JP2000178834A - Water and oil repellent and antifouling polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain polyester fibers having excellent water and oil repellence and antifouling properties due to an uneven shape possessed on the fiber surface and synergistic effects of water and oil repellent and antifouling effects caused by the uneven shape and the effects developed by a fluorine-based polymer contained in protruding parts. SOLUTION: The water and oil repellent and antifouling polyester fibers comprise a fluorine-based polymer or a polyester resin containing >=1 wt.% of the fluorine-based polymer as a component A and a polyester resin as a component B, have the plural components A and B alternately divided and arranged with rotation symmetry in the cross-sectional shape and assume an uneven structure in which at least a part of the component A is protruded to the fiber surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester fiber containing a fluoropolymer, having irregularities on the fiber surface, and having excellent water / oil / oil repellency.

[0002]

2. Description of the Related Art Conventionally, in order to impart water repellency, oil repellency, and antifouling properties to fibers, after forming a fabric, it is treated with a fluorine-based or silicone-based treating agent to form these films on the fabric surface. The method of making it widely used was adopted.

[0003] However, these fabrics have the problem that the water-repellent, oil-repellent, and antifouling properties are significantly reduced because the coating is peeled off or cracked when repeatedly worn and washed. there were.

Therefore, Japanese Patent Application Laid-Open No. 62-238822 proposes a fiber obtained by melting and kneading a fluorine-based resin, and Japanese Patent Application Laid-Open No. 2-26919 discloses a kneaded fiber made of fluorine-containing polymer particles. The fiber obtained in is proposed,
These fibers were not considered in terms of fiber shape, and the effects of water repellency, oil repellency, and stain resistance were not sufficiently satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and has irregularities on the fiber surface. An object of the present invention is to provide a polyester fiber having excellent water repellency, oil repellency and antifouling property by a synergistic effect of these effects developed by containing a fluorine-containing polymer.

[0006]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to a fluorine-containing polymer or a polyester resin containing 1% by weight or more of a fluorine-containing polymer as a component A and a polyester resin as a component B.
Water-repellent, oil-repellent and antifouling polyester, characterized in that a plurality of components A and B are alternately and rotationally symmetrically divided, and the fiber surface has an uneven structure in which at least a part of the component A protrudes. The gist is a fiber.

[0007]

Next, the present invention will be described in detail. The water-repellent, oil-repellent, and antifouling polyester fiber of the present invention comprises component A and component B, and component A is a fluoropolymer or a polyester resin containing 1% by weight or more of the fluoropolymer. is there. That is, the component A may be either a fluoropolymer alone or a polyester resin containing 1% by weight or more of the fluoropolymer.

The fluoropolymer is used as a water-repellent, oil-repellent and antifouling agent, and is not particularly limited as long as it is thermoplastic, and a known fluoropolymer can be used. Among them, those having not only a melt viscosity suitable for melt molding but also having a similar melt viscosity near the spinning temperature to the polyester resin are preferable.

For example, a terpolymer ("THV-500G" manufactured by Sumitomo 3M Limited) obtained by copolymerizing three kinds of monomers of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride can be mentioned.

The content of the fluoropolymer is at least 1% by weight, preferably at least 5% by weight. When the content of the fluoropolymer is less than 1% by weight, water repellency, oil repellency and antifouling performance become insufficient.

As the polyester resin used in the component A, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate and the like are preferably used. These polyesters may contain a small amount of a copolymer component as long as the effect is not impaired, and further, a heat-resistant agent, a light stabilizer, a fluorescent agent, an antioxidant,
Matting agents, antistatic agents, pigments, colorants, flame retardants, reinforcing agents,
It may contain a lubricant, an antistatic agent and the like.

The component B is a polyester resin, and the same polyester resin as the component A described above can be used. Above all, in order to improve the effects of water repellency, oil repellency and antifouling properties, it is preferable to contain a fluoropolymer in an amount of 1 to 10% by weight. In the polyester fiber of the present invention, the cross-sectional shape of the fiber is special as described below,
In addition, since most of the effects of water repellency, oil repellency and antifouling properties are exhibited by the component A containing the fluoropolymer, the amount of the fluoropolymer in the component B may be smaller than that of the component A. It is sufficient to include 10% by weight. When the content of the fluoropolymer exceeds 10% by weight, the fiber properties such as the strength and elongation of the fiber as a whole, the dyeability, and the like tend to be reduced.

