whole stretching magnification to 9.0 in a dry heat bath at 120 ° C. It is shown that a second-stage stretching was performed so as to increase the size by a factor of two, and a relaxation heat treatment was performed in a dry heat bath at 100 ° C. to produce a high-strength monofilament.
- the polyamide is melt-spun and rapidly cooled to form an undrawn yarn, and this undrawn yarn is rapidly drawn.
- the molecular chains stretched at the time of stretching cause orientational crystallization, and the orientation is fixed in both the crystalline part and the amorphous part, thereby exhibiting excellent mechanical strength.
- polyesteramide copolymer when such a spinning / drawing method is applied to a polyesteramide copolymer, it is difficult to obtain a fiber having sufficiently improved mechanical strength. That is, the polyamide segment of the polyesteramide copolymer is designed to have a short chain length so as not to impair the biodegradability of the copolymer. For this reason, polyester amide copolymer Has low crystallinity and is less likely to be oriented and crystallized than a polyamide homopolymer, or has a low crystallization rate. Therefore, if the amorphous undrawn yarn obtained by quenching is drawn, the orientation of the amorphous part cannot be fixed sufficiently, and the mechanical strength cannot be sufficiently improved.
- a polyesteramide copolymer designed to have a short chain length of polyamide segment is used as an amorphous undrawn yarn. If stretching is performed under relatively high temperature conditions exceeding C, fusing tends to occur and it is difficult to stretch satisfactorily.
- Adjusting the cooling and solidification conditions such as the cooling temperature of the undrawn yarn, and crystallizing a part of it does not provide sufficient crystallinity, or it is difficult to precisely control the crystallinity.
- a polyester amide copolymer designed with a short polyamide segment chain length is melt-spun and cooled and solidified in a cooling medium adjusted to a relatively high temperature.
- the spun yarn is still in a molten state, so it may be stretched or meandered and deformed due to the resistance of the cooling medium or the resistance of the roll.
- a polyesteramide copolymer obtained by copolymerizing an aliphatic polyester and a polyamide is expected to be a resin having both the biodegradability of an aliphatic polyester and the toughness of a polyamide. It was difficult to produce polyesteramide fibers with an excellent balance between biodegradability and mechanical strength and sufficiently high strength. Disclosure of the invention
- An object of the present invention is to provide a high-strength polyester amide fiber having remarkably high linear tensile strength, moderate elongation, and showing biodegradability, and a method for producing the same.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, found that the linear tensile strength can be significantly improved by adjusting the main dispersion peak temperature in the dynamic viscoelasticity measurement of polyesteramide fibers.
- the high-strength polyester amide fiber of the present invention is obtained by melt spinning a polyester amide copolymer, and immediately, an inert cooling medium having a temperature of 20 ° C or less, preferably 15 ° C or less, more preferably 10 ° C or less. After cooling and solidifying in a non-drawn yarn, a substantially amorphous undrawn yarn is obtained. After increasing the crystallinity of the undrawn yarn to 10 to 30% by weight, the total drawing ratio is 4.5 times or more.
- it can be produced by stretching in one step or multiple steps so that the ratio becomes 5 times or more.
- the undrawn yarn is allowed to stand at room temperature for 24 hours, for example, to sufficiently promote crystallization.
- an undrawn yarn having a crystallinity of 10 to 30% by weight is stretched in one or multiple stages at a temperature of 20 to 12 Ots so that the total draw ratio becomes 4.5 times or more.
- at least one stretching step of stretching at a stretching ratio of 1.3 times or more at 50 to 120 ° C., more preferably at 70 to 110 ° C. is particularly preferable.
- the result can be obtained.
- a substantially amorphous undrawn yarn may be drawn into a drawn yarn, and the crystallinity of the drawn yarn may be increased to 10 to 30% by weight.
- a strong polyesteramide fiber can be obtained. The present invention has been completed based on these findings.
- a fiber comprising a polyesteramide copolymer, wherein the main dispersion peak temperature in the dynamic viscoelasticity measurement of the fiber is larger than the main dispersion peak temperature of an unoriented material comprising the polyesteramide copolymer. Higher than 10 ° C A high-strength polyesteramide fiber is provided.
