CA1314673C - High-tenacity conjugated fiber and process for preparation thereof - Google Patents
High-tenacity conjugated fiber and process for preparation thereofInfo
- Publication number
- CA1314673C CA1314673C CA000579481A CA579481A CA1314673C CA 1314673 C CA1314673 C CA 1314673C CA 000579481 A CA000579481 A CA 000579481A CA 579481 A CA579481 A CA 579481A CA 1314673 C CA1314673 C CA 1314673C
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- Canada
- Prior art keywords
- fiber
- sheath
- denier
- core
- polyester
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S57/00—Textiles: spinning, twisting, and twining
- Y10S57/902—Reinforcing or tire cords
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
Abstract
HIGH-TENACITY CONJUGATED FIBER AND PROCESS
FOR PREPARATION THEREOF
ABSTRACT OF THE DISCLOSURE
A conjugated fiber having a sheath-core conjugated structure-comprising a polyester core component composed mainly of polyethylene terephthalate and a polyamide sheath component composed mainly of polyhexamethylene adipamide, is disclosed, which has excellent mechanical properties such as a high tenacity, a high modulus, and an improved dimensional stability, and an improved adhesion to a rubber, especially a high-temperature adhesion, an improved heat resistance in a rubber, and a high fatigue resistance, and thus is useful as an industrial material. By adopting a high-speed spinning procedure in the fiber preparing process, the peel resistance in the interface of the sheath-core conjugated structure is greatly improved, and the following valuable characteristics not possessed by conventional conjugated yarns can be obtained:
(1) Excellent adhesion and high-temperature adhesion comparable to those of a polyamide, which cannot be obtained in a polyester.
(2) High modulus and dimensional stability comparable to those of a polyester, which cannot be obtained in a polyamide.
(3) A heat resistance in a rubber and a fatigue resistance superior to those of a polyester.
FOR PREPARATION THEREOF
ABSTRACT OF THE DISCLOSURE
A conjugated fiber having a sheath-core conjugated structure-comprising a polyester core component composed mainly of polyethylene terephthalate and a polyamide sheath component composed mainly of polyhexamethylene adipamide, is disclosed, which has excellent mechanical properties such as a high tenacity, a high modulus, and an improved dimensional stability, and an improved adhesion to a rubber, especially a high-temperature adhesion, an improved heat resistance in a rubber, and a high fatigue resistance, and thus is useful as an industrial material. By adopting a high-speed spinning procedure in the fiber preparing process, the peel resistance in the interface of the sheath-core conjugated structure is greatly improved, and the following valuable characteristics not possessed by conventional conjugated yarns can be obtained:
(1) Excellent adhesion and high-temperature adhesion comparable to those of a polyamide, which cannot be obtained in a polyester.
(2) High modulus and dimensional stability comparable to those of a polyester, which cannot be obtained in a polyamide.
(3) A heat resistance in a rubber and a fatigue resistance superior to those of a polyester.
Description
- 1 131'~673 HIGH-TENACITY CONJUGATED FIBER AND PROCESS
FOR PREPARATION THEREOF
BACKGROUND OF THE INVENTII:~N
(1) Field of the Invention The present invention relates to a high-~enacity conjugated fiber having an excellent durability, and suitable for industrial uses, especially as a rubber reinforcement. More particularly, the present invention relates to a conjugated fiber for industrial uses, which has excellent mechanical properties such as a high tenacity, a high modulus and an improved dimensional stability, and an improved adhesion to a rubber, especially a high-temperature adhesion, a good heat resistance in a high-temperature rubber, and an improved fatigue resistance.
FOR PREPARATION THEREOF
BACKGROUND OF THE INVENTII:~N
(1) Field of the Invention The present invention relates to a high-~enacity conjugated fiber having an excellent durability, and suitable for industrial uses, especially as a rubber reinforcement. More particularly, the present invention relates to a conjugated fiber for industrial uses, which has excellent mechanical properties such as a high tenacity, a high modulus and an improved dimensional stability, and an improved adhesion to a rubber, especially a high-temperature adhesion, a good heat resistance in a high-temperature rubber, and an improved fatigue resistance.
(2) Description of the Related Art Polyester fibers represented by polyethylene terephthalate fibers are widely utilized or various industrial purposes because they are characterized by a high tenacity and a high elastic modulus, and these fibers are advantageously used as rubber reinforcements such as tire cords, transmission belts and conveyor belts.
Nevertheless~,ipolyester fibers have a poor heat resistance when embedded in a rubber. Namely, at a high temperature, ester bonds of polyester fibers are broken by the action of water or an amine compound contained in a rubber, resulting in a degradation of the tenacity. Furthermore, polyester fibers have a poor adhesion to a rubber, and when the polyester fibers are repeatedly exposed to a hiyh-temperature atmosphere for a long time, a problem such as drasti.c degradation of the adhesion to a rubber arises.
Tire cords composed of polyester fibers have been used in large quantities as carcass cords of radial - 2 - 1 31 '')73 tires for passenger cars, where the characteristics of a high tenacity and a high modulus are utilized. But, when these tire cords are used for larger vehicles such as vans, trucks and buses, since the heat generated during running is easily accumulated in the tire, the tenacity is reduced by thermal degradation and the adhesion to a rubber is lost, resulting in peeling.
Accordingly, the heat resistance of polyesters in a rubber must be improved to increase the adhesion at a high temperature.
Many attempts to improve the poor adhesion, a defect of polyester fibers, have been made, and in one of these attempts, a method was proposed in which the surface of a polyester is covered with a polyamide. For example, Japanese Unexamined Patent Publication No.
49-85315 discloses a process for the preparation o a conjugated yarn comprising a polyester core and a nylon 6 sheath, in which the polymerization degrees of the constituent polymers and the ratio of the core ~o polymer are specified and the spinning is carried out by applying a non-humid lubricant and carxying out a direct spin-drawing. Furthermore, Japanese Unexamined Patent Publication No. 56-140128 discloses a rubber rein~orce-ment composed of a sheath-core type conjugated fiber having a polyester core and a polyamide sheath, in which the ratio of the polyamide sheath component is 7 to 30%
by weight and an epoxy adhesive is applied to the surface of the polyamide sheath component.
In the sheath-core type conjugated yarns proposed in Japanese Unexamined Patent Publication No.
49-85315 and Japanese Unexamined Patent Publication No.
56-140128, the adhesion to a rubber is improved by the polyamide component as the sheath and the modulus or dimensional stability is maintained at a high level by the polyester component as the core. Namely, the adhesion is suficiently improved according to this process, but the modulus and dimensional stability are 1 7)1 '1673 degraded with an increase of the amount of the polyamide component as the sheath, and thus it is impossible to retain the satisfactory modulus and dimensional stability inherently possessed by the polyester fiber.
s Moreover, the heat resistance in a rubber, the fatigue resistance, and other characteristics possessed by the polyamide component, are not sufficiently utilized.
Since the compatibility between an ordinary polyester such as polyethylene terephthalate and an ordinary polyamide such as nylon 6 or nylon 66 is poor, if a conjugated fiber is prepared according to the usual spinning method, peeling or stripping often occurs at the polymer interface of the sheath-core conjugated structure, and the conjugated fiber does not have a fatigue resistance sufficient for practical applications. Especially, ~he polymer interface is destroyed by the repeated elongation-compression fatigue undergone by the fibers at the drawing step, the tire cord-processing step such as the twisting or dipping step, the tire-curing step, and during running, and thus the required performances cannot be obtained from the sheath-core conjugated ~iber.
SllM~RY OF THE INVENTION
A primary ob~ect of the present invention is to solve the foregoing problems and provide a con~ugated fiber suitable as a rubber reinforcement, having an excellent adhesion to a rubber, a high modulus and a high dimensional stability, when compared to those of a polyester, and an improved heat resistance and fatigue resistance in a rubber. Especially, the present invention provides a conjugated fiber having a high modulus and an improved dimensional stability that cannot be obtained by the conventional techniques, an improved heat resistance in a rubber, and a satisfactory resistance to peeling and stripping of the polymers at the sheath-core interface boundary.
In accordance with the present invention, there is 131 lS73 provided a high-tenacity conjugated fiber having a sheath-core conjugated structure consisting essentially of a polyester composed mainly of ethylene terephthalate units as the core component and a polyamide as the sheath component, wherein the ratio of the core compo-nent to the sum of the core component and sheath compo-nent is 30 to 90% by weight, and the conjugated fiber has (a) a dynamic elasticity (E'20) at 20C of at least 8 x 104 dyne/denier and a dynamic elasticity (E'lso) at 150C of at least 3 x 104 dyne/denier, as measured at 110 Hz, and a main dispersion peak temperature (T~) of at least 140C in the mechanic loss tangent (tan ~
curve, (b) a creep rate (CR20) not larger than 2.0% as measured at 20C after 48 hours' standing under a load of 1 g/denier and a creep rate (CRlso) not larger than 3.0% as measured at 150C after 48 hours' standing under a load of 1 g/denier, (c) an intrinsic viscosity ([~]) of at least 0.8 and a birefringence (~n) of 160 x 10-3 to 190 x 10-3 in the polyester core component, and (d) a sulfuric acid relative viscosity (~r) of at least 2.8 and a birefringence (~n) of at least 50 x 10-3 in the polyamide sheath component.
In the high~tenacity conjugated fiber of the present invention, preferably, the polyester core component has a density (P) of at least 1.395 g/cm3 and the polyamide sheath component has a density (P) of at least 1O135 g/cm3. The polyester core component prefer-ably has an initial modulus in tension (Mi) at least ~0 g/denier and a terminal modulus in tension (Mt) not larger than 20 g/denier. Furthermore, the high-tenacity conjugated fiber of the present invention preferably has a tenacity (T/D) of at least 7.5 g/denier, an initial tensile resistance (Mi) of at least 60 g/denier, and a dry heat shrinkage (~S1so) as measured at 150C not larger than 7~.