Further, in order to suppress yarn loosening, clinging, adhesion of dust and the like due to generation of static electricity at the time of spinning and wearing, the component B contains a known antistatic agent having antistatic properties. Is preferred.

Next, the fiber of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing one embodiment of the polyester fiber of the present invention. The fiber of the present invention has a concave-convex structure in which a plurality of components A and B are alternately and rotationally symmetrically divided in the cross-sectional shape, and the component A protrudes from the fiber surface.

As described above, the fiber of the present invention has a concave-convex structure on the fiber surface, thereby making it difficult for dirt and moisture to adhere to the fiber surface. In other words, when it is made into a cloth, it has water repellency, oil repellency,
Shows antifouling effect. In addition, the fiber of only the fluoropolymer cannot be dyed, and the application is limited.However, the fiber of the present invention has the component A and the component B that are alternately divided and arranged.
Even if only the fluoropolymer is used as the component A, it has good dyeability.

The number of each of the components A and B is not particularly limited, and can be variously changed according to the brand and the desired water repellency, oil repellency and antifouling performance. However, if the number is too small, the effect such as the lotus leaf and the taro leaf described above is reduced, so that the number is 3 or more (the number of divisions is 6 or more).
It is preferable that

Further, the fibers of the present invention include those in which a part of the component A is not a convex portion. It is preferable that all of the components A protrude from the fiber surface as in 1.

The polyester fiber of the present invention can be obtained by melt-spinning and drawing using a spinneret having such an uneven shape. Component B is made of an alkali-soluble polyester, and FIG. As shown in the drawing, a fiber having a shape in which the fiber surface is covered with the component B may be obtained by melt-spinning, drawing, and then performing an alkali weight reduction treatment. At this time, since the component B on the fiber surface having a higher alkali weight reduction rate than the component A and a part of the component B in the vicinity of the fiber surface divided and arranged are reduced by the alkali weight reduction process,
The component A as shown in FIG. 1 is a fiber having a convex-concave shape.

By coating the fiber surface with the component B in this manner, even when the component A is only a fluoropolymer, the oil agent at the time of spinning can be uniformly applied, and the yarn on the take-up roller or the drawing roller can be applied. It is possible to suppress the slipping of the strip and the generation of white powder, and it is possible to stably take up the fiber, and to obtain a fiber having a clear uneven shape by the subsequent weight reduction treatment.

In the case where an alkali-soluble polyester is used as the component B, it is preferable that the copolymer be mainly composed of polyethylene terephthalate and contain isophthalic acid, 5-sodium sulfoisophthalic acid, an ethylene oxide adduct of bisphenol A, or the like as a copolymerization component.

Further, another shape of the polyester fiber of the present invention will be described with reference to FIG. In the present invention, it is preferable that the component C exists near the center in the cross-sectional shape, and the component C contains a conductive component. As the conductive component, a known component may be used, for example, conductive carbon black or metal powder (silver, nickel, copper, iron),
Metal compounds such as copper sulfide, copper iodide, and zinc sulfide are exemplified.

By having the component C which is a conductive portion,
As in the case where an antistatic agent is contained in the component B, it is possible to suppress the occurrence of yarn loosening, clinging, adhesion of dust, and the like due to generation of static electricity at the time of spinning and wearing. In addition, if the ratio of the component C is increased, the physical properties of the thread are reduced or the cost is increased. Therefore, the content is preferably 20% by weight or less.

Next, a method for producing the polyester fiber of the present invention will be described. The water-repellent, oil-repellent, and antifouling polyester fiber of the present invention can be produced by a conventional method. First, in the case where a fluorine-based polymer is contained in the polyester resin in the component A or the component B, a method in which each chip is melt-kneaded in an extruder is preferable. In addition, a method of preparing a master chip containing a fluoropolymer by this method, diluting the master chip with a polyester chip, and spinning the yarn may be employed. When the component A is 100% by weight of the fluoropolymer, only the fluoropolymer is melted in the extruder.

