JP3280469B2 - Composite fiber with excellent light resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide and having excellent light resistance. The fiber is excellent in color development, has a good deep color tone and luster, is stiff and bulky, has excellent shape stability and light fastness, and also has good washing durability, and has a brush, mop, It is useful for cleaning articles such as napping cloth, pile mats and the like.

[0002]

2. Description of the Related Art Water-retaining fibers such as cotton, rayon, and polyvinyl alcohol fibers have been widely used in cleaning articles such as nap-up cloths and mops. There have been proposed many cleaning articles made of synthetic fibers provided with a polymer (Japanese Patent Publication Nos. 59-30419, 60-246725, 63-9418, and 63-92320). JP-A-63-2
No. 81613, JP-A-63-28614, etc.). And wax to improve cleaning performance,
Cleaning oils such as paraffin oil and surfactants are used. Also, in the case of a pile mat, a pile mat is produced using a spun yarn mainly composed of water-retaining fibers such as rayon and polyvinyl alcohol fiber as a pile yarn, and a pile mat impregnated with a lubricant or the like is used. ing.

[0003] However, cleaning articles made of synthetic fibers provided with a cleaning oil agent have problems that the oily agent causes the fibers to become sticky, making them inconvenient to use, and causing secondary contamination of the object to be cleaned. In addition, the pile mat described above has a problem in that the fibers have a weak stiffness, particularly when wet, and the pile fibers are remarkably stiff and the pile lays down. is there. Furthermore, since the spun yarn is used as a pile yarn, there is a problem that there are a lot of loose hairs, hair loss occurs at the time of washing and use, and the loose hairs easily cause secondary contamination in the room.

[0004] In order to solve the above-mentioned problems, excellent color development, good deep color tone and gloss can be maintained for a long period of time, bulkiness, good handleability and tactile sensation, and washing resistance. There has been proposed a composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide, which is favorable, has no hair loss, and is suitable for cleaning articles and pile mats. However, since the conjugate fiber uses polyamide, the light resistance is remarkably inferior, and there is a problem that when exposed to sunlight, the conjugate fiber is deteriorated and the strength is reduced in a short time.

In order to improve the light resistance, phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, etc. are added to the polymer as light-resistant agents and antioxidants. However, simply adding such a compound to the polyamide component of a composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide does not sufficiently improve the light resistance, and deteriorates the light resistance. And coloring, and only those having low practical value can be obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned problems of conventional cleaning articles and pile mats.
It is excellent in color development, can maintain good deep color tone and gloss for a long time, is bulky, has good handleability and tactile sensation, has good washing resistance, no hair loss, etc., and also has light resistance It is to provide an excellent conjugate fiber.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted research. As a result, in a composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide, it was found that light resistance was significantly improved by including a specific metal compound in the polyamide, thereby completing the present invention. did. It is well known that metal compounds have a degrading effect on polymers.
However, it is surprising that certain metal compounds do not degrade the polymer, and even improve the lightfastness of the polymer.

That is, the present invention relates to a method for producing
Is 25 to 70 mol%, the degree of saponification is 95% or more , and the number average
Polyamide 80 to 20 containing 20 to 80% by weight of a saponified ethylene-vinyl acetate copolymer having a molecular weight of 500 or less and 0.01 to 5% by weight of a halide of a metal belonging to Group Ib of the Periodic Table. % Of the composite fiber having a black panel temperature of 83 ° C. and a strength retention after carbon arc irradiation treatment of 400 hours of 60% or more.

In the present invention, "a saponified ethylene-vinyl acetate copolymer" which is one of the components constituting the composite fiber.
(Hereinafter referred to as a saponified Et.VAc copolymer) is a copolymer in which a vinyl acetate unit is hydrolyzed by saponification into a vinyl alcohol unit in an ethylene-vinyl acetate copolymer. Say.

In the present invention, the proportion of ethylene units in the saponified Et.VAc copolymer is preferably in the range of 25 to 70 mol%, particularly preferably 30 to 70 mol%. When the proportion of ethylene units in the copolymer is less than 25 mol%, the spinnability during fiberization becomes poor, and single yarn breakage and breakage during spinning and stretching increase, resulting in lack of flexibility. Becomes In addition, when the saponified Et.VAc-based copolymer and the polyamide are melt-spun at a temperature of 250 ° C. or higher to produce a composite fiber, the saponified Et.VAc-based copolymer has poor heat resistance. And spinning is difficult to be performed smoothly. On the other hand, when the proportion of the ethylene unit exceeds 70 mol%, the proportion of the saponified vinyl acetate unit (that is, the vinyl alcohol unit) is inevitably reduced, and the coloring property,
The bulkiness is reduced, the usability is reduced, and the appearance is inferior.

Further, in the saponified Et.VAc copolymer, it is preferable that 95% or more of the vinyl acetate units are saponified. When the saponification degree of the vinyl acetate unit is less than 95 mol%, the crystallinity of the saponified Et.VAc-based copolymer is reduced, the fiber properties such as strength are reduced, and it is likely to cause trouble during the processing step. .

It is preferable to use a saponified Et.VAc copolymer having a number average molecular weight of 250 or more. Here, the number average molecular weight means saponified Et.VAc.
When each of the ethylene unit, the saponified vinyl acetate unit (vinyl alcohol unit) and the unsaponified vinyl acetate unit constituting the copolymer is regarded as one repeating unit, the total of these units in the copolymer is obtained. It shows the average of a number of polymers (number of degrees of polymerization).

The upper limit of the number average molecular weight of the saponified Et.VAc copolymer is not particularly limited. However, if the degree of polymerization is too high, the melt fluidity of the polymer during melt spinning deteriorates, and the fiberization process However, it is usually preferable to use those having a number average molecular weight of 500 or less.
In particular, saponification E having a number average molecular weight in the range of 300 to 400.
It is preferable to use a t-VAc-based copolymer.

Such a saponified Et.VAc copolymer can be obtained by polymerization and saponification by a known method. It is also commercially available under the trade name EVAL @ R from Kuraray Co., Ltd. and under the trade name SOAR @ R from Nippon Synthetic Chemical Industry Co., Ltd., and is easily available.

In any case, when a saponified Et.VAc-based copolymer contains a metal ion such as an alkali metal ion such as sodium ion or potassium ion or an alkaline earth metal ion such as calcium or magnesium, the saponification occurs. Excessive cross-linking, main chain scission, side chain elimination, etc., occur in the Et.VAc-based copolymer, and the gelation of the copolymer is apt to occur. Heat resistance during composite spinning is likely to decrease. Therefore, saponified Et.
In order to stably and continuously spin a conjugate fiber composed of a VAc-based copolymer and a polyamide for a long time, the content of each metal ion in the saponified Et • VAc-based copolymer should be 100 pp.
m or less.

In order to improve the softening point, heat resistance, hot water resistance and the like of the saponified Et / VAc copolymer, the saponified Et / VAc copolymer in the composite fiber may be crosslinked in some cases. May be. As a crosslinking method, any method known as a method for crosslinking a vinyl alcohol unit-containing copolymer can be employed. For example, crosslinking with an organic crosslinking agent such as an aldehyde compound such as monoaldehyde or dialdehyde, or polyisocyanate such as diisocyanate, crosslinking with an inorganic crosslinking agent such as a boron compound, crosslinking with radiation or light such as γ-ray or electron beam. And the like. When performing a cross-linking treatment with a dialdehyde, it is preferable to use a strong acid such as sulfuric acid or hydrochloric acid, and if unreacted aldehyde is present after the cross-linking treatment, discoloration or the like of a dyed substance may be caused. It is preferable to prepare a carboxylic acid or a salt thereof by oxidation treatment with an agent or the like.

In the present invention, the polyamide, which is another component constituting the conjugate fiber, has a good bonding property with the saponified Et / VAc copolymer and can be used in various composite forms.
Saponified Et.V even when complex spinning with t-VAc copolymer
No interfacial delamination occurs at the joint surface between the Ac copolymer and the polyamide, and the fiberization processability is good. Polyamide has relatively good recontamination property during washing, and has a saponified Et.
In combination with the extremely excellent recontamination resistance of the VAc-based copolymer, it is possible to obtain a fiber product having extremely excellent recontamination resistance during washing.

Further, polyamide has a very high refractive index,
Colored fibers made of polyamide alone tend to have a whitish luster, but by combining it with a saponified Et / VAc copolymer having a low refractive index, the color tone is good, deep, and has a good luster. Can be. In particular, when a composite is formed with a polyamide using a saponified Et.VAc copolymer having a refractive index of 1.55 or less, the color tone and gloss of the obtained composite fiber are further improved.

The polyamide may be nylon 6, nylon 66, nylon 12, or two or three of them.
It is preferable to use the mixture of the above from the viewpoint of the fiberization processability. These polyamides may be used in combination with a small amount of a polyamide obtained by copolymerizing another third component, if necessary.

In the present invention, the halide of a metal belonging to Group Ib of the Periodic Table (hereinafter, sometimes simply referred to as halide) contained in the polyamide as a light stabilizer is chloride, bromide or iodide of copper. , Silver chloride, bromide, iodide and the like, and these can be used alone or as a mixture of two or more. The content of the halide with respect to the polyamide is 0.01 to 5%.
% By weight, preferably in the range of 0.05 to 3% by weight. When the content of the halide is less than 0.01% by weight, the improvement of the light resistance of the conjugate fiber is insufficient. On the other hand, when the content exceeds 5% by weight, the composite spinnability and stretchability are reduced,
Intense coloring by halides.

By using the halide in combination with other additives, for example, a heat-resistant agent such as mercaptobenzimidazole, various properties can be imparted to the conjugate fiber. Examples of the method of adding the halide to the polyamide include a method of adding the compound during the polymerization of the polyamide and a method of adding the compound directly to the polyamide chip during the composite spinning. In addition, a master chip with a high concentration added to polyamide is prepared, and this is mixed with polyamide and diluted to a predetermined concentration.
The so-called master-batch method is used.

The composite ratio of the saponified Et.VAc-based copolymer and the polyamide in the composite fiber is determined by the saponified Et.VA
c-based copolymer: polyamide = 20: 80 to 80:20,
It is particularly preferable that the ratio be 30:70 to 70:30 (weight ratio). When the ratio of the saponified Et.VAc-based copolymer in the conjugate fiber is less than 20% by weight, the fiberization process becomes poor, and the ratio of the alcoholic hydroxyl group in the conjugate fiber decreases, and the gloss and Inviting a drop in color,
Recontamination resistance during washing is apt to decrease. On the other hand, saponified Et.
If the proportion of the VAc-based copolymer exceeds 80% by weight, processability such as spinning, drawing, and entanglement tends to be poor, and fiber properties such as fiber strength and strength retention are also reduced.

The composite form of the composite fiber may be any form such as a core-sheath type, a sea-island type, a bonded type, and a mixed type thereof. In the case of a core-sheath type, any of a two-layer core-sheath type and a multilayer core-sheath type having three or more layers may be used. In the case of the sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and some of the islands may be exposed on the fiber surface. Furthermore, in the case of the bonding type, in the name fiber cross section perpendicular to the fiber length direction, the bonding surface may be any of a linear shape, an arc shape, or any other random curved shape, and further a plurality of bonding portions It may be parallel to each other, radial, or any other shape.

As described above, in the composite fiber, the saponified E
t: VAc-based copolymer and polyamide in 20: 80-8
It is preferable that the compound is compounded at a weight ratio of 0:20,
The saponified Et.VAc copolymer has a surface area of 6 of the composite fiber.
It is desirable to occupy 0% or more. In particular,
Polyamide with high refractive index is converted into saponified Et.V with low refractive index
When the composite form is covered with the Ac-based copolymer, it is possible to obtain a product which is not whitish, has a wet-like depth and has good gloss and color tone.

The cross-sectional shape of the conjugate fiber of the present invention may be any shape, and may be circular or irregular. In the case of an irregular cross section, it can be any shape such as a flat shape, a square shape such as a tri-octagonal shape, a T-shape, a multilobe shape, an oval shape, and the like. Specific examples of the composite fiber of the present invention include, for example, those having a composite form and a cross-sectional shape shown in FIGS. Further, the above-mentioned conjugate fiber may contain optional additives such as a fluorescent whitening agent, a stabilizer, a flame retardant, and a coloring agent, which are generally used in the fiber-forming polymer, if necessary.

The conjugate fiber of the present invention is a saponified Et.VAc
It can be produced by spinning a melt composite using a base copolymer and a halide-containing polyamide, and subjecting it to a stretching treatment, a heat treatment, and the like, if necessary. Various conditions such as spinning temperature, take-up speed, stretching temperature, stretching ratio, heat treatment temperature, etc.
It can be appropriately selected and set according to the component composition and saponification degree of the saponified Et.VAc-based copolymer to be used, the kind of polyamide, the composite ratio, the composite form and the like. As such a spinning method, any of the conventional melt composite spinning techniques for producing composite fibers from two types of thermoplastic polymers can be used.
For example, each of a saponified Et.VAc-based copolymer and a halide-containing polyamide are melted in separate extruders to form respective molten polymer streams, and the molten polymer streams are spun with a composite spin pack. A composite fiber can be produced by introducing into an apparatus, merging and compounding in a spinning pack, and spinning. The melting of each polymer at that time is usually 28
The spinning is performed at 5 ° C. or lower, and a temperature in the range of 250 to 285 ° C. is adopted as the spinning temperature.

When the composite fiber thus obtained is irradiated with carbon arc at a black panel temperature of 83 ° C. for 400 hours, the strength retention is 60% or more. The retention may exceed 80%, which is very practical. A composite fiber of a halide-free polyamide and a saponified Et.VAc-based copolymer has a strength retention of at most 42.5% after being treated under the above conditions, and has a deteriorating effect on the polymer. By containing a metal compound which is said to have in polyamide, the strength retention is greatly improved to 60% or more, and the light resistance is remarkably improved.

The filaments of the conjugate fiber thus obtained are combined to form a multifilament yarn, and a plurality of the multifilament yarns can be combined and used directly as a nap fiber (pile yarn). Further, for example, twisting, air processing, blending, or the like is performed to form a yarn having a predetermined thickness, and this yarn is used as a yarn for napping, or a multifilament is subjected to interface processing using hot air, Stuffing process and conventional BCF method (Bulk
After performing bulk processing by imparting crimp by the ed Continuous Filament method), a plurality of the bulk processed yarns are combined, twisted, air-processed, and blended, and the resulting yarn is used as a yarn for napping. be able to.

As described above, when a yarn for napping is produced from the multifilament yarn composed of the conjugate fiber of the present invention, even if the same multifilament yarn is combined, the multifilament yarn composed of the conjugate fiber and the multifilament yarn of another fiber are used. Filament yarns may be combined. As a multifilament yarn of other fibers, a multifilament yarn composed of an aromatic polyamide fiber, a fatty polyamide fiber, a polyester fiber, or the like can be used. In that case,
The mixing ratio of the multifilament yarn of the other fiber is preferably less than 50% by weight, and particularly preferably less than 40% by weight of the fiber constituting the napped yarn.

In addition to the multifilament yarn, the above-described conjugate fiber is cut into short fibers of about 30 to 100 mm, and these are singly or mixed with natural fibers such as cotton and hemp, and other synthetic fibers. It is also possible to form a spun yarn and use this spun yarn as a yarn for napping. Above all, hair loss resistance,
From the viewpoint of bulkiness and form stability, a multifilament yarn mainly composed of a conjugate fiber is desirable.

Various products can be manufactured by using the above-mentioned thread for raising hair. For example, a pile fabric can be formed by weaving a pile fabric using the thread for the nap, and this can be used as a cleaning article. Further, the napping yarn is knitted and woven to produce a normal woven or knitted fabric, which is then buffed by buffing or other means to produce a fabric having napping (napping) made of the composite fiber of the present invention. It can also be used as a cleaning product. Further, the napping yarn is cut to form short fibers of about 30 to 100 mm, and from these short fibers, an entangled nonwoven fabric, a nonwoven fabric fixed with a binder fiber or a binder resin are formed. Raising by a suitable means, and raising the nap of the composite fiber of the present invention (napping)
Can be used as a cleaning article. In preparing the above-mentioned cleaning article, the thickness of the fibers or yarns for raising or raising the brush is usually preferably about 2 to 20 denier. These cloths having raised or raised hairs may be cut into a predetermined size and used as a cleaning product in the form of a cloth, used as a cleaning product in a mitten-shaped bag, or may be used in any other manner. May be used.

In the case of mop yarns, multifilament yarns or spun yarns which have been subjected to crimping and other treatments or not, which are mainly composed of the conjugate fiber of the present invention, are twisted to give a total denier. Produces a mop yarn of about 250 to 500 denier. Then, such mop yarns are arