JP2000096348A - Water-repelling, oil-repelling and antisoiling fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repelling, oil-repelling and antisoiling fiber having excellent water-repelling, oil-repelling and antistaining properties which are not largely deteriorated, even when repeatedly washed, and capable of satisfying fiber-producing operability and fiber quality performance. SOLUTION: This water-repelling, oil-repelling and antisoiling fiber comprises a sheath-core conjugate fiber comprising a core component and a sheath component. The core component comprises a thermoplastic resin, and the sheath component comprises a thermoplastic resin containing a fluorinated copolymer in an amount of 1-100 wt.%. The core component is contained in an amount of 30-98 wt.% based on the total weight of the fiber, and the fluorinated copolymer of the sheath component is homogeneously dispersed in a portion near to the surface of the fiber. The water-repelling, oil-repelling and antisoiling fiber is obtained by melt-spinning polymers, drawing the spun fiber, winding up the fiber and subsequently thermally treating the fiber at 160-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a core-in-sheath type conjugate fiber comprising a thermoplastic resin containing a fluorine-based copolymer as a sheath component, which has excellent water repellency, oil repellency and stain resistance. However, the present invention relates to a fiber whose performance does not significantly decrease even after repeated washing.

[0002]

2. Description of the Related Art Conventionally, a fiber having water-repellent, oil-repellent and antifouling properties is obtained by forming a film having these properties on the surface of the fiber by treating it with a fluorine-based or silicone-based composition. Has been widely adopted. However,
Such a fiber has a problem that the water repellency, oil repellency, and antifouling performance are significantly reduced because the film is peeled or cracked when washing is repeated.

Therefore, Japanese Patent Application Laid-Open No. Sho 62-238822 proposes a fiber obtained by melt-kneading a fluorine-based resin, and Japanese Patent Application Laid-Open No. 2-26919 discloses a method in which fluorine-based polymer particles are kneaded. However, these fibers could not satisfy all of the effects of water repellency, oil repellency, antifouling property, yarn operability, and yarn quality.

Further, Japanese Patent Application Laid-Open No. 9-302523,
No. 302524 discloses a fiber obtained by kneading a fluorine-based resin as a fiber having excellent water repellency without performing post-processing, and at least a fluorine-based fiber in a fiber cross section at least near the fiber surface. Polyester fibers in which the resin is dispersed as independent island components are described.

According to these fibers, a certain degree of water repellency,
The oil repellency and antifouling effects have been improved, but since the fluorine resin is dispersed unevenly on the fiber surface, there is unevenness in the water repellency, oil repellency and antifouling effect, and these performances are maintained for a long time I couldn't. In addition, since the fluorine-based resin is agglomerated and dispersed to some extent as an island component, yarn breakage is likely to occur during spinning and drawing, and the yarn-making operability has not been sufficiently satisfactory.

[0006] Further, Japanese Patent Application Laid-Open No. 10-121329 proposes a core-in-sheath type conjugate fiber containing a fluorine-containing polymer in a sheath portion. Since the resin in which the fluoropolymer is kneaded almost uniformly in the sheath portion is used, the resin has water-repellent, oil-repellent, and antifouling performance without unevenness, and can be obtained with good spinning properties. However, in order to maintain the performance for a long period of time, it was necessary to increase the ratio of the sheath to some extent.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides excellent water repellency even when the proportion of the sheath containing a fluoropolymer is small.
It is an object of the present invention to provide a fiber having oil repellency and antifouling property, its performance is not largely reduced even when repeatedly washed, and which can satisfy the yarn operability and the yarn quality performance.

[0008]

Means for Solving the Problems The inventors of the present invention have studied to solve such a problem, and as a result, have made a core-sheath structure in which a fluorine-based copolymer is uniformly contained in a sheath portion, and melt-spun. After being obtained by stretching and winding, the fiber is further subjected to a heat treatment, whereby the water repellency, oil repellency, and antifouling performance are improved, and even when the ratio of the sheath portion containing the fluorine-based copolymer is small. The inventors have found that the fibers have sufficient water repellency, oil repellency and antifouling performance, and have reached the present invention.