Next, as described above, when the fiber of the present invention having an uneven shape is directly spun from a spinneret and when a weight reduction treatment is performed, a spinning temperature of 270 to 310 is applied using a general composite spinning apparatus. Spinning out of a die at ℃, solidification by cooling, taking off at a speed of 500 to 4000 m / min, and subsequently, at a temperature of 100 to 250 ° C. and a cutting elongation of 10 to 40%
What is necessary is just to stretch | stretch by the magnification which becomes about. It is also possible to adopt a high-speed spinning method in which the spun yarn is taken up at a high speed of 3000 to 8000 m / min and wound up without stretching.

In the case of performing the alkali weight reduction treatment, a usual treatment method may be used, but in the case of clothing fibers, it is preferable to carry out the treatment in the state of a woven or knitted fabric.

Further, the polyester fiber of the present invention comprises:
By performing the heat treatment at 60 ° C. or higher, the bonds in the fluoropolymer are caused to undergo thermal molecular motion, and the water repellency, oil repellency, and antifouling performance can be further improved. As the heat treatment method,
A dry heat treatment using a heater or a method of irradiating a laser beam may be used.

[0027]

Next, the present invention will be described specifically with reference to examples. In addition, various measurements and evaluations in the examples were performed as follows. (A) Relative viscosity of polyester component Measured by an ordinary method under the conditions of 0.5 g / dl and a temperature of 20 ° C. using an equal weight mixture of phenol and tetrachloroethane as a solvent. (B) Melt flow rate According to ASTM D 1238, temperature 265 ° C, load 5
It was measured under the condition of kg. (C) High elongation The obtained fiber was made into a 1/1 plain woven fabric as described in Examples, and after scouring, alkali weight reduction, dyeing, and dry heat treatment, the fiber was taken out from the woven fabric, and Was measured as follows. Using an Autograph DSS-500 manufactured by Shimadzu Corporation, the sample was elongated at a sample length of 30 cm, a grip interval of 5 cm, and a tensile speed of 30 cm / min, and the obtained load value at cutting was converted into a unit thickness, and the average value was calculated. Was defined as the fiber strength. The average of the elongation rates at the time of cutting obtained at the same time was defined as the elongation. (The number of measurements was 20.) (d) Water repellency The obtained fiber was made into a 1/1 plain woven fabric as described in Examples, and after scouring, alkali reduction, dyeing, and dry heat treatment, The woven fabric was evaluated according to JIS L-1092. (E) Oil repellency AATCC-118 was evaluated for the woven fabric in the same manner as in (d). (F) Antifouling property As in (d), the woven fabric is contaminated with a mixture of sauce, coffee, mayonnaise and beer, left for 10 minutes, and then subjected to JIS.
Cleaning was performed in the same manner as in L-1045, and from the degree of removal of contamination, の (good), Δ (somewhat good), × (bad)
It was evaluated on a scale. (G) Dyeability When dyeing was carried out under the conditions described in the examples, the dye concentration in the residual liquid after dyeing was measured with a spectrophotometer, and the amount of dye absorbed into the fiber (dye exhaustion) was determined. evaluated. (H) Half life According to JIS L-1094A method, temperature 20 ° C, humidity 4
It was measured at 0% RH. (I) Friction band voltage According to JIS L-1094B method, temperature 20 ° C, humidity 4
It was measured at 0% RH. In addition, only Example 14 was measured in the state of a woven fabric, and other Examples and Comparative Examples were measured in the state of a fiber.