- (IV) A step of drawing one or more stages of a drawn yarn having a crystallinity of 10 to 30% by weight so that the total draw ratio becomes 4.5 times or more.
- the polyester amide copolymer used in the present invention has a polymer in the molecular chain. It is a polymer having a mid unit and a polyester unit.
- the proportion of each unit is preferably from 5 to 80 mol%, more preferably from 20 to 70 mol%, particularly preferably from 30 to 60 mol%, of the polyamide unit. Is preferably 20 to 95 mol%, more preferably 30 to 80 mol%, and particularly preferably 40 to 70 mol%. If the proportion of the polyamide unit is too small, the mechanical strength is poor. If the proportion is too large, biodegradability is impaired.
- the polyester unit various known polyamides are used. If a polyamide having an excessively high melting point is used, the polyester segment may be thermally decomposed during melt molding, so that polyamide 6 (nylon 6), polyamide 66 (nylon 66), or a copolymer thereof is used.
- an aliphatic polyester is preferably used from the viewpoint of biodegradability. However, as long as it shows biodegradability, an alicyclic polyester such as polycyclohexylenedimethyl adipate or an aromatic polyester is preferred. May be used alone or in combination with the aliphatic polyester.
- polybutylene adipate, polyethylene adipate, polylactone and the like are preferable.
- the method for synthesizing the polyesteramide copolymer is not particularly limited.
- a method in which a polyamide is introduced into an aliphatic polyester alternately by an amide transesterification reaction to form a polyester-amide copolymer JP-A-54-120727
- polyamide-forming compound for example, ⁇ -force prolactam
- dicarboxylic acid and polyester diol for example, polylactone diol
- Polyamide-forming compounds for example, ⁇ -force prolactam
- polyester-forming compounds for example, dibasic acid and diol; lactone
- the polyester may be Polyamide, polyethylene adipate, polybutylene adipate, etc., and polyamides include nylon 6, nylon, 66, nylon 69, nylon 61, nylon 61, 12, nylon 11, nylon 12, etc. I can do it.
- polyamide-forming compound examples include ⁇ -aminobutyric acid, ⁇ -aminovaleric acid, ⁇ -aminocaproic acid, ⁇ -aminoenanthic acid, ⁇ -aminopurilic acid, ⁇ -aminoberalgonic acid, and ⁇ -aminoundecane Acids, ⁇ —Amino carboxylic acids having 4 to 12 carbon atoms such as amino dodecanoic acid; lactams having 4 to 12 carbon atoms such as aptyrolactam, ⁇ -caprolactam, enantholactam, capryloractam, laurolactam; Is mentioned.
- polyamide-forming compound examples include a nylon salt composed of a dicarboxylic acid and a diamine.
- dicarboxylic acid include succinic acid, dataltalic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and the like.
- Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as azelaic acid and dodecanedioic acid; alicyclic dicarboxylic acids such as hydrogenated terephthalic acid and hydrogenated isophthalic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid Acid; and the diamines include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, and the like.
- dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid and dodecandioic acid; hydrogenated terephthalic acid, Alicyclic dicarboxylic acids such as hydrogenated isophthalic acid; terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such asucic acid and fluoric acid; and the like.
- aliphatic dicarboxylic acids such as succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid and dodecandioic acid
- hydrogenated terephthalic acid Alicyclic dicarboxylic acids such as hydrogenated isophthalic acid
- terephthalic acid isophthalic acid
- Aromatic dicarboxylic acids such asucic acid and fluoric acid; and the like
- examples of the polyester diol include a polylactone diol having an average molecular weight of 500 to 400, and using a dalicol compound as a reaction initiator, Synthesized from 2 lactones.
- examples of the lactone include 3-propiolactone, / 3-butyl lactone, ⁇ -valerolactone, ⁇ -force prolactone, enanthlactone, caprylolactone, laurolactone and the like.
- examples of the dibasic acid include adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, and dodecandionic acid
- examples of the diol include ethylene glycol and 1,3-propane diol.