The high-tenacity conjugated fiber of the present invention can be prepared according to a process which _ 5 ~ 3 comprises forming, by melt spinning, a sheath-core high-tenacity conjugated fiber having a core formed of a polymer composed substantially of high-polymerization-degree polyethylene terephthalate having an intrinsic viscosity ([~]) of at least 0.80 and a sheath formed of a high-polymeri~ation-degree polyamide polymer having a sulfuric acid relative viscosity of at least 2.8, in which the ratio of the core component to the sum of the core component and sheath component is 30 to 90% by weight, said process being characterized in that a molten polymer fiber extruded from a spinneret is passed through an atmosphere, a portion of which over a length of at least 10 cm below the spinneret is maintained at a temperature of at least 200C; the molten pol~ner fiber is rapidly cooled to be solidified; an oiling agent is applied to the solidified polymer fiber; the fiber is taken up at a speed of at least 1,500 m/min to form an undrawn fiber in which the polyamide sheath component has a birefringence of 25 x 10-3 to 40 x 10-3 and the polyester core component has a birefringence of 25 x 20 x 10-3 to 70 x 10-3; and the undrawn fiber is subjected to multi-stage drawing including at least two stages.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The conjugated fiber of the present invention has the above-mentioned structure, and the intended mainte-nance of the modulus and dimensional stability at levels comparabla to those of a polyester, that cannot be obtained by the conventional techniques r and the intended improvement of the heat resistance and fatigue resistance in a rubber and the resistance to peeling and stripping of the polymers at the sheath-core interface can be obtained by the combination of the specific birefringences, densities, and other characteristics of the polyester as the core component and the polyamide as the sheath component. The completion of the intended fiber structure in the present invention is supported by the peculiar dynamic viscoelasticity behavior and low 1 3 1 ~
creep rate of the conjugated fiber of ~he present invention.
The respective constituent elements of the present invention and the functional effects thereof will now be described in detail.
The core component of the conjugated fiber of the present invention consists essentially of a polyester composed mainly of ethylene terephthalate units. The polyester may contain units derived from a comonomer in an amount not causing a substantial degradation of the physical and chemical properties of the polyethylene terephthalate polymer, for example, in an amount of up to 10% by weight. As the comonomer component, there can be mentioned dicarboxylic acids such isophthalic acid, naphthalene-dicarboxylic acid and diphenyl-dicarboxylic acid, diols such as propylene glycol and butylene glycol, and ethylene oxide. To attain a tenacity of at least 7 t 5 gtdenier in the conjugated fiber of the present invention, the polyethylene terephthalate fiber as the core component must have an intrinsic viscosity [~] of at least 0.8, preferably at least 0.9. To obtain an excellent heat resistance in a rubber to the conju-gated fiber of the present invention, preferably the concentration of the terminal carboxyl group in the polyester as the core component is not larger than 20 eq~106 g.
As the polyamide used as the sheath component, there can be mentioned ordinary polyamides such as polycapramide, polyhexamethylene adipamide, polytetra-methylene adipamide, polyhexamethylene sebacamide andpolyhexamethylene dodecamide. A blend or copolymer of two or more thereof can be used. Among the above, polyhexamethylene adipamide is especially preferred. To obtain the high-tenacity conjugated fiber of the present invention, the polyamide as the sheath component must also have a high degree of polymerization. Namely, the sulfuric acid relative viscosity (~r) of the polyamide ! 7 3 must be at least 2.8, preferably at least 3Ø Pref-erably, ~hat a cupric salt or other organic or inorganic compound is incorporated as a heat stabilizer in the polyamide component. Usually, 30 to 500 ppm as copper of a cupric salt such as cupric iodide, cupric acetate, cupric chloride or cupric stearate, 0.01 to 0.5% by weight of an alkali metal halide such as potassium iodide, sodium iodide or potassium bromide and/or 10 to 500 ppm as phosphorus of an organic or inorganic phosphorus compound can be incorporated.
The ratio of the core component in the conjugated fiber of the present invention is 30 to 90~ by weight.
If the ratio of the core component is lower than 30% by weight, it is difficult to maintain the modulus and dimensional stability of the con~ugated fiber at levels comparable ~o those of the polyester. If the ratio of the polyester core component exceeds 90~ by weight, the adhesion of the conjugated fiber to a rubber and the heat resistance in a rubber are not sufficiently im-proved, and attainment of the intended effects of thepresent inventicn cannot be properly obtained.
The conjugated fiber of the present invention is characterized in that either the polyester core fiber or the polyamide sheath fiber is highly orientated and crystalliz~d. More specifically, the birefringence (~n) of the polyester core component fiber is 160 x 10-3 to 190 x 10-3. If the birefringence is lower than 16~ x 10-3, a tenacity (T/D) of at least 7.5 g/denier and an initial tensile resistance (Mi) of at least 60 g/denier cannot be obtained in the conjugated fiber. On the other hand, if the birefringence exceeds 190 x 10-3, the dimensional stability and ~atigue resistance cannot be improved. The conjugated fiber prepared by the novel process of the present invention, described hereinafter, usually, has a birefringence not larger than 190 x 10-3.
The polyamide component fiber constituting the sheath is highly orientated so that the birefringence . .
- 8 - ~ 7 3 (~n) is at least 50 x 10-3, usually at least 55 x 10-3.
I-f the birefringence is lower than 50 x 10-3, a conjugated fiber having a high tenacity and a high initial modulus in tension cannot be obtained.
The measurement of the birefringence (~n) of the coresheath conjugated fiber can be carried out in the following manner. More specifically, the birefringence of the sheath is directly measured by a transmission interference microscope, and in the measurement of the birefringence of the core component, only the core polyester component fiber is sampled by dissolving the polyamide of the sheath component by hydxochloric acid, formic acid, sulfuric acid or fluorinated alcohol, and the birefringence of the core component is measured by a transmission interference microscope or by the usual Berek compensator method.
In the conjugated fiber of the present invention, the polyester as the core component has a density (P) of at least 1.395 g/cm3 and the polyamide as the sheath component has a density (P) of at least 1.135 gJcm3, and both the components are highly crystallized. If the densities are lower than the above-mentioned critical levels, the dimensional stability, the fatigue resistance and the heat resistance in a rubber are improved to only a minor degree in the conjugated fiber.
The density (P~ of the polyester as the core component is measured after removing the polyamide by dissolution in hydrochloric acid, formic acid, sulfuric acid or fluorinated alcohol. The density of the poly-amide as the component of the sheath can be calculatedfrom the density of the conjugated fiber, the density of the polyester component, and the conjugation ratio.
The above-mentioned structural features of the conjugated fiber of the present invention are supported by a specific dynamic viscoelasticity behavior and a low creep rate. More specifically, the elasticities (E'20 and E'1so) at 20C and 150C of the conjugated fiber of i i 7 the present invention as measured at 110 Hz are at least 8 x 104 dyne/denier and at least 3 x 104 dyne/denier, respectively. The dynamic elasticity at 20C of ~he conjugated fiber of the present invention is somewhat lower than that of the polyester fiber, and varies depending upon the content of the polyamide component.
At a higher temperature of 150C, the dynamic elasticity of the conjugated fiber of the present invention is comparable to or higher than that of the polyester fiber. Of course, the dynamic elasticities of the conjugated fiber of the present invention are ml~ch higher than the dynamic elasticities (E'20 and E'1so) at 20C and 150C of the nylon 66 fiber, which are about 6 x 104 dyne/denier and about 1.5 x 104 dyne/denier, respectively. The main dispersion peak temperature (T~) in the mechanic loss tangent (tan ~) curve of the conjugated fiber of the present invention is at least 140C. This value is larger than the value of nylon 6Ç, that is, about 125C, and is comparable to or larger than the value of the polyester fiber. The above-men-tioned viscoelasticity behavior cannot be explained only by combining the behaviors of the conventional polyester fiber and polyamide fiber and it is considered that this specific viscoelasticity behavior is due to the peculiar effect manifested by conjugating both the polymer components according to the present invention.
In the conjugated fiber of the present invention, the creep rates (CR20) and (CRlso) as measured at 20C
and 150C after 48 hours' standing under a load of 1 g/denier are not larger than 2.0% and not larger than 3.0%, respectively.
Although the creep rates (CR20) and (CR1so) at 20C
and 150C of nylon 66 fibers are about 5% and about 4.5%, respectively, the creep rates (CR~o) and (CRlso) at 20C and 150C of the conjugated fiber of the present invention are about 1.5% and about 2.5%, regardless of the conjugation ratio. These values are substantially 1 ') 1 ~ ;S 7 i comparable to those of the polyester fiber, and the value at a high temperature of 150~C is lower than that of the polyester fiber.
The conjugated fiber of the present invention is characterized in that, although a considerable amount of the polyamide component is contained, the presence of the polyamide component is not manifested in connection with the creep characteristics. This creep behavior of the conjugated fiber of the present invention cannot be explained only by combining the characteristics of the conventional polyester fiber and polyamide fiber, and it is considered that this specific creep behavior is due to the specific effect manifested by conjugating both the polymer components according to the present inven-tion.
The conjugated fiber of the present inventioncharacterized by the above-mentioned fiber structure preferably has a tenacity of at least 7.5 g/denier~ an initial modulus in tension of at least 60 g/denier and a dry heat shrinkage (~S1so) not larger than 7% as mea-sured at 150C. More preferable conjugated fiber char-acteristics are a tenacity of at least 8 g/denier, an initial modulus in tension of at least 70 g/denisr and a dry heat shrinkage t~Slso) not larger than 5~, and these characteristics can be obtained by appropriately combin-ing the above-mentioned structural characteristics.