Examples 1 to 12 and Comparative Examples 1 to 4 As component A, polyethylene terephthalate (hereinafter abbreviated as PET) having a relative viscosity of 1.38 and a fluoropolymer having a melting point of 170 ° C. and a melt flow rate of 170 ° C. Rate is 10
g / 10 min "THV-500G" manufactured by Sumitomo 3M Limited
(Hereinafter abbreviated as THV), and PET and THV are shown in Table 1.
Were mixed at a weight ratio as shown in FIG. As component B, PET obtained by copolymerizing 2.5 mol% of 5-sodium sulfoisophthalic acid and 13.3% by weight of ethylene glycol having a molecular weight of 6000, and TH as a fluoropolymer
Using V, copolymerized PET and THV were mixed at a weight ratio as shown in Table 1. Component A and Component B were spun from a composite spinneret having a pore size of 0.25 mm and 36 holes at a spinning temperature of 290 ° C. and a total discharge rate of 42.5 g / min. At this time, in the cross section of the fiber, as shown in FIG. 2, the surface of the fiber was covered with the component B, and the number of the components A and B was eight (the number of divisions was 16). Then, the spun yarn was heated at a temperature of 18 ° C. and a wind speed of 0.8 from the annular spray device.
After cooling and solidifying with a cooling air of m / sec and applying a spinning oil, it was taken up at a speed of 3000 m / min by a take-off roller at a temperature of 80 ° C. Subsequently, the take-off roller and the speed 4260
After stretching (1.42 times the stretching ratio) with a heating stretching roller (temperature: 140 ° C.) at m / min, winding was performed at a speed of 4200 m / min to obtain a 75d / 36f fiber yarn. The obtained fiber yarn is made into a 1/1 plain woven fabric, and scouring, alkali weight reduction processing, and dyeing processing (disperse dye: Terasil Navy SGL 5% ow, manufactured by Ciba Geigy) are performed by a conventional method.
f, Dispersant manufactured by Meisei Chemical Co .: Disper TL 1 g /
l, dyeing assistant: ammonium sulfate 2 g / l and acetic acid
Using a 0.1 cm3 / l dye bath, the fibers are
Drying heat treatment was performed at 170 ° C. for 3 minutes. As shown in FIG. 1, the cross-sectional shape of the fiber after these treatments was such that all of the components A formed convexes on the fiber surface.

Comparative Example 5 As the component A, the weight ratio between PET and THV was 99/1 (P
ET / THV), the same PET as the component A was used as the component B, and all the components A did not form the convex portions as shown in FIG. The melt spinning was performed using a composite spinning apparatus such that each of the fibers had eight (number of divisions: 16) fibers having a round cross-sectional shape. After spinning, stretching and winding are performed in the same manner as in Example 1, and 75 d
/ 36f fiber yarn was obtained. The obtained fiber yarn was made into a 1/1 plain woven fabric under the same conditions as in Example 1 and subjected to scouring, alkali weight reduction processing and dyeing dry heat treatment. The cross-sectional shape of the fiber after the treatment was a circular cross-sectional shape as shown in FIG.

Example 13 To the polyester component B, 5% by weight of an antistatic PET obtained by copolymerizing 2.0 mol% of 5-sodium sulfoisophthalic acid and 23.0% by weight of ethylene glycol as an antistatic agent was added. Except for the above, a fiber yarn was obtained in the same manner as in Example 2.

Example 14 As a component C, 10 parts of conductive carbon black was added to PET.
A fiber yarn was obtained in the same manner as in Example 2 except that the composite yarn containing the above-described composition was used and the composite spinning was performed so that the fiber had a cross-sectional shape as shown in FIG.

Reference Example 1 Only PET having a relative viscosity of 1.38 was used, and the pore size was 0.25.
Except that a single spinneret having a diameter of 36 mm and a number of holes of 36 was used, melt spinning and drawing were carried out in the same manner as in Example 1 to obtain a 75d / 36f fiber yarn.

Examples 1 to 14, Comparative Examples 1 to 5, Reference Example 1
Table 1 shows the physical properties of the fiber obtained in the above and the values of each evaluation.

[0034]

[Table 1]

As apparent from Table 1, Examples 1 to 14
The fiber had an uneven shape in which the component A was a convex, and had excellent water / oil / oil repellency / antifouling properties. In particular, Examples 1 to 9 and 13 were excellent in dyeability and thread properties as well as the polyester fiber of the reference example. Further, since the fiber of Example 13 contained an antistatic agent in Component B,
Since the fiber of Example 14 had the component C, which is a conductive part, near the center, the fibers could be prevented from becoming loose, clinging, and attaching dust due to the generation of static electricity at the time of spinning and wearing. Further, in Example 3, the woven fabric obtained after the weight loss treatment was subjected to home washing 30 times according to JIS L-1096 (103 method), and then the water repellency, oil repellency, and antifouling performance were evaluated. The evaluation results were water repellency of 100, oil repellency of 5, and antifouling property of ○, showing good water repellency, oil repellency and antifouling performance even after washing. On the other hand, the fibers of Comparative Examples 1 to 4 had satisfactory thread quality performance because the content of THV in the component A was too small, but were poor in water repellency, oil repellency, and antifouling properties. Was. Since the fiber of Comparative Example 5 had a shape without irregularities on the fiber surface, the water repellency and the oil repellency were inferior to those of the examples.

[0036]

As described above, the polyester fiber of the present invention has a concave-convex structure in which the fluorine polymer or the polyester resin containing the fluoropolymer has a concave-convex structure protruding from the fiber surface. Water, oil repellency, antifouling effect, and a synergistic effect of these effects expressed by the component A constituting the convex portion containing the fluoropolymer,
Has excellent water repellency, oil repellency and antifouling properties. In particular, when the other component B is a polyester resin containing 1 to 10% by weight of a fluoropolymer, the number of each of the components A and B is three or more, and all of the components A have a shape protruding from the fiber surface. ,
It is particularly excellent in water repellency, oil repellency, and stain resistance. Furthermore, when the antistatic agent is contained in the component B, it is possible to suppress the occurrence of yarn loosening, clinging, and adhesion of dust due to generation of static electricity during spinning and wearing.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one embodiment of a water-repellent, oil-repellent, and antifouling polyester fiber of the present invention.

FIG. 2 is a schematic cross-sectional view showing one embodiment of a polyester fiber which becomes a water-repellent, oil-repellent, and stain-resistant polyester fiber of the present invention by performing an alkali weight loss treatment.

FIG. 3 is a schematic sectional view showing another embodiment of the water-repellent, oil-repellent, and antifouling polyester fiber of the present invention.

FIG. 4 is a schematic cross-sectional view of a fiber of Comparative Example 5 having no convex portion on the fiber surface.

[Explanation of symbols]

 A component A B component B C component C

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D01F 1/09 D01F 1/09 (72) Inventor Yoshitaka Nagara 23 Uji Kozakura, Uji-shi, Kyoto 23 Unitika Co., Ltd. Central F-term in the laboratory (Reference) 4J002 BD14W BD15W BD16W CF05W CF05X CF06W CF06X CF07W CF07X CF14Y DA036 DA076 DA086 DD086 DG026 FD10Y FD116 GK01 4L035 DD02 EE13 EE20 FF10 JJ03 4L041 AA08 BA18A18AA18 BC CA47 CB02 CB25 CB28 DD01 DD11 DD18 DD19 DD21 EE08 EE15 EE20

Claims (4)

[Claims] (1) a fluorine-based polymer or a fluorine-based polymer:
Component A and polyester B each containing a polyester resin containing at least part by weight of a component A and a plurality of components B alternately and rotationally symmetrically in the cross-sectional shape, and at least a part of the component A on the fiber surface. A water-repellent, oil-repellent, and stain-resistant polyester fiber having an uneven structure with protruding portions. 2. Component B is a polyester resin containing 1 to 10% by weight of a fluoropolymer, wherein the number of each of component A and component B is 3 or more, and all of component A protrudes from the fiber surface. The water-repellent, oil-repellent, and antifouling polyester fiber according to claim 1. 3. The water-repellent, oil-repellent, and antifouling polyester fiber according to claim 1, wherein the component B contains an antistatic agent. 4. A component C near the center of the cross-sectional shape
4. The water-repellent, oil-repellent, and antifouling polyester fiber according to claim 1, wherein component C contains a conductive component.