- 1,4-butanediol 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol, 2,5-hexanediol, 2-methyl-1,4-butanediol, 3-Methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,3-dimethyl-2,3-butanediol, etc. No.
- examples of the lactone include / 3-propiolactone, i3-butyrolactone, ⁇ 5-valerolactone, ⁇ -force prolactone, enanthlactone, caprylolactone, laurolactone, and the like.
- glycolic acid, glycolide, lactic acid,] 3-hydroxybutyric acid, ⁇ -hydroxyvaleric acid and the like can also be mentioned as polyester-forming compounds.
- Polyester amide copolymers include nylon 6 ⁇ polybutylene adipate copolymer, nylon 6.6 ⁇ polybutylene adipate copolymer, and nylon 6 from the viewpoint of balance between mechanical strength and biodegradability.
- ⁇ Polyethylene copolymer, Nylon 66 / polyethylene adipate copolymer, Nylon 6 / Polycaprolactone copolymer, Nylon 66 ⁇ Poly A force prolactone copolymer is preferred.
- the melting point (Tm) of the polyesteramide copolymer is preferably at least 90 ° C, more preferably at least 100 ° C, and in many cases, about 90 to 180 ° C.
- the melting point (T m) of the polyester amide copolymer is the crystal melting peak temperature measured with a differential scanning calorimeter at a heating rate of 10 ° CZ. When multiple melting peaks appear Means the peak temperature with the largest calorific value. If the melting point is too low, the heat resistance of the polyesteramide fiber is not sufficient, and problems such as a decrease in strength in a high-temperature environment and fusing due to frictional heat during use are likely to occur. On the other hand, if the melting point is too high, the melt spinning temperature will be high, and the polyester segment will be easily decomposed.
- the relative viscosity of the polyesteramide copolymer is preferably at least 1.0, more preferably at least 1.3, and often from 1.0 to 3.0.
- the relative viscosity of the polyesteramide copolymer was determined by using hexafluoroisopropanol (HFIP) as the solvent at a concentration of 0.4 g / d1 (0.4 g of polymer per 100 m1 of solvent). Is a value measured using an Ubbelohde viscometer in an atmosphere at a temperature of 10 ° C. If the relative viscosity is too low, the degree of polymerization (or molecular weight) is too low, and it is difficult to obtain a fiber with excellent mechanical strength. If the relative viscosity is too high, unevenness in the diameter and strength of the fiber tends to occur, resulting in a uniform It becomes difficult to obtain fibers having physical properties.
- a polyesteramide fiber is produced by the following production process using a polyesteramide copolymer.
- the polyesteramide fiber is usually a monofilament, but may be a multifilament if desired.
- the method for producing a polyesteramide fiber of the present invention comprises the steps of: melt-spinning a polyesteramide copolymer; and stretching the obtained undrawn yarn.
- the polyesteramide copolymer is melt-spun and immediately cooled in an inert cooling medium at 20 ° C or lower, preferably 15 ° C or lower, more preferably 10 ° C or lower. Solidifies to obtain a substantially amorphous undrawn yarn.
- the spinning temperature during melt spinning is usually about 100 to 200 ° C.
- the spinning take-off speed is usually about 1 to 50 m / min for monofilament, and for multifilament. Usually, it is 20 to 1, 000 m / min.
- the lower limit temperature of the cooling medium depends on the type of the cooling medium, but is preferably about 0 ° C.
- the cooling medium include a liquid compound inert to a polyester amide copolymer such as water, glycerin, and ethylene glycol, and a mixture thereof. Of these, water is preferred.
- a substantially amorphous undrawn yarn having a crystallinity of preferably 5% or less, more preferably 3% or less, and often 0% is obtained.
- the crystallinity of the substantially amorphous undrawn yarn is increased to 10 to 30% by weight, preferably 12 to 28% by weight.
- Unstretched In order to increase the crystallinity of the yarn, there is a method in which the undrawn yarn obtained in the step (1) is placed in an atmosphere at 10 to 80 ° C for 10 minutes to 72 hours. Generally, it is preferable to adjust the crystallinity to a desired range by lowering the processing time as the ambient temperature is lower and shortening the processing time as the temperature is higher.