That is, according to the present invention, the core component is composed of a thermoplastic resin, the sheath component is composed of a thermoplastic resin containing 1 to 100% by weight of a fluorine-based copolymer, and the weight of the core component is 30% of the total fiber.
9898% by weight, which is a core-sheath type composite fiber in which the fluorine-based copolymer of the sheath component is uniformly dispersed in the vicinity of the fiber surface, and is obtained by melt-spinning, stretching and winding up, and
The gist of the present invention is a water-repellent, oil-repellent, and antifouling fiber which has been subjected to a heat treatment at 200 to 200 ° C.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the thermoplastic resin used for the core component and the sheath component of the fiber of the present invention include polyester polymers such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and nylon 4, nylon 6, nylon 66, nylon 11, and the like. And the like. Above all, polyethylene terephthalate and nylon 6 are preferable from the viewpoint of cost, spinnability and the like.

[0011] These polyester-based polymers and polyamide-based polymers may contain a copolymer component, if necessary, as long as the effect is not impaired.
In addition, heat stabilizers, light stabilizers, fluorescent agents, antioxidants, matting agents, antioxidants, antistatic agents, pigments, colorants, flame retardants,
A reinforcing agent, a lubricant, an antistatic agent and the like may be contained.

Particularly in the case of polyethylene terephthalate,
As copolymerization components, isophthalic acid, phthalic anhydride, 5-
Sodium sulfoisophthalic acid, naphthalenedicarboxylic acid, diethylene glycol, propylene glycol,
1,4-cyclohexanedimethanol, pentaerythritol, 4-hydroxybenzoic acid, ε-caprolactam,
Adipic acid, sebacic acid, 1,4-butanediol, 1,
6-hexanediol, polyethylene glycol and the like.

Above all, polyethylene terephthalate having a relative viscosity of 1.2 to 1.8 is preferable. If the relative viscosity is larger than this range, spinning stress is high, and it becomes difficult to control oriented crystallization. If it is smaller than this range, the fiber strength tends to be inferior.

In the case of nylon 6, the relative viscosity is 2.
If the relative viscosity is higher than this range, the spinnability tends to decrease sharply, and if the relative viscosity is lower than this range, the fiber strength tends to be inferior.

In the composite fiber of the present invention, the thermoplastic resin of the core component and the thermoplastic resin of the sheath component may be the same or different. The cross-sectional shape may be any cross-section such as a circular cross-section, an elliptical shape, a flat shape, a six-lobe shape, a triangular shape, a star-shaped cross-section, or a hollow cross-section.

In the conjugate fiber of the present invention, the sheath component is composed of the thermoplastic resin as described above and a fluorocopolymer of 1 to 100.
% By weight. Fluorinated copolymer
When the content is 100% by weight, the sheath component is composed of only a fluorine-based copolymer and does not contain the above-described thermoplastic resin. Further, a more preferable range of the content of the fluorine-based copolymer as the sheath component that improves the spinnability is 1 to 20% by weight or 90 to 100% by weight. If the content of the fluorocopolymer is less than 1% by weight, the fiber does not have water repellency, oil repellency and antifouling performance.

As the fluorine-based copolymer as a water-repellent, oil-repellent, or antifouling agent to be contained in the sheath component, a known fluorine-based copolymer can be used. It is preferable that the resin has a melt viscosity and is similar in melt viscosity to the thermoplastic resin used.

For example, a terpolymer (THV500G manufactured by Sumitomo 3M Limited) obtained by polymerizing three kinds of monomers of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride can be mentioned. This polymer not only has a melt viscosity suitable for melt molding itself, but also has a melt viscosity near the spinning temperature of polyethylene terephthalate similar to that of polyethylene terephthalate. Is preferred.