The conjugated fiber of the present invention having the above-mentioned characteristics is prepared according to the following novel process.
To prepare the polyester core fiber having the above-mentioned physical properties, it is necessary to use a polymer composed substantially of polyethylene terephthalate having an intrinsic viscosity ([~]) of at least 0.80, usually at least 0.85. To obtain a fiber having an excellent heat resistance, preferably a polymer having a low terminal carboxyl group concentra-tion is spun. For example, a low-temperature polymer-, 73 ization method or a method in which a blocking agent isadded at the polymerization or spinning step can be adopte~. As the blocking agent, there can be used, for example, oxazolines, epoxides, carbodiimides, ethylene S carbonate~ oxalic acid esters and maloic acid esters.
The polyamide used as the sheath component is a high-polymerization-degree polymer having a sulfuric acid relative viscosity of at least 2.8, us-lally at least 3Ø In general, a heat stabilizer as mentioned above is added at the polymerization or spinning step.
Two extruder type spinning machines are preferably used for melt-spinning the respective polymers. The polyester core component molten by one extruder and the polyamide sheath component molten by the other extruder are guided to a conjugated spinning pack and are ex-truded through a conjugated spinning spinneret into a conjugated fiber having the polyester core component and the polyamide sheath component.
The spinning velocity is at least 1,500 m/min, preferably at least 2,000 m/min. The mol-ten polymer fiber is passed through an atmosphere, a portion of which over a length of at least 10 cm, preferably a length of 10 cm to 1 m, below the spinneret is main-tained at a temperature of at least 200C, preferably at least 260C. This high-temperature atmosphere is produced by arranging a warming cylinder, a heating cylinder or the like. After the fiber has passed through this high-temperature atmosphere, the fiber is rapidly cooled to be solidified by cold air, an oiling agent is applied to the solidified fiber and the fiber is taken up by a take-up roller for controlling the spinning speed. In the present invention, this control of the high-temperature atmosphere below the spinneret is very important for obtaining a good spinnability at the high-speed spinning step. The taken-up undrawn fiber is subsequently drawn without being once wound, although a method can be adopted in which the undrawn - 12 ~ S7~) fiber is once wound and then drawn in a different zone.
In the undrawn yarn which has just passed through the take-up roller, the polyamide sheath component has a birefringence of 25 x 10-3 to 40 x 10-3 and the poly-ester core component has a birefringence of at least 20 x 10 3, ordinarily 30 x 10-3 to 70 x 10-3, and the undrawn fiber is relatively hiyhly orientated.
The high-speed spinning according to the present invention effectively improves the modulus, dimensional stabiliky and fatigue resistance of the conjugated fiber, and another effect can be obtained of an improvement of the peel resistance of the sheath-core conjugation interface. Although a relativ~ly crystallized polyamide component is conjugated with an amorphous polyester component in the conventional low-speed spinning technique, in the high-speed spinning method adopted in the present invention, orientation and crystallization are advanced in both of the polyamide component and the polyester component and a low draw ratio is sufficient after the spinning operation. It is considered that these features contribute to an enhancement of the peel resistance in the sheath-core interface.
The undrawn fiber is then hot-drawn at a tempera-ture of at least 180C, preferably 210 to 240C. Amulti-stage drawing method including at least two stages, usually at least 3 stages, is adopted, and the draw ratio is in the range of from 1.4 to 3.5. In the present invention, also the adoption of this high-temperature hot-drawing method makes a great contribution to the enhancement of the peel resistance in the sheath-core interface. For example, where the drawing temperature at the final stage is low, e.g., below 160C, peeling often occurs in the sheath-core interface when drawing. Furthermore, it has been confirmed that, if the drawing temperature is lower than 180C, when the conjugated fiber is used as the tire .
- 13 ~ ) 7 `
cord, interface peeling OCCUX5 at the tire cord-processing step or tire-curing step or during running.
Thus, high-temperature drawing is important for obtaining the conjugated fiber of the present invention, which is substantially the same with the conventional polyester or nylon fiber for industrial uses.
The conjugated fiber of the present invention is for superior to the conventional polyester fiber with regard to the heat resistance in a rubber, the adhesion, especially the high-temperature adhesion after the high-temperature heat history, and the fatigue resistance. Furthermore, the high-tenacity conjugated fiber has an excellent durability and a combination of a high modulus and high dimensional stability as not obtained by the conventional polyamide fiber.
Accordingly, when the conjugated fiber of the present invention is used for a tire cord, the fatigue resistance of the tire cord during running is greatly improved, and therefore, the conjugated fiber is suitable as the cord material of tires for which a high fati~ue resistance is required, for example, tires of relatively large vehicles such as vans, trucks and buses and cars, driven at a high speed, such as racing cars.
Since the conjugated fiber of the present invention has the above-mentioned characteristics, it is valuable for use ~or rubber reinforcements other than tlre cords, for example, as transmission belts, conveyor belts, rubber hoses, and air springs, and for ordinary industrial materials such as sawing threads, seat belts, fishing nets, car seats, slings, cables, and ropes.
The present invention will now be described in detail with reference to the following examples. The definitions and methods of measuring the fiber charac-teristics and cord characteristics mentioned in the text of the specification and the examples are as follows.
Characteristics of Polyester Core ComPonent Fiber The polyamide as the sheath component was dissolved - 14 - 1 3 - I 7 ) out and removed from the sample by formic acid, and the remaining polyester core fiber was used for the measure-ment.
(a) Intrinsic Viscosity (~]) The sample was dissolved in o-chlorophenol and the intrinsic viscosity was measured at 25C by an Ostwald viscometer.
(b) 3irefringence (~n) The birefringence was measured by a usual serek compensator method using a sodium D-ray as the light source.
(c) Density (P) The density was measured at 25C by using a density gradient tube assembled by using carbon tetra-chloride as the heavy liquid and n~heptane as the lightliquid.
(d) Initial Modulus in Tension (Mi) and Terminal Modulus in Tension (Mt) The initial modulus in tension is defined and was measured according to JIS L~1017. The specific conditions of the tensile test for obtaining the load-elongation curve are as follows.
A sample in the shape of a shank was used and allowed to stand in a chamber maintained at a temperature of 20C and a relative humidity of 65% for more than 24 hours, and the measurement was carried out at a sample length of 25 cm and a pulling rate of 30 cm/min by using a ten5ile tester (Tensilon ~trade mark) UTL-4L supplied by Orientec K.K.).
The terminal modulus (g/denier) was determined by di~iding the stress increase between the stress at the point of the elongation smaller by 2.4% than the elongation at break in the load-elongation curve and the stress at the breaking point by 2.4 x 10-2.
Characteristics of_Polyamide Sheath Component Fiber (e) Sulfuric Acid Relative Viscosity (~r) ! The sample was dissolved in formic acid, and i ~ .
- 15 - 1 31~)7~'~
the dissolved portion was precipitated, washed and dried by usual procedures to obtain a sample for the measurement.
Then, 1 g of the sample was dissolved in 25 cc of 98% sulfuric acid and the viscosity was measured at 25C by an Ostwald viscometer.
(f) Birefringence (~n) The measurement was conducted only on the polyamide sheath at intervals of 2 ~m from the side face of the fiber toward the center, by the interference fringe method using a transmission interference microscope supplied by Karl-Zeitz-Iena Inc., and the average value was calculated.
(g) Density (P) The densities of the conjugated fiber and the polyester core fiber component were measured, and the density of the polyamide fiber component was calculated from these densities and the conjugation ratio.
Characteristics of Coniuqated Fiber ~h) Tenacity (T/D), Elongati~n (E) and Initial Modulus in Tension (Mi) The tenacity and initial modulus are defined and were measured according to JIS L-1017. The condi-tions for obtaining the load-elongation curve were the same as described above with respect to the polyester core component fiber.
(i) Dry Heat Shrinkage (~S150) A sample in the shape of a shank was used and allowed to stand in a chamber maintained at a temperature of 20C and a relative humidity of 65~ for more than 24 hours, and the sample having a length L0 as measured under a load of 0.1 g/denier was treated in the unstretched state in an oven maintained at 150C for 30 minute~. The treated sample was air-dried and allowed to stand in the above-mentioned conditioned chamber for more than 24 hours. Then, the length Ll was measured under the above-mentioned load. The dry heat shrinkage - 16 - ¦ ..J ~ ~r ~.~ 7 was calculated according to -the following formula:
Dry heat shrinkage (%) = [(L0 - L1)/L0] x 100 (j) Dynamic Elasticities (E'20 and E'150) and Main Dispersion Peak Temperature (T~) The measurement was carried out in an air bath at a frequency of 110 Hz and a temperature-ele~ating rate of 3C/m.in by using Vibron (trade mark) DDV-II
supplied by Orientec X.K.
(k) Creep Rates (CR20 and CRlso) A sample having a length L0 was allowed to stand under a load of 1 g/denier for 48 hours and ~he length L1 of the sample was measured at 20C and 150C
by using a thermal shock static viscoelasticity tester supplied by Iwamoto Seisakusho K.~., and the creep rates (CR20 and CR1so) were calculated according to the following formula:
CR20 or CR150 = [tLl - L0)/L0] x 100 (~) Characteristics of Coniuqated Fiber Cord (1) Tenacity (T/D), Elongation (E), Initial Modulus in Tension (Mi) and Medium Elongation ~ME) The measurement was conducted in the same manner as described above with respect to the fiber components. The medium elongation is the elongation at which the cord shows the tenacity of (6.75 x D
x n)/(1500 x 2) kg where D stands for the fineness o~
the drawn yarn and n stands for the number of the raw yarns. For example, in the case of a cord 1500/2 formed ! by twisting two drawn yarns each having a fineness o 1500 denier, the elongation at which the tenacity is 6.75 ~g is the medium elongation.
(m) Dry Heat Shrinkage (~S177) The measurement was conducted in the same manner as described in (i) above with respect to the conjugated fiber except that the heat treatment tempera-ture was changed to 177C.
, (n) GY Fatigue Life The GY fatigue life was determined according ~D~ ' - 17 1 ~S 1 ~j i`,73 to the mathod A of JIS L1017-1.3.2.1. The bending angle was adjusted to 90.
(o) GD Fatigue Test The GD fatigue test was carried out according ~o JIS L1017-1.3.2.2. The elongation was 6.3% and the compression was 12.6%.
(p) Adhesion The adhesion was determined according to ~he method A of JIS L1017-3.3.1.
(q) High-Temperature Adhesion The high-temperature adhesion was evaluated in the same manner as described in ~p) above except that the curing heat treatment was carried out at 170C for 50 minutes.
(r) Heat Resistance (Maintenance of Tenacity~ in Rubber Dipped cords were arranged on a rubber sheet, another rubber sheet was placed on the dipped cords to sandwich the dipped cords between the rubber sheets, and the assembly was heat-treated for 3 hours under a pressure of 50 kg/cm2 by a pressing machine heated at 170C. The tenacity of the cords was measured before and after the heat treatment and the tenacity retention ratio was calculated as the criteria of the heat resistance.
E~amples 1 throuqh 4 and Comparative Examples 1 throuq~ 4 Polyethylene therephthalate (PET) having an in-trinsic viscosity ([~]) of O . 9 6 and a terminal carboxyl group concentration of 9.0 eq/106 g was used as the core component and nylon 66 (N66, sulfuric acid relative viscosity ~r = 3. 6 ) containing 0.02% by weight of cupric iodide, 0.1% by weight of potassium iodide and 0.1~ by weight of potassium bromide was used as the sheath component, and both polymers were melted by extruder type spinning machines having a diameter of 40 mm, guided intb a conjugated spinning pack and extruded from , ..
- 18 - 1 3 1 ' ~?~
a sheath-core conjugated spinning spinneret in the form of a conjugated fiber comprising the core of PET and the sheath o~ N66. The ratios of the core and sheath components were as shown in Table 1. The spinneret used had 120 orifices, each ha~ing a diameter of 0.~ mm. PET
when the core was melted at 295C and N66 when the sheath was melted at 290C, and spinning was carried out at a spinning pack temperature of 295C. A heating cylinder having a length of 15 cm was attached j~lSt below the spinneret and h~ating was effected so that the atmosphere in the cylinder was maintained at 290C. The atmosphere temperature was the temperature of the atmos-phere at the point 10 cm below the spinneret surface and apart inwardly by 1 cm from the ~3utermost circumference of a bundle of spun fibers. ~ lateral uniflow chimney having a length of 120 cm was attached below the heating cylinder and cold air maintained at 20C was blown at a rate of 30 m/min at a right angle to -the spun fibers to effect a rapid cooling. Then, an oiling agent was applied to the spun fibers, and the fi~er speed was controlled by a ta~e-up roll rotated at a speed shown in Table 1. The take-up roll temperature was 60C.
The fibers were continuously drawn without being once wound. Three-stage drawing was carried out by using five pairs of Nelson rolls. The first drawing roll temperature was 110C, the second drawing roll temperature was 190C, and the third drawing roll temperature was 230C. The tension control roller arranged downstream from the third drawing rollers was not heated. The draw ratio at the first stage was 70%
of the total draw ratio and the remaining draw ratio was obtained at the second and third stages. The drawn fibers were subjected to a relax annealing treatment to give a 3% relaxation to the drawn fibers, and then wound.
Various fibers were prepared by adopting different spinning speeds and total draw ratios, but the extrusion - 19 131 ~iS73 rate was changed accordinq to the spinning speed and draw ratio so ~hat the fineness of the drawn fibers was about 500 denier. Three bundles of drawn fibers were combined to form a drawn yarn having a fineness of 1500 denier.
For comparison, the polyester and polyamide used for the conjugated fibers were independently spun and drawn to obtain drawn fibers. For the polyamide, the same spinning and drawing conditions as described above were adopted, and the polyester was spun and drawn in the same manner as described above except that the temperature of the third drawing roller was changed to 2~5C
The fiber-preparing conditions are shown in Table 1, the characteristics and fiber structure parame-ters of the obtained drawn fibers are shown in columns of Examples 1 through 4 and Comparative Examples 1 and 3 in Table 2, and the results of the measurement of the characteristics of a commercially available PET fiber for a tire cord (1500D-288fil-702C) [Comparative Exam-ple 2] and a commercially available N66 fiber ~1260D-204fil-1781) [Comparative Example 4] are shown in Table 20 The conjugated fibers of the present invention (Examples 1 through 4) show dynamic elasticity and creep rate characteristics similar to those of the polyester fiber, although a large quantity of the N66 component is contained, and it can be s~en that the conjugated fibers of the present invention are extraordinary.
Green cords of 1500D/2 were prepared by using the conjugated fibers of the present invention (Examples 1 through 4) and PET fibers [Comparative Examples 1 and 2]
and applying first and second twists of 40 T/10 cm in the opposite directions. Furthermore, green cords of 35 1260D~2 were prepared by using N66 fibers [Comparative Examples 3 and 4] and applying first and second twists of 39 T/10 cm in the opposite directions.
1 3 1 ~1 S / -) The green cord composed of the conjugated fibers of the present in~ention was formed into a di~ped cord by applying the adhesive and carrying out the heat treatment by usual procedures using a "Computreater"
dipping machine supplied by C.A. Litzler Inc. The dipping solution contained 20~ by weight of an adhesive component composed of a resorcine, formalin and latex, and the treatment was carried out so that the adhesive component was applied to the cord in an amount of about 4% by weight. The heat treatment was conducted at 225C
for 80 seconds while the cord was stretched so that the medium elongation of the dipped cord was about 5%.
The green cord of N66 fibers [Comparative Exam-ples 3 and 4] was heat-treated in the same manner as described above with respect to the conjugated fibers o~
the present invention except that stretching was per-formed so that the medium elongation was set at a level of about 9%, generally applied to an ordinary N66 tire cord.
The green cord of ~E~ fibers [Comparative ~xam-ples 1 and 2] was subjected to the customary two-bath adhesion treatment, the heat treatment was carried out at 240C for 120 seconds, and s~retching was performed so that the medium elongation was set at a level of about 5%, generally applied to an ordinary PET tire cord.
The tire cord characteristics of the thus-obtained dipped cords, such as the heat resistance in a rubber, the adhesion and the fatigue resistance were evaluated.
The results are shown in Table 3.
It can be seen that the dipped cord composed of the conjugated fibers of the present invention has an initial modulus and dimensional stability comparable to those of the conventional dipped cord composed of PET
fibers and this dip cord is a high-tenacity dipped cord having a highly improved heat resistance in a rubber, high-temperature adhesion, and fatigue resistance.
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Nevertheless~,ipolyester fibers have a poor heat resistance when embedded in a rubber. Namely, at a high temperature, ester bonds of polyester fibers are broken by the action of water or an amine compound contained in a rubber, resulting in a degradation of the tenacity. Furthermore, polyester fibers have a poor adhesion to a rubber, and when the polyester fibers are repeatedly exposed to a hiyh-temperature atmosphere for a long time, a problem such as drasti.c degradation of the adhesion to a rubber arises.
Tire cords composed of polyester fibers have been used in large quantities as carcass cords of radial - 2 - 1 31 '')73 tires for passenger cars, where the characteristics of a high tenacity and a high modulus are utilized. But, when these tire cords are used for larger vehicles such as vans, trucks and buses, since the heat generated during running is easily accumulated in the tire, the tenacity is reduced by thermal degradation and the adhesion to a rubber is lost, resulting in peeling.
Accordingly, the heat resistance of polyesters in a rubber must be improved to increase the adhesion at a high temperature.
Many attempts to improve the poor adhesion, a defect of polyester fibers, have been made, and in one of these attempts, a method was proposed in which the surface of a polyester is covered with a polyamide. For example, Japanese Unexamined Patent Publication No.
49-85315 discloses a process for the preparation o a conjugated yarn comprising a polyester core and a nylon 6 sheath, in which the polymerization degrees of the constituent polymers and the ratio of the core ~o polymer are specified and the spinning is carried out by applying a non-humid lubricant and carxying out a direct spin-drawing. Furthermore, Japanese Unexamined Patent Publication No. 56-140128 discloses a rubber rein~orce-ment composed of a sheath-core type conjugated fiber having a polyester core and a polyamide sheath, in which the ratio of the polyamide sheath component is 7 to 30%
by weight and an epoxy adhesive is applied to the surface of the polyamide sheath component.
In the sheath-core type conjugated yarns proposed in Japanese Unexamined Patent Publication No.
49-85315 and Japanese Unexamined Patent Publication No.
56-140128, the adhesion to a rubber is improved by the polyamide component as the sheath and the modulus or dimensional stability is maintained at a high level by the polyester component as the core. Namely, the adhesion is suficiently improved according to this process, but the modulus and dimensional stability are 1 7)1 '1673 degraded with an increase of the amount of the polyamide component as the sheath, and thus it is impossible to retain the satisfactory modulus and dimensional stability inherently possessed by the polyester fiber.
s Moreover, the heat resistance in a rubber, the fatigue resistance, and other characteristics possessed by the polyamide component, are not sufficiently utilized.
Since the compatibility between an ordinary polyester such as polyethylene terephthalate and an ordinary polyamide such as nylon 6 or nylon 66 is poor, if a conjugated fiber is prepared according to the usual spinning method, peeling or stripping often occurs at the polymer interface of the sheath-core conjugated structure, and the conjugated fiber does not have a fatigue resistance sufficient for practical applications. Especially, ~he polymer interface is destroyed by the repeated elongation-compression fatigue undergone by the fibers at the drawing step, the tire cord-processing step such as the twisting or dipping step, the tire-curing step, and during running, and thus the required performances cannot be obtained from the sheath-core conjugated ~iber.
SllM~RY OF THE INVENTION
A primary ob~ect of the present invention is to solve the foregoing problems and provide a con~ugated fiber suitable as a rubber reinforcement, having an excellent adhesion to a rubber, a high modulus and a high dimensional stability, when compared to those of a polyester, and an improved heat resistance and fatigue resistance in a rubber. Especially, the present invention provides a conjugated fiber having a high modulus and an improved dimensional stability that cannot be obtained by the conventional techniques, an improved heat resistance in a rubber, and a satisfactory resistance to peeling and stripping of the polymers at the sheath-core interface boundary.
In accordance with the present invention, there is 131 lS73 provided a high-tenacity conjugated fiber having a sheath-core conjugated structure consisting essentially of a polyester composed mainly of ethylene terephthalate units as the core component and a polyamide as the sheath component, wherein the ratio of the core compo-nent to the sum of the core component and sheath compo-nent is 30 to 90% by weight, and the conjugated fiber has (a) a dynamic elasticity (E'20) at 20C of at least 8 x 104 dyne/denier and a dynamic elasticity (E'lso) at 150C of at least 3 x 104 dyne/denier, as measured at 110 Hz, and a main dispersion peak temperature (T~) of at least 140C in the mechanic loss tangent (tan ~
curve, (b) a creep rate (CR20) not larger than 2.0% as measured at 20C after 48 hours' standing under a load of 1 g/denier and a creep rate (CRlso) not larger than 3.0% as measured at 150C after 48 hours' standing under a load of 1 g/denier, (c) an intrinsic viscosity ([~]) of at least 0.8 and a birefringence (~n) of 160 x 10-3 to 190 x 10-3 in the polyester core component, and (d) a sulfuric acid relative viscosity (~r) of at least 2.8 and a birefringence (~n) of at least 50 x 10-3 in the polyamide sheath component.
In the high~tenacity conjugated fiber of the present invention, preferably, the polyester core component has a density (P) of at least 1.395 g/cm3 and the polyamide sheath component has a density (P) of at least 1O135 g/cm3. The polyester core component prefer-ably has an initial modulus in tension (Mi) at least ~0 g/denier and a terminal modulus in tension (Mt) not larger than 20 g/denier. Furthermore, the high-tenacity conjugated fiber of the present invention preferably has a tenacity (T/D) of at least 7.5 g/denier, an initial tensile resistance (Mi) of at least 60 g/denier, and a dry heat shrinkage (~S1so) as measured at 150C not larger than 7~.
The high-tenacity conjugated fiber of the present invention can be prepared according to a process which _ 5 ~ 3 comprises forming, by melt spinning, a sheath-core high-tenacity conjugated fiber having a core formed of a polymer composed substantially of high-polymerization-degree polyethylene terephthalate having an intrinsic viscosity ([~]) of at least 0.80 and a sheath formed of a high-polymeri~ation-degree polyamide polymer having a sulfuric acid relative viscosity of at least 2.8, in which the ratio of the core component to the sum of the core component and sheath component is 30 to 90% by weight, said process being characterized in that a molten polymer fiber extruded from a spinneret is passed through an atmosphere, a portion of which over a length of at least 10 cm below the spinneret is maintained at a temperature of at least 200C; the molten pol~ner fiber is rapidly cooled to be solidified; an oiling agent is applied to the solidified polymer fiber; the fiber is taken up at a speed of at least 1,500 m/min to form an undrawn fiber in which the polyamide sheath component has a birefringence of 25 x 10-3 to 40 x 10-3 and the polyester core component has a birefringence of 25 x 20 x 10-3 to 70 x 10-3; and the undrawn fiber is subjected to multi-stage drawing including at least two stages.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The conjugated fiber of the present invention has the above-mentioned structure, and the intended mainte-nance of the modulus and dimensional stability at levels comparabla to those of a polyester, that cannot be obtained by the conventional techniques r and the intended improvement of the heat resistance and fatigue resistance in a rubber and the resistance to peeling and stripping of the polymers at the sheath-core interface can be obtained by the combination of the specific birefringences, densities, and other characteristics of the polyester as the core component and the polyamide as the sheath component. The completion of the intended fiber structure in the present invention is supported by the peculiar dynamic viscoelasticity behavior and low 1 3 1 ~
creep rate of the conjugated fiber of ~he present invention.
The respective constituent elements of the present invention and the functional effects thereof will now be described in detail.
The core component of the conjugated fiber of the present invention consists essentially of a polyester composed mainly of ethylene terephthalate units. The polyester may contain units derived from a comonomer in an amount not causing a substantial degradation of the physical and chemical properties of the polyethylene terephthalate polymer, for example, in an amount of up to 10% by weight. As the comonomer component, there can be mentioned dicarboxylic acids such isophthalic acid, naphthalene-dicarboxylic acid and diphenyl-dicarboxylic acid, diols such as propylene glycol and butylene glycol, and ethylene oxide. To attain a tenacity of at least 7 t 5 gtdenier in the conjugated fiber of the present invention, the polyethylene terephthalate fiber as the core component must have an intrinsic viscosity [~] of at least 0.8, preferably at least 0.9. To obtain an excellent heat resistance in a rubber to the conju-gated fiber of the present invention, preferably the concentration of the terminal carboxyl group in the polyester as the core component is not larger than 20 eq~106 g.
As the polyamide used as the sheath component, there can be mentioned ordinary polyamides such as polycapramide, polyhexamethylene adipamide, polytetra-methylene adipamide, polyhexamethylene sebacamide andpolyhexamethylene dodecamide. A blend or copolymer of two or more thereof can be used. Among the above, polyhexamethylene adipamide is especially preferred. To obtain the high-tenacity conjugated fiber of the present invention, the polyamide as the sheath component must also have a high degree of polymerization. Namely, the sulfuric acid relative viscosity (~r) of the polyamide ! 7 3 must be at least 2.8, preferably at least 3Ø Pref-erably, ~hat a cupric salt or other organic or inorganic compound is incorporated as a heat stabilizer in the polyamide component. Usually, 30 to 500 ppm as copper of a cupric salt such as cupric iodide, cupric acetate, cupric chloride or cupric stearate, 0.01 to 0.5% by weight of an alkali metal halide such as potassium iodide, sodium iodide or potassium bromide and/or 10 to 500 ppm as phosphorus of an organic or inorganic phosphorus compound can be incorporated.
The ratio of the core component in the conjugated fiber of the present invention is 30 to 90~ by weight.
If the ratio of the core component is lower than 30% by weight, it is difficult to maintain the modulus and dimensional stability of the con~ugated fiber at levels comparable ~o those of the polyester. If the ratio of the polyester core component exceeds 90~ by weight, the adhesion of the conjugated fiber to a rubber and the heat resistance in a rubber are not sufficiently im-proved, and attainment of the intended effects of thepresent inventicn cannot be properly obtained.
The conjugated fiber of the present invention is characterized in that either the polyester core fiber or the polyamide sheath fiber is highly orientated and crystalliz~d. More specifically, the birefringence (~n) of the polyester core component fiber is 160 x 10-3 to 190 x 10-3. If the birefringence is lower than 16~ x 10-3, a tenacity (T/D) of at least 7.5 g/denier and an initial tensile resistance (Mi) of at least 60 g/denier cannot be obtained in the conjugated fiber. On the other hand, if the birefringence exceeds 190 x 10-3, the dimensional stability and ~atigue resistance cannot be improved. The conjugated fiber prepared by the novel process of the present invention, described hereinafter, usually, has a birefringence not larger than 190 x 10-3.
The polyamide component fiber constituting the sheath is highly orientated so that the birefringence . .
- 8 - ~ 7 3 (~n) is at least 50 x 10-3, usually at least 55 x 10-3.
I-f the birefringence is lower than 50 x 10-3, a conjugated fiber having a high tenacity and a high initial modulus in tension cannot be obtained.
The measurement of the birefringence (~n) of the coresheath conjugated fiber can be carried out in the following manner. More specifically, the birefringence of the sheath is directly measured by a transmission interference microscope, and in the measurement of the birefringence of the core component, only the core polyester component fiber is sampled by dissolving the polyamide of the sheath component by hydxochloric acid, formic acid, sulfuric acid or fluorinated alcohol, and the birefringence of the core component is measured by a transmission interference microscope or by the usual Berek compensator method.
In the conjugated fiber of the present invention, the polyester as the core component has a density (P) of at least 1.395 g/cm3 and the polyamide as the sheath component has a density (P) of at least 1.135 gJcm3, and both the components are highly crystallized. If the densities are lower than the above-mentioned critical levels, the dimensional stability, the fatigue resistance and the heat resistance in a rubber are improved to only a minor degree in the conjugated fiber.
The density (P~ of the polyester as the core component is measured after removing the polyamide by dissolution in hydrochloric acid, formic acid, sulfuric acid or fluorinated alcohol. The density of the poly-amide as the component of the sheath can be calculatedfrom the density of the conjugated fiber, the density of the polyester component, and the conjugation ratio.
The above-mentioned structural features of the conjugated fiber of the present invention are supported by a specific dynamic viscoelasticity behavior and a low creep rate. More specifically, the elasticities (E'20 and E'1so) at 20C and 150C of the conjugated fiber of i i 7 the present invention as measured at 110 Hz are at least 8 x 104 dyne/denier and at least 3 x 104 dyne/denier, respectively. The dynamic elasticity at 20C of ~he conjugated fiber of the present invention is somewhat lower than that of the polyester fiber, and varies depending upon the content of the polyamide component.
At a higher temperature of 150C, the dynamic elasticity of the conjugated fiber of the present invention is comparable to or higher than that of the polyester fiber. Of course, the dynamic elasticities of the conjugated fiber of the present invention are ml~ch higher than the dynamic elasticities (E'20 and E'1so) at 20C and 150C of the nylon 66 fiber, which are about 6 x 104 dyne/denier and about 1.5 x 104 dyne/denier, respectively. The main dispersion peak temperature (T~) in the mechanic loss tangent (tan ~) curve of the conjugated fiber of the present invention is at least 140C. This value is larger than the value of nylon 6Ç, that is, about 125C, and is comparable to or larger than the value of the polyester fiber. The above-men-tioned viscoelasticity behavior cannot be explained only by combining the behaviors of the conventional polyester fiber and polyamide fiber and it is considered that this specific viscoelasticity behavior is due to the peculiar effect manifested by conjugating both the polymer components according to the present invention.
In the conjugated fiber of the present invention, the creep rates (CR20) and (CRlso) as measured at 20C
and 150C after 48 hours' standing under a load of 1 g/denier are not larger than 2.0% and not larger than 3.0%, respectively.
Although the creep rates (CR20) and (CR1so) at 20C
and 150C of nylon 66 fibers are about 5% and about 4.5%, respectively, the creep rates (CR~o) and (CRlso) at 20C and 150C of the conjugated fiber of the present invention are about 1.5% and about 2.5%, regardless of the conjugation ratio. These values are substantially 1 ') 1 ~ ;S 7 i comparable to those of the polyester fiber, and the value at a high temperature of 150~C is lower than that of the polyester fiber.
The conjugated fiber of the present invention is characterized in that, although a considerable amount of the polyamide component is contained, the presence of the polyamide component is not manifested in connection with the creep characteristics. This creep behavior of the conjugated fiber of the present invention cannot be explained only by combining the characteristics of the conventional polyester fiber and polyamide fiber, and it is considered that this specific creep behavior is due to the specific effect manifested by conjugating both the polymer components according to the present inven-tion.
The conjugated fiber of the present inventioncharacterized by the above-mentioned fiber structure preferably has a tenacity of at least 7.5 g/denier~ an initial modulus in tension of at least 60 g/denier and a dry heat shrinkage (~S1so) not larger than 7% as mea-sured at 150C. More preferable conjugated fiber char-acteristics are a tenacity of at least 8 g/denier, an initial modulus in tension of at least 70 g/denisr and a dry heat shrinkage t~Slso) not larger than 5~, and these characteristics can be obtained by appropriately combin-ing the above-mentioned structural characteristics.
The conjugated fiber of the present invention having the above-mentioned characteristics is prepared according to the following novel process.
To prepare the polyester core fiber having the above-mentioned physical properties, it is necessary to use a polymer composed substantially of polyethylene terephthalate having an intrinsic viscosity ([~]) of at least 0.80, usually at least 0.85. To obtain a fiber having an excellent heat resistance, preferably a polymer having a low terminal carboxyl group concentra-tion is spun. For example, a low-temperature polymer-, 73 ization method or a method in which a blocking agent isadded at the polymerization or spinning step can be adopte~. As the blocking agent, there can be used, for example, oxazolines, epoxides, carbodiimides, ethylene S carbonate~ oxalic acid esters and maloic acid esters.
The polyamide used as the sheath component is a high-polymerization-degree polymer having a sulfuric acid relative viscosity of at least 2.8, us-lally at least 3Ø In general, a heat stabilizer as mentioned above is added at the polymerization or spinning step.
Two extruder type spinning machines are preferably used for melt-spinning the respective polymers. The polyester core component molten by one extruder and the polyamide sheath component molten by the other extruder are guided to a conjugated spinning pack and are ex-truded through a conjugated spinning spinneret into a conjugated fiber having the polyester core component and the polyamide sheath component.
The spinning velocity is at least 1,500 m/min, preferably at least 2,000 m/min. The mol-ten polymer fiber is passed through an atmosphere, a portion of which over a length of at least 10 cm, preferably a length of 10 cm to 1 m, below the spinneret is main-tained at a temperature of at least 200C, preferably at least 260C. This high-temperature atmosphere is produced by arranging a warming cylinder, a heating cylinder or the like. After the fiber has passed through this high-temperature atmosphere, the fiber is rapidly cooled to be solidified by cold air, an oiling agent is applied to the solidified fiber and the fiber is taken up by a take-up roller for controlling the spinning speed. In the present invention, this control of the high-temperature atmosphere below the spinneret is very important for obtaining a good spinnability at the high-speed spinning step. The taken-up undrawn fiber is subsequently drawn without being once wound, although a method can be adopted in which the undrawn - 12 ~ S7~) fiber is once wound and then drawn in a different zone.
In the undrawn yarn which has just passed through the take-up roller, the polyamide sheath component has a birefringence of 25 x 10-3 to 40 x 10-3 and the poly-ester core component has a birefringence of at least 20 x 10 3, ordinarily 30 x 10-3 to 70 x 10-3, and the undrawn fiber is relatively hiyhly orientated.
The high-speed spinning according to the present invention effectively improves the modulus, dimensional stabiliky and fatigue resistance of the conjugated fiber, and another effect can be obtained of an improvement of the peel resistance of the sheath-core conjugation interface. Although a relativ~ly crystallized polyamide component is conjugated with an amorphous polyester component in the conventional low-speed spinning technique, in the high-speed spinning method adopted in the present invention, orientation and crystallization are advanced in both of the polyamide component and the polyester component and a low draw ratio is sufficient after the spinning operation. It is considered that these features contribute to an enhancement of the peel resistance in the sheath-core interface.
The undrawn fiber is then hot-drawn at a tempera-ture of at least 180C, preferably 210 to 240C. Amulti-stage drawing method including at least two stages, usually at least 3 stages, is adopted, and the draw ratio is in the range of from 1.4 to 3.5. In the present invention, also the adoption of this high-temperature hot-drawing method makes a great contribution to the enhancement of the peel resistance in the sheath-core interface. For example, where the drawing temperature at the final stage is low, e.g., below 160C, peeling often occurs in the sheath-core interface when drawing. Furthermore, it has been confirmed that, if the drawing temperature is lower than 180C, when the conjugated fiber is used as the tire .
- 13 ~ ) 7 `
cord, interface peeling OCCUX5 at the tire cord-processing step or tire-curing step or during running.
Thus, high-temperature drawing is important for obtaining the conjugated fiber of the present invention, which is substantially the same with the conventional polyester or nylon fiber for industrial uses.
The conjugated fiber of the present invention is for superior to the conventional polyester fiber with regard to the heat resistance in a rubber, the adhesion, especially the high-temperature adhesion after the high-temperature heat history, and the fatigue resistance. Furthermore, the high-tenacity conjugated fiber has an excellent durability and a combination of a high modulus and high dimensional stability as not obtained by the conventional polyamide fiber.
Accordingly, when the conjugated fiber of the present invention is used for a tire cord, the fatigue resistance of the tire cord during running is greatly improved, and therefore, the conjugated fiber is suitable as the cord material of tires for which a high fati~ue resistance is required, for example, tires of relatively large vehicles such as vans, trucks and buses and cars, driven at a high speed, such as racing cars.
Since the conjugated fiber of the present invention has the above-mentioned characteristics, it is valuable for use ~or rubber reinforcements other than tlre cords, for example, as transmission belts, conveyor belts, rubber hoses, and air springs, and for ordinary industrial materials such as sawing threads, seat belts, fishing nets, car seats, slings, cables, and ropes.
The present invention will now be described in detail with reference to the following examples. The definitions and methods of measuring the fiber charac-teristics and cord characteristics mentioned in the text of the specification and the examples are as follows.
Characteristics of Polyester Core ComPonent Fiber The polyamide as the sheath component was dissolved - 14 - 1 3 - I 7 ) out and removed from the sample by formic acid, and the remaining polyester core fiber was used for the measure-ment.
(a) Intrinsic Viscosity (~]) The sample was dissolved in o-chlorophenol and the intrinsic viscosity was measured at 25C by an Ostwald viscometer.
(b) 3irefringence (~n) The birefringence was measured by a usual serek compensator method using a sodium D-ray as the light source.
(c) Density (P) The density was measured at 25C by using a density gradient tube assembled by using carbon tetra-chloride as the heavy liquid and n~heptane as the lightliquid.
(d) Initial Modulus in Tension (Mi) and Terminal Modulus in Tension (Mt) The initial modulus in tension is defined and was measured according to JIS L~1017. The specific conditions of the tensile test for obtaining the load-elongation curve are as follows.
A sample in the shape of a shank was used and allowed to stand in a chamber maintained at a temperature of 20C and a relative humidity of 65% for more than 24 hours, and the measurement was carried out at a sample length of 25 cm and a pulling rate of 30 cm/min by using a ten5ile tester (Tensilon ~trade mark) UTL-4L supplied by Orientec K.K.).
The terminal modulus (g/denier) was determined by di~iding the stress increase between the stress at the point of the elongation smaller by 2.4% than the elongation at break in the load-elongation curve and the stress at the breaking point by 2.4 x 10-2.
Characteristics of_Polyamide Sheath Component Fiber (e) Sulfuric Acid Relative Viscosity (~r) ! The sample was dissolved in formic acid, and i ~ .
- 15 - 1 31~)7~'~
the dissolved portion was precipitated, washed and dried by usual procedures to obtain a sample for the measurement.
Then, 1 g of the sample was dissolved in 25 cc of 98% sulfuric acid and the viscosity was measured at 25C by an Ostwald viscometer.
(f) Birefringence (~n) The measurement was conducted only on the polyamide sheath at intervals of 2 ~m from the side face of the fiber toward the center, by the interference fringe method using a transmission interference microscope supplied by Karl-Zeitz-Iena Inc., and the average value was calculated.
(g) Density (P) The densities of the conjugated fiber and the polyester core fiber component were measured, and the density of the polyamide fiber component was calculated from these densities and the conjugation ratio.
Characteristics of Coniuqated Fiber ~h) Tenacity (T/D), Elongati~n (E) and Initial Modulus in Tension (Mi) The tenacity and initial modulus are defined and were measured according to JIS L-1017. The condi-tions for obtaining the load-elongation curve were the same as described above with respect to the polyester core component fiber.
(i) Dry Heat Shrinkage (~S150) A sample in the shape of a shank was used and allowed to stand in a chamber maintained at a temperature of 20C and a relative humidity of 65~ for more than 24 hours, and the sample having a length L0 as measured under a load of 0.1 g/denier was treated in the unstretched state in an oven maintained at 150C for 30 minute~. The treated sample was air-dried and allowed to stand in the above-mentioned conditioned chamber for more than 24 hours. Then, the length Ll was measured under the above-mentioned load. The dry heat shrinkage - 16 - ¦ ..J ~ ~r ~.~ 7 was calculated according to -the following formula:
Dry heat shrinkage (%) = [(L0 - L1)/L0] x 100 (j) Dynamic Elasticities (E'20 and E'150) and Main Dispersion Peak Temperature (T~) The measurement was carried out in an air bath at a frequency of 110 Hz and a temperature-ele~ating rate of 3C/m.in by using Vibron (trade mark) DDV-II
supplied by Orientec X.K.
(k) Creep Rates (CR20 and CRlso) A sample having a length L0 was allowed to stand under a load of 1 g/denier for 48 hours and ~he length L1 of the sample was measured at 20C and 150C
by using a thermal shock static viscoelasticity tester supplied by Iwamoto Seisakusho K.~., and the creep rates (CR20 and CR1so) were calculated according to the following formula:
CR20 or CR150 = [tLl - L0)/L0] x 100 (~) Characteristics of Coniuqated Fiber Cord (1) Tenacity (T/D), Elongation (E), Initial Modulus in Tension (Mi) and Medium Elongation ~ME) The measurement was conducted in the same manner as described above with respect to the fiber components. The medium elongation is the elongation at which the cord shows the tenacity of (6.75 x D
x n)/(1500 x 2) kg where D stands for the fineness o~
the drawn yarn and n stands for the number of the raw yarns. For example, in the case of a cord 1500/2 formed ! by twisting two drawn yarns each having a fineness o 1500 denier, the elongation at which the tenacity is 6.75 ~g is the medium elongation.
(m) Dry Heat Shrinkage (~S177) The measurement was conducted in the same manner as described in (i) above with respect to the conjugated fiber except that the heat treatment tempera-ture was changed to 177C.
, (n) GY Fatigue Life The GY fatigue life was determined according ~D~ ' - 17 1 ~S 1 ~j i`,73 to the mathod A of JIS L1017-1.3.2.1. The bending angle was adjusted to 90.
(o) GD Fatigue Test The GD fatigue test was carried out according ~o JIS L1017-1.3.2.2. The elongation was 6.3% and the compression was 12.6%.
(p) Adhesion The adhesion was determined according to ~he method A of JIS L1017-3.3.1.
(q) High-Temperature Adhesion The high-temperature adhesion was evaluated in the same manner as described in ~p) above except that the curing heat treatment was carried out at 170C for 50 minutes.
(r) Heat Resistance (Maintenance of Tenacity~ in Rubber Dipped cords were arranged on a rubber sheet, another rubber sheet was placed on the dipped cords to sandwich the dipped cords between the rubber sheets, and the assembly was heat-treated for 3 hours under a pressure of 50 kg/cm2 by a pressing machine heated at 170C. The tenacity of the cords was measured before and after the heat treatment and the tenacity retention ratio was calculated as the criteria of the heat resistance.
E~amples 1 throuqh 4 and Comparative Examples 1 throuq~ 4 Polyethylene therephthalate (PET) having an in-trinsic viscosity ([~]) of O . 9 6 and a terminal carboxyl group concentration of 9.0 eq/106 g was used as the core component and nylon 66 (N66, sulfuric acid relative viscosity ~r = 3. 6 ) containing 0.02% by weight of cupric iodide, 0.1% by weight of potassium iodide and 0.1~ by weight of potassium bromide was used as the sheath component, and both polymers were melted by extruder type spinning machines having a diameter of 40 mm, guided intb a conjugated spinning pack and extruded from , ..
- 18 - 1 3 1 ' ~?~
a sheath-core conjugated spinning spinneret in the form of a conjugated fiber comprising the core of PET and the sheath o~ N66. The ratios of the core and sheath components were as shown in Table 1. The spinneret used had 120 orifices, each ha~ing a diameter of 0.~ mm. PET
when the core was melted at 295C and N66 when the sheath was melted at 290C, and spinning was carried out at a spinning pack temperature of 295C. A heating cylinder having a length of 15 cm was attached j~lSt below the spinneret and h~ating was effected so that the atmosphere in the cylinder was maintained at 290C. The atmosphere temperature was the temperature of the atmos-phere at the point 10 cm below the spinneret surface and apart inwardly by 1 cm from the ~3utermost circumference of a bundle of spun fibers. ~ lateral uniflow chimney having a length of 120 cm was attached below the heating cylinder and cold air maintained at 20C was blown at a rate of 30 m/min at a right angle to -the spun fibers to effect a rapid cooling. Then, an oiling agent was applied to the spun fibers, and the fi~er speed was controlled by a ta~e-up roll rotated at a speed shown in Table 1. The take-up roll temperature was 60C.
The fibers were continuously drawn without being once wound. Three-stage drawing was carried out by using five pairs of Nelson rolls. The first drawing roll temperature was 110C, the second drawing roll temperature was 190C, and the third drawing roll temperature was 230C. The tension control roller arranged downstream from the third drawing rollers was not heated. The draw ratio at the first stage was 70%
of the total draw ratio and the remaining draw ratio was obtained at the second and third stages. The drawn fibers were subjected to a relax annealing treatment to give a 3% relaxation to the drawn fibers, and then wound.
Various fibers were prepared by adopting different spinning speeds and total draw ratios, but the extrusion - 19 131 ~iS73 rate was changed accordinq to the spinning speed and draw ratio so ~hat the fineness of the drawn fibers was about 500 denier. Three bundles of drawn fibers were combined to form a drawn yarn having a fineness of 1500 denier.
For comparison, the polyester and polyamide used for the conjugated fibers were independently spun and drawn to obtain drawn fibers. For the polyamide, the same spinning and drawing conditions as described above were adopted, and the polyester was spun and drawn in the same manner as described above except that the temperature of the third drawing roller was changed to 2~5C
The fiber-preparing conditions are shown in Table 1, the characteristics and fiber structure parame-ters of the obtained drawn fibers are shown in columns of Examples 1 through 4 and Comparative Examples 1 and 3 in Table 2, and the results of the measurement of the characteristics of a commercially available PET fiber for a tire cord (1500D-288fil-702C) [Comparative Exam-ple 2] and a commercially available N66 fiber ~1260D-204fil-1781) [Comparative Example 4] are shown in Table 20 The conjugated fibers of the present invention (Examples 1 through 4) show dynamic elasticity and creep rate characteristics similar to those of the polyester fiber, although a large quantity of the N66 component is contained, and it can be s~en that the conjugated fibers of the present invention are extraordinary.
Green cords of 1500D/2 were prepared by using the conjugated fibers of the present invention (Examples 1 through 4) and PET fibers [Comparative Examples 1 and 2]
and applying first and second twists of 40 T/10 cm in the opposite directions. Furthermore, green cords of 35 1260D~2 were prepared by using N66 fibers [Comparative Examples 3 and 4] and applying first and second twists of 39 T/10 cm in the opposite directions.
1 3 1 ~1 S / -) The green cord composed of the conjugated fibers of the present in~ention was formed into a di~ped cord by applying the adhesive and carrying out the heat treatment by usual procedures using a "Computreater"
dipping machine supplied by C.A. Litzler Inc. The dipping solution contained 20~ by weight of an adhesive component composed of a resorcine, formalin and latex, and the treatment was carried out so that the adhesive component was applied to the cord in an amount of about 4% by weight. The heat treatment was conducted at 225C
for 80 seconds while the cord was stretched so that the medium elongation of the dipped cord was about 5%.
The green cord of N66 fibers [Comparative Exam-ples 3 and 4] was heat-treated in the same manner as described above with respect to the conjugated fibers o~
the present invention except that stretching was per-formed so that the medium elongation was set at a level of about 9%, generally applied to an ordinary N66 tire cord.
The green cord of ~E~ fibers [Comparative ~xam-ples 1 and 2] was subjected to the customary two-bath adhesion treatment, the heat treatment was carried out at 240C for 120 seconds, and s~retching was performed so that the medium elongation was set at a level of about 5%, generally applied to an ordinary PET tire cord.
The tire cord characteristics of the thus-obtained dipped cords, such as the heat resistance in a rubber, the adhesion and the fatigue resistance were evaluated.
The results are shown in Table 3.
It can be seen that the dipped cord composed of the conjugated fibers of the present invention has an initial modulus and dimensional stability comparable to those of the conventional dipped cord composed of PET
fibers and this dip cord is a high-tenacity dipped cord having a highly improved heat resistance in a rubber, high-temperature adhesion, and fatigue resistance.
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Claims (5)
1. A high-tenacity conjugated fiber having a sheath-core conjugated structure consisting essentially of a polyester composed mainly of ethylene terephthalate units as the core component and a polyamide as the sheath component, wherein the ratio of the core compo-nent to the sum of the core component and sheath compo-nent is 30 to 90% by weight, and the conjugated fiber has (a) a dynamic elasticity (E'20) at 20°C of at least 8 x 104 dyne/denier and a dynamic elasticity (E'150) at 150°C of at least 3 x 104 dyne/denier, as measured at 110 Hz, and a main dispersion peak temperature (T.alpha.) of at least 140°C in the mechanical loss tangent (tan .delta.) curve, (b) a creep rate (CR20) not larger than 2.0% as measured at 20°C after 48 hours' standing under a load of 1 g/denier and a creep rate (CR150) not larger than 3.0% as measured at 150°C after 48 hours' standing under a load of 1 g/denier, (c) an intrinsic viscosity ([.pi.]) of at least 0.8 and a birefringence (.DELTA.n) of 160 x 10-3 to 190 x 10-3 in the polyester core component, and (d) a sulfuric acid relative viscosity (.pi.r) of at least 2.8 and a birefringence (.DELTA.n) of at least 50 x 10-3 in the polyamide sheath component.
2. A high-tenacity conjugated fiber as set forth in claim 1, wherein the polyester core component has a density (?) of at least 1.395 g/cm3 and the polyamide sheath component has a density (?) of at least 1.135 g/cm3.
3. A high-tenacity conjugated fiber as set forth in claim 1, wherein the polyester core component has an initial modulus in tension (Mi) at least 90 g/denier and a terminal modulus in tension (Mt) not larger than 20 g/denier.
4. A high-tenacity conjugated fiber as set forth in claim 1, which has a tenacity (T/D) of at least 7.5 g/denier, an initial modulus in tension (Mi) of at least 60 g/denier, and a dry heat shrinkage (.DELTA.S150) as measured at 150°C of not larger than 7%.
5. A process for the preparation of a sheath-core type high-tenacity conjugated fiber having an improved peel resistance in the sheath-core interface, which comprises forming, by melt spinning, a sheath-core high tenacity conjugated fiber having a core formed of a polymer composed substantially of high-polymerization-degree polyethylene terephthalate having an intrinsic viscosity ([?]) of at least 0.80 and a sheath formed of a high-polymerization-degree polyamide polymer having a sulfuric acid relative viscosity of at least 2.8, in which the ratio of the core component to the sum of the core component and sheath component is 30 to 90% by weight, said process being characterized in that a molten polymer fiber extruded from a spinneret is passed through an atmosphere, a portion of which over a length of at least 10 cm below the spinneret is maintained at a temperature of at least 200°C; the molten polymer fiber is rapidly cooled to be solidified; an oiling agent is applied to the solidified polymer fiber; the fiber is taken up at a speed of at least 1,500 m/min to form an undrawn fiber in which the polyamide sheath component has a birefringence of 25 x 10-3 to 40 x 10-3 and the polyester core component has a birefringence of 20 x 10-3 to 70 x 10-3; and the undrawn fiber is subjected to multi-stage drawing including at least two stages to obtain a conjugated fiber having (a) a dynamic elas-ticity (E'20) at 20°C of at least 8 x 104 dyne/denier and a dynamic elasticity (E'150) at 150°C of at least 3 x 104 dyne/denier, as measured at 110 Hz and a main dispersion peak temperature (T.alpha.) of at least 140°C in the mechanic loss tangant (tan .delta.) curve, (b) a creep rate (CR20) not larger than 2.0% as measured at 20°C
after 48 hours' standing under a load of 1 g/denier and a creep rate (CR150) not larger than 3.0% as measured at 150°C after 48 hours' standing under a load of 1 g/denier, (c) an intrinsic viscosity ([?]) of at least 0.8 and a birefringence (.DELTA.n) of 160 x 10-3 to 190 x 10-3 in the polyester core component, and (d) a sulfuric acid relative viscosity (?r) of at least 2.3 and a birefrin-gence (.DELTA.n) of at least 50 x 10-3 in the polyamide sheath component.
after 48 hours' standing under a load of 1 g/denier and a creep rate (CR150) not larger than 3.0% as measured at 150°C after 48 hours' standing under a load of 1 g/denier, (c) an intrinsic viscosity ([?]) of at least 0.8 and a birefringence (.DELTA.n) of 160 x 10-3 to 190 x 10-3 in the polyester core component, and (d) a sulfuric acid relative viscosity (?r) of at least 2.3 and a birefrin-gence (.DELTA.n) of at least 50 x 10-3 in the polyamide sheath component.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-253125 | 1987-10-07 | ||
| JP62-253126 | 1987-10-07 | ||
| JP62253125A JP2659724B2 (en) | 1987-10-07 | 1987-10-07 | Manufacturing method of high strength composite fiber |
| JP62253126A JPH0197230A (en) | 1987-10-07 | 1987-10-07 | Pneumatic radial tire |
| JP63223771A JPH0274612A (en) | 1988-09-07 | 1988-09-07 | Conjugate fiber having high tenacity |
| JP63-223771 | 1988-09-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1314673C true CA1314673C (en) | 1993-03-23 |
Family
ID=27330819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000579481A Expired - Fee Related CA1314673C (en) | 1987-10-07 | 1988-10-06 | High-tenacity conjugated fiber and process for preparation thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4987030A (en) |
| EP (1) | EP0311386B1 (en) |
| AU (1) | AU606462B2 (en) |
| CA (1) | CA1314673C (en) |
| DE (1) | DE3889282T2 (en) |
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| US5384082A (en) * | 1986-01-30 | 1995-01-24 | E. I. Du Pont De Nemours And Company | Process of making spin-oriented polyester filaments |
| JP2850004B2 (en) | 1988-05-09 | 1999-01-27 | 横浜ゴム株式会社 | Pneumatic textile radial tire |
| US5221384A (en) * | 1988-05-10 | 1993-06-22 | The Yokohama Rubber Co., Ltd. | Pneumatic radial tire with a belt covering layer reinforced with core-sheath composite fiber cords |
| US5419951A (en) * | 1991-04-19 | 1995-05-30 | Murdock Webbing Company, Inc. | Cut and abrasion resistant webbing and multifilament bicomponent yarn used in the manufacturing thereof |
| US5658655A (en) * | 1993-02-19 | 1997-08-19 | Hoechst Celanese Corporation | Heterofilaments for cord reinforcement in rubber goods |
| EP0649921B1 (en) * | 1993-02-23 | 2000-05-17 | Toray Industries, Inc. | High-strength polyamide fiber |
| EP0721522B1 (en) * | 1993-09-28 | 1997-05-28 | E.I. Du Pont De Nemours And Company | Iridescent fabrics |
| US5582913A (en) * | 1995-08-23 | 1996-12-10 | Hoechst Celanese Corporation | Polyester/polyamide composite fiber |
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| US6690419B1 (en) * | 1997-07-15 | 2004-02-10 | Silverbrook Research Pty Ltd | Utilising eye detection methods for image processing in a digital image camera |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1207062A (en) * | 1967-01-27 | 1970-09-30 | Toray Industries | An improved composite polyamide polyester, sheath-core filament and a method for manufacturing the same |
| GB1165853A (en) * | 1967-01-31 | 1969-10-01 | Du Pont | Oriented Concentric Sheath-Core Filaments and Pneumatic Tires Reinforced therewith |
| US3975351A (en) * | 1969-12-19 | 1976-08-17 | Imperial Chemical Industries Inc. | Plasticizers as adhesion promoters in polyester/polyamide heterofilaments |
| GB1331752A (en) * | 1970-09-10 | 1973-09-26 | Ici Ltd | Conjugate filaments |
| US4195052A (en) * | 1976-10-26 | 1980-03-25 | Celanese Corporation | Production of improved polyester filaments of high strength possessing an unusually stable internal structure |
| AU525860B2 (en) * | 1978-03-03 | 1982-12-02 | Akzo N.V. | Fibre structures of split multicomponent fibres |
| JPS5865008A (en) * | 1981-09-08 | 1983-04-18 | Toyobo Co Ltd | Polyamide fiber with high strength and its production |
| JPS58136823A (en) * | 1982-02-06 | 1983-08-15 | Toyobo Co Ltd | Polyamide fiber |
| US4851508A (en) * | 1986-07-02 | 1989-07-25 | Toyo Boseki Kabushiki Kaisha | Polyester fibers having high strength and high modulus and process for producing the same |
-
1988
- 1988-10-04 US US07/253,135 patent/US4987030A/en not_active Expired - Lifetime
- 1988-10-05 AU AU23435/88A patent/AU606462B2/en not_active Ceased
- 1988-10-06 DE DE3889282T patent/DE3889282T2/en not_active Expired - Fee Related
- 1988-10-06 EP EP88309296A patent/EP0311386B1/en not_active Expired - Lifetime
- 1988-10-06 CA CA000579481A patent/CA1314673C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3889282D1 (en) | 1994-06-01 |
| AU606462B2 (en) | 1991-02-07 |
| EP0311386A2 (en) | 1989-04-12 |
| EP0311386A3 (en) | 1989-11-15 |
| AU2343588A (en) | 1989-04-13 |
| EP0311386B1 (en) | 1994-04-27 |
| DE3889282T2 (en) | 1994-08-11 |
| US4987030A (en) | 1991-01-22 |
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| MKLA | Lapsed | ||
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