- the substantially amorphous undrawn yarn obtained in the step (1) is wound, for example, on a roll, and then wound in an atmosphere adjusted to a predetermined temperature condition.
- the wound undrawn yarn is usually placed in an atmosphere adjusted to a predetermined temperature in the range of 10 to 35 ° C for 5 to 72 hours. It is desirable to leave it still for about 10 to 30 hours.
- an undrawn yarn having a crystallinity of 10 to 30% by weight is subjected to single-stage or multi-stage drawing so that the total drawing ratio becomes 4.5 times or more.
- this step may be referred to as a crystal stretching step.
- the stretching temperature is preferably from 20 to 120 ° C., and the upper limit is adjusted so as not to exceed the melting point (Tm) of the polyester amide copolymer used.
- the stretching temperature is adjusted using a dry heat gas or a liquid heating medium adjusted to a predetermined temperature.
- the stretching is performed in one stage or in multiple stages of two or more stages.
- the stretching temperature is preferably adjusted to 50 to 120 ° C., more preferably to 70 to 110 ° C. It is particularly desirable to arrange a stretching step of stretching at a stretching temperature of 1.3 times or more at a stretching temperature in order to obtain a high-strength fiber.
- the stretching is preferably performed in a dry hot gas.
- the stretching in this stretching step can be carried out in the case of single-stage stretching, for example, by a method of performing single-stage stretching at a stretching temperature of 70 to 110 ° C. and a stretching ratio of 5 to 7 times.
- a stretching step with a stretching ratio of 1.3 times or more in the above temperature range is arranged, other stretching is, for example, less than 50 ° C such as 25 ° C. It may be performed at a temperature.
- the stretching in this stretching step can be performed in one stage or in multiple stages, and the stretching ratio is preferably 1.3 times or more and 12 times or less.
- the total stretching ratio is 4.5 times or more, preferably 5 times or more, and the upper limit is about 15 times. If the total draw ratio is too low, sufficient mechanical strength cannot be obtained.
- heat treatment may be performed at a temperature equal to or lower than the melting point (T m) in a fixed or relaxed state.
- a high-strength polyesteramide fiber having an excellent balance between biodegradability and mechanical strength can be produced by the following steps. (I) a step of melt-spinning the polyesteramide copolymer and immediately cooling and solidifying in an inert cooling medium at a temperature of 20 ° C. or lower to obtain an amorphous undrawn yarn;
- the spinning temperature during melt spinning is usually about 100 to 200 ° C., and the spinning take-off speed is usually about 1 to 50 m / min.
- the temperature of the medium is preferably 15 ° C. or less, more preferably 10 ° C.
- the stretching temperature is preferably from 0 to 40 ° C, more preferably from 10 to 35 ° C, and the stretching ratio is preferably at least 2 times, more preferably at least 3 times. Yes, in many cases, good results can be obtained with a factor of 4 to 10 times.
- this step (II) when the stretching ratio is to be increased, it is desirable to carry out multistage stretching at a stretching temperature of about 10 to 35 ° C. for about 2 to 5 times.
- the step (II) is an amorphous drawing step of drawing a substantially amorphous undrawn yarn.
- the drawn yarn obtained in the step (II) increases the degree of crystallinity to 10 to 30% by weight, preferably 12 to 28% by weight.
- the drawn yarn is preferably wound for 5 to 72 hours in an atmosphere adjusted to a predetermined temperature in the range of 10 to 35 ° C. It is preferable to leave it still for about 10 to 30 hours.
- the crystallinity of the drawn yarn is increased to the range of 10 to 30% by weight, and then the drawing step (IV) is arranged to sufficiently increase the mechanical strength. Can be enhanced.
- a drawn yarn having a crystallinity of 10 to 30% by weight is subjected to single-stage or multi-stage drawing so that the total drawing ratio becomes 4.5 times or more.
- the stretching temperature is preferably 20 to 120 ° C.
- the adjustment of the stretching temperature is performed using a dry heat gas or a liquid heating medium adjusted to a predetermined temperature.
- the stretching temperature is adjusted to preferably 50 to 120 ° C, more preferably 70 to 110 ° C, and at the stretching temperature, a stretching ratio of 1.3 times or more. It is particularly desirable to arrange a drawing step for drawing at a high temperature in order to obtain a high-strength fiber. Other stretching conditions are the same as in the above-described method.
- the main dispersion peak temperature in the dynamic viscoelasticity measurement of the fiber is at least 10 ° C higher than the main dispersion peak temperature of the non-oriented material composed of the polyesteramide copolymer, preferably Higher than 12 ° C.
- the fact that the main dispersion peak temperature of the drawn fiber is higher than that of the non-oriented one by 10 ° C or more indicates that the amorphous molecular chains are highly restricted in tension. In other words, the elongation was performed effectively, and as a result, not only the molecular chains in the crystal part of the fiber but also the molecular chains in the amorphous part were highly oriented.
- the upper limit of the temperature difference between the main dispersion peak temperatures is about 17 ° C, and often about 15 ° C.
- the crystallinity (% by weight) A of the fiber and the long period (A) B measured by small-angle X-ray scattering are represented by the following formula (I).
- the crystallinity A and the long period B measured by small angle X-ray scattering are more preferably expressed by the formula (II)
- the product of the crystallinity A and the long period B measured by small-angle X-ray scattering corresponds to the thickness of the crystal formed by crystallization of the polyamide segment.
- Fibers whose (AX B) / 100 is less than 5 have low crystallinity due to the short chain length of the polyamide segment, and the polyamide units introduced into the molecular chain are sufficient for improving mechanical strength. May not contribute.
- the biodegradability may be impaired because the chain length of the polyamide segment is too long.
- the degree of crystal orientation of the polyesteramide fiber of the present invention is preferably 90% or more, more preferably 93% or more.
- the upper limit of crystal orientation is 98% It is about. Due to the high degree of fiber crystal orientation, it has excellent mechanical strength.
- Such a polyester amide fiber can be obtained by the above-mentioned production method, and has excellent linear tensile strength and moderate elongation.
- the polyesteramide fiber of the present invention can be obtained by increasing the crystallinity of an amorphous undrawn yarn made of a polyesteramide copolymer to 10 to 30% by weight and then drawing. Further, the polyesteramide fiber of the present invention stretches an amorphous undrawn yarn made of a polyesteramide copolymer, and then increases the crystallinity of the obtained drawn yarn to 10 to 30% by weight. Thereafter, it can be obtained by further stretching.
- the linear tensile strength of the polyesteramide fiber of the present invention is usually at least 300 MPa, preferably at least 35 OMPa, more preferably at least 380 MPa, particularly preferably at least 40 OMPa.
- the linear tensile strength is often around 380 to 700 MPa.
- the elongation of the polyester amide fiber of the present invention is usually at least 10%, preferably at least 15%, and in many cases about 10 to 50%.
- the polyesteramide fiber of the present invention has good biodegradability.
- the polyesteramide fiber of the present invention When the polyesteramide fiber of the present invention is buried in soil for 6 months and then taken out, the fiber loses its shape or its linear tensile strength decreases to 50% or less of the value before the burying. Therefore, it can be evaluated that microbial degradability is good.
- the diameter of the polyester amide fiber of the present invention is usually about 50 to 400 Om in the case of a monofilament, and usually 1 to 50 mm in the case of a multifilament.
- the polyesteramide fiber of the present invention can contain various additives such as a pigment, a dye, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary.
- the sample was allowed to stand for 24 hours in an atmosphere of 23 ° C and 50% RH (relative humidity), and the distance between chucks was 20 mm using a dynamic viscoelasticity measuring device RSA manufactured by Rheometrics.
- RSA dynamic viscoelasticity measuring device manufactured by Rheometrics.
- the temperature was raised from 100 ° C to 120 ° C at a rate of 2 ° CZ, and a temperature dispersion curve with a loss tangent tan ⁇ 5 was measured.
- the temperature at which this temperature dispersion curve shows a maximum was defined as the main dispersion peak temperature (° C).
- the drawing directions of the fibers were aligned, arranged in a strip shape having a length of 20 mm and a width of 4 mm, and this was fixed with a cyanoacrylate adhesive to prepare a sample.
- X-rays were incident in a direction perpendicular to the drawing direction of the fiber of this sample.
- Ryukyu Flex RU-200B manufactured by Rigaku Denki Co., Ltd. was used as the X-ray generator, and the CuK line passed through a Ni filter at 40 kV-200 OmA was used as the X-ray source.
- the sample was exposed at a distance of 50 Omm between the imaging plate and an exposure time of 24 hours, and R-AX ISDS3 manufactured by Rigaku Denki was used. hand, A scattering angle intensity distribution curve on the meridian was created. The long period (A) was determined from the peak angle of the scattering angle intensity distribution curve.
- the fibers were oriented in the drawing direction, aligned in a strip shape with a length of 20 mm and a width of 4 mm, and fixed with a cyanoacrylate adhesive to prepare a sample.
- X-rays were incident in a direction perpendicular to the drawing direction of the fiber of this sample.
- Rotorflex RU-200B manufactured by Rigaku Corporation was used as an X-ray generator, and a Cu K wire passed through a Ni filter at 30 kV-100 mA was used as an X-ray source.
- the orientation degree (%) is calculated from the sum of the half-widths W i (degrees) ⁇ W i (degrees) at two points on the equator line ( ⁇ angles of 90 ° and 270 °) by ).
- the sample was left for 24 hours in a temperature and humidity controlled room at 23 ° C and 50% RH, and the initial sample length (distance between chucks) was set in the same room using Tensilon UTM-3 manufactured by Toyo Paul Douin.
- a tensile test was performed at 300 mm and a crosshead speed of 300 mm, the breaking stress (MPa) was determined, and the measured value was defined as the linear tensile strength (MPa).
- the sample is buried in the soil for 6 months and then removed, and the fiber of the sample has lost its shape or its linear tensile strength is 50% of the value before the burying. The case where it decreased below was evaluated as having good biodegradability.
- Tm melting point
- the undrawn yarn was wound up on a roll and allowed to stand at room temperature (25 ° C.) for 24 hours.
- the crystallinity of the undrawn yarn after standing was 14.7% by weight.
- the undrawn yarn having the increased crystallinity is drawn at a draw ratio of 5 in a dry heat path adjusted to a temperature of 80 ° C. to obtain a drawn fiber (monofilament: diameter of 16.5 zxm). .
- this fiber was heated and pressed at 140 ° C. for 5 minutes to form a pressed sheet having a thickness of 250 m, which was used as a non-oriented sample of the polyesteramide copolymer.
- the main dispersion peak temperature of this non-oriented sample was -11 ° C.
- Example 1 a drawn fiber was obtained in the same manner as in Example 1 except that the draw ratio of the undrawn yarn was changed from 5 times to 6 times (Example 2) or 7 times (Example 3).
- Example 2 a drawn fiber was obtained in the same manner as in Example 1 except that the draw ratio of the undrawn yarn was changed from 5 times to 6 times (Example 2) or 7 times (Example 3).
- Example 1 the stretching process was divided into two stages, the first stage was stretched 4.5 times at 45 ° C, and then the second stage was stretched 1.3 times at 75 ° C.
- a drawn fiber was produced in the same manner as in Example 1 except that the draw ratio was 6 times.
- Example 1 except that the stretching ratio of the undrawn yarn was changed from 5 times to 2 times (Comparative Example 1) or 3 times (Comparative Example 2) or 4 times (Comparative Example 3), In the same manner as in Example 1, drawn fibers were obtained.
- Polyester amide copolymer (Bayer BAK1095) was supplied to a 30 mm ⁇ single screw extruder, melted at an extruder tip temperature of 140 C, and adjusted to a temperature of 140 ° C. It was extruded from a spinning nozzle having a diameter of 1.5 mm, immediately cooled in a water bath adjusted to a temperature of 5 ° C, and pulled at a take-up speed of 1 OmZ to obtain an undrawn yarn having a diameter of 740 m. Without winding the undrawn yarn, the drawn fiber (monofilament: diameter: 197 ⁇ m) is drawn immediately to a draw ratio of 3.5 in a dry heat bath adjusted to a temperature of 25 ° C. Obtained.
- Comparative Example 4 the stretching process was divided into three stages, the first stage was stretched 4.5 times at 25 ° C, and the second stage was stretched 1.44 times at 25 ° C. Then, a drawn fiber was produced in the same manner as in Comparative Example 4 except that the third stage was stretched to 1.15 times at 25 ° C. and the total draw ratio was increased to 7.5 times.
- the crystallinity of the drawn fiber after standing was 26.2% by weight.
- the drawn fiber having the increased crystallinity was drawn 1.6 times at a temperature of 80 ° C., and the total drawing ratio was set to 12 times.
- Nylon 6 (homopolymer) is fed to a 3 Ommc /) single-screw extruder, and extruder is melted at a tip temperature of 260 ° C and is adjusted to a temperature of 260 ° C with a diameter of 1.5 It was extruded from a spinning nozzle having a diameter of 5 mm and immediately cooled in a water bath adjusted to a temperature of 5 ° C., and was taken out at a take-up speed of 10 mZ to obtain an undrawn yarn having a diameter of 740 m.
- Table 1 shows the stretching conditions employed in these Examples and Comparative Examples
- Table 2 shows the measurement results of physical properties.
- 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
- a high-strength polyesteramide fiber having high linear tensile strength, moderate elongation, and biodegradability, and a method for producing the same.
- the high-strength polyesteramide fiber of the present invention can be suitably applied to uses as industrial materials such as fishing lines, fishing nets, and agricultural nets.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020027010187A KR20020074506A (en) | 2000-02-10 | 2001-02-05 | High-strength polyester-amide fiber and process for producing the same |
US10/203,140 US20030032767A1 (en) | 2001-02-05 | 2001-02-05 | High-strength polyester-amide fiber and process for producing the same |
EP01902765A EP1270775A1 (en) | 2000-02-10 | 2001-02-05 | High-strength polyester-amide fiber and process for producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-33775 | 2000-02-10 | ||
JP2000033775A JP4475481B2 (en) | 2000-02-10 | 2000-02-10 | Method for producing high-strength polyesteramide fiber |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001059191A1 true WO2001059191A1 (en) | 2001-08-16 |
Family
ID=18558207
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/000792 WO2001059191A1 (en) | 2000-02-10 | 2001-02-05 | High-strength polyester-amide fiber and process for producing the same |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1270775A1 (en) |
JP (1) | JP4475481B2 (en) |
KR (1) | KR20020074506A (en) |
CN (1) | CN1401021A (en) |
TW (1) | TW503269B (en) |
WO (1) | WO2001059191A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 kind of polyesteramide parallel type conjugate complex condensating fiber |
CN106633044A (en) * | 2016-11-30 | 2017-05-10 | 彭州市运达知识产权服务有限公司 | Liquid crystal polyarylester and preparation method thereof |
JPWO2020230807A1 (en) * | 2019-05-13 | 2020-11-19 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2000
- 2000-02-10 JP JP2000033775A patent/JP4475481B2/en not_active Expired - Lifetime
-
2001
- 2001-02-05 KR KR1020027010187A patent/KR20020074506A/en not_active Application Discontinuation
- 2001-02-05 TW TW090102318A patent/TW503269B/en not_active IP Right Cessation
- 2001-02-05 EP EP01902765A patent/EP1270775A1/en not_active Withdrawn
- 2001-02-05 WO PCT/JP2001/000792 patent/WO2001059191A1/en not_active Application Discontinuation
- 2001-02-05 CN CN01804782A patent/CN1401021A/en active Pending
Patent Citations (4)
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 |
Also Published As
Publication number | Publication date |
---|---|
TW503269B (en) | 2002-09-21 |
EP1270775A1 (en) | 2003-01-02 |
KR20020074506A (en) | 2002-09-30 |
JP4475481B2 (en) | 2010-06-09 |
JP2001226824A (en) | 2001-08-21 |
CN1401021A (en) | 2003-03-05 |
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