Further, the above terpolymer is preferably one having a melt viscosity of 5000 to 10,000 poise. If the melt viscosity is higher than this range, yarn breakage is likely to occur during spinning, and the melt viscosity is high. Is smaller than this range, it is easy to form a yarn.

The ratio of the core component and the sheath component in the composite fiber of the present invention is such that the core component is 30 to 98% by weight, preferably 40 to 98% by weight, and more preferably 70 to 98% by weight of the total fiber. If the ratio of the core component is larger than this range, the sheath portion becomes too thin, causing a peeling phenomenon, making it difficult to form a core-sheath composite structure. If the ratio of the core component is smaller than this range, sufficient strength cannot be obtained,
Draft breakage often occurs during spinning, and even if it can be collected, the cost increases, which is not preferable.

The fiber of the present invention has a sufficient water repellency, oil repellency and antifouling performance even if the ratio of the sheath portion is considerably reduced by heat treatment after spinning, drawing and winding. is there. Specifically, the ratio of the sheath component is 2 to 30% by weight.
Since these properties are sufficient even to the extent, and the performance will be maintained for a long time, the fiber of the present invention can reduce the cost and increase the ratio of the core,
Excellent in physical properties such as strength and elongation.

The fluorine-based copolymer as the sheath component must be uniformly dispersed in the fiber cross section near the fiber surface. Uniformly dispersed state means that the fiber
Thermoplastic resin and fluororesin cannot be distinguished from each other in an electron micrograph at 2000 times magnification. If the fluorine-based resin is not uniformly dispersed, unevenness in water repellency, oil repellency, and antifouling properties may occur, and yarn-making operability may be deteriorated, resulting in fibers having poor elongation.

As a method of uniformly dispersing the fluorine-containing copolymer as a sheath component in a thermoplastic resin, a static mixer is placed in an extruder line, or after kneading and dispersing in an extruder, a metal filter or a sintering filter is used. What is necessary is just to filter with a binding metal filter, but it is especially preferable to prepare the master chip of a thermoplastic resin and a fluororesin.

The fiber of the present invention is obtained by melt-spinning, drawing and winding, and then subjected to a heat treatment at 160 to 200 ° C. Melt spinning, stretching, winding method is not particularly limited,
Either a two-step method in which the undrawn yarn is once wound and then drawn, or a one-step method in which the undrawn yarn is continuously drawn without being wound may be used.

The stretching may be either cold stretching or hot stretching. In the case of hot stretching, heat treatment may be performed using a heating roller, a heat plate, a steam jet device, or the like. Performing multi-stage stretching using these devices as appropriate,
The drawn yarn may be further subjected to a heat treatment or a relaxation treatment.

The fiber thus obtained has 16
Heat treatment at 0 to 200 ° C. Thereby, the bonding of the fluorine-based copolymer can be caused to undergo thermal molecular motion, and the water repellency, oil repellency and antifouling performance are further improved. If the heat treatment temperature is lower than this range, the bond of the fluorine-based copolymer does not undergo thermal molecular motion, so that the water repellency, oil repellency, and antifouling performance are the same as before heat treatment. In addition, when heat treatment is performed at a temperature exceeding 200 ° C., the fluorine-based resin is melted, and spots are formed and performance such as high elongation is reduced.

Examples of the heat treatment method include a dry heat treatment using a heater and a method of irradiating a laser beam. The heat treatment may be performed in the state of a yarn or in the state of a fabric after knitting and weaving. The heat treatment time may be appropriately adjusted, but is generally about 15 seconds to 5 minutes. The reason why such a heat treatment is performed after stretching and winding into a package is that if the heat treatment is performed at a high temperature of 160 to 200 ° C. before winding, the yarn will oscillate and the winding will be performed in a good winding shape. Is likely to be difficult.

[0028]

Next, the present invention will be described specifically with reference to examples. The measurement and evaluation of the characteristic values in the examples were performed as follows. (a) Melt viscosity Using a Shimadzu flow tester CFT-500D and a die having L = 10 mm and D = 1 mm, the melt viscosity was measured at 280 ° C. and a load of 100 kg with a preheating time of 300 seconds. (b) Relative viscosity of polyethylene terephthalate Measured at a concentration of 0.5 g / dl and a temperature of 20 ° C. using an equal weight mixture of phenol and tetrachloroethane as a solvent. (c) Relative viscosity of polyamide 96% sulfuric acid was used as a solvent and the concentration was measured at a concentration of 1.0 g / dl at a temperature of 25 ° C. (d) Water repellency and oil repellency The obtained fibers were made into a woven fabric (1/1 plain weave), and the woven fabric was evaluated for AATCC-118. (e) Antifouling property The same woven fabric as in (d) is contaminated with a mixture of sauce, coffee and beer, left for 10 minutes, washed in the same manner as JIS-L 1045, and from the degree of contamination removal, antifouling The properties were evaluated as ○, △, ×. (f) High elongation After heat treatment in the state of a woven fabric, take out the fiber and use JIS
It was measured according to the method described in L-1013 7.5.

Example 1 Polyethylene terephthalate (PET) having a relative viscosity of 1.38
The chip is dried under reduced pressure, and as a fluorine-based copolymer,
Tetrafluoroethylene, hexafluoropropylene,
Terpolymers obtained by polymerizing three types of vinylidene fluoride monomers (THV500 manufactured by Sumitomo 3M Limited)
G) chips (melt viscosity 8940 poise) were mixed to prepare a master chip, and dried under reduced pressure. Then, using a normal composite spinning apparatus, the sheath component was made into PET containing 5% by weight of THV-500G, the core component was made only of PET, and the pore diameter was 0.5 mm.
Was extruded at 290 ° C. from a spinneret having 24 circular holes. The blend of the sheath component, THV-500G, and PET was kneaded with an extruder for 20 minutes. Then, the composite melt spinning was performed by changing the discharge amount so that the core component was 80% by weight with respect to all components and the single yarn fineness was 5.1 denier. Then, after passing the yarn spun from the die through a heating cylinder having a temperature of 300 ° C. and a length of 5 cm,
Cooling air with a temperature of 18 ° C is blown by a cooling air blowing device (length 100cm).
It was solidified by spraying at a wind speed of 0.8 m / sec, and after applying an oil agent, was wound up at 3300 m / min to obtain a POY yarn. The obtained POY yarn was taken up with a heating roller at 90 ° C. and stretched through a heat plate at 170 ° C. so as to have a stretching ratio of 1.626.
Winding was performed at a speed of 80 m / min to obtain a fiber of 76d / 24f. The obtained fiber was used as a woven fabric and heat-treated at 200 ° C. for 3 minutes using a heater.

Comparative Example 1 The procedure of Example 1 was repeated, except that the core-sheath type composite fiber was not used, and the fiber was made only of PET containing no fluorine-based copolymer.

Examples 2 to 7 and Comparative Examples 2 to 4 The same procedures as in Example 1 were carried out except that the ratio of the core component and the sheath component and the content of THV-500G in the sheath component were changed as shown in Table 1. went.

Comparative Example 5 The procedure of Example 1 was repeated, except that the heat treatment was not performed after the wound fiber was turned into a woven fabric.

Example 8 A nylon 6 chip having a relative viscosity of 2.5 was dried. THV
A master chip was prepared by mixing -500G chips and dried under reduced pressure. Then, using a conventional composite melt spinning apparatus, the sheath component was made of nylon 6 containing 5% by weight of THV-500G, the core component was made of only nylon 6, and the spinneret having 24 circular holes having a hole diameter of 0.5 mm was used. Extruded at 260 ° C. The blend of the sheath component THV-500G and nylon 6 was carried out by kneading with an extruder for 20 minutes. By changing the discharge amount, the core component is 80% by weight based on all components,
The composite melt spinning was performed by adjusting the single yarn fineness to 4.1 denier. Then, the yarn spun from the die is heated
After passing through a heating cylinder of 250 ° C. and 5 cm in length, a cooling air blowing device (100 cm in length) blows cooling air at a temperature of 18 ° C. at a wind speed of 0.8 m / sec to solidify, and after applying oil, 4300 m
/ Min to obtain a POY yarn. The obtained POY yarn
The fiber was taken up with a heating roller at 90 ° C., drawn through a heat plate at 170 ° C. so as to have a draw ratio of 1.297, and wound up at a speed of 680 m / min to obtain a fiber of 76d / 24f. The obtained fiber is made into a woven fabric (1/1 plain weave), and heated to 200 ° C.
For 3 minutes.

Comparative Example 6 The procedure of Example 8 was repeated, except that the core-sheath type composite fiber was not used, and a fiber consisting of only nylon 6 containing no fluorine-based copolymer was used.

Examples 9 to 12 Comparative Examples 7 to 9 Comparative examples 7 to 9 were carried out in the same manner as in Example 8 except that the ratio of the core component and the sheath component and the content of THV-500G in the sheath component were changed as shown in Table 1. Was.

Example 13 Comparative Example 10 The procedure of Example 1 was repeated except that the temperature of the fabric after the heat treatment was 160 ° C. (Example 13) and 100 ° C. (Comparative Example 10).
The same was done.

Table 1 shows the evaluation results of the fibers obtained in the examples and comparative examples with respect to the elongation, water repellency, oil repellency, and antifouling properties.

[0038]

[Table 1]

As apparent from Table 1, Examples 1 to 13
The fiber obtained in the above was also excellent in water repellency, oil repellency and antifouling properties, and was excellent in these properties even when the ratio of the sheath portion was small. In addition, all of them were excellent in physical properties such as strength and elongation, and could be obtained with good spinnability. On the other hand, Comparative Examples 1 and 6 were excellent in yarn quality because they were fibers containing no fluorine-based copolymer, but did not have water repellency, oil repellency, and antifouling performance. . In Comparative Examples 2 and 7, since the ratio of the sheath component was too large, the draft was cut during spinning, and no yarn could be obtained. In Comparative Examples 3 and 8, since the ratio of the sheath component was too small, the sheath portion was too thin to be partially peeled off, and did not have a core-sheath composite structure, resulting in unevenness in water repellency. In Comparative Examples 4 and 9, the content of the fluorine-based copolymer was too small, and in Comparative Example 5, no heat treatment was performed. In Comparative Example 10, the heat treatment temperature was too low. Oil and antifouling performance were insufficient.

[0040]

The fiber of the present invention has excellent water repellency, oil repellency and antifouling property even if the ratio of the sheath component is small, and its performance is not significantly reduced even if it is repeatedly washed. In addition, the yarn can be obtained with good yarn-making operability, and the yarn quality performance is also excellent.

Continued on the front page (72) Inventor Sou Yamaguchi 23 Uji Kozakura, Uji-city, Kyoto, Japan Unitika Co., Ltd. Central Research Laboratory (72) Inventor Kazuaki Taruishi 23 Uji Kozakura, Uji-city, Kyoto, Japan 23 Unitika Co., Ltd. Central Research Laboratory F-term (Reference) 4L041 AA08 AA17 AA18 AA19 AA20 AA25 BA02 BA05 BA21 BC01 BC02 BC20 BD14 CA06 CA21 CA47 DD01 DD14 DD18

Claims (1)

[Claims] 1. The core component is made of a thermoplastic resin, and the sheath component is made of a thermoplastic resin containing 1 to 100% by weight of a fluorocopolymer. The weight of the core component is 30 to 98% by weight of the whole fiber, It is a core-sheath type composite fiber in which the fluorine-containing copolymer of the sheath component is uniformly dispersed in the vicinity of the fiber surface, and is obtained by melt-spinning, drawing and winding, and then subjected to a heat treatment at 160 to 200 ° C. A water-repellent, oil-repellent, and antifouling fiber characterized by being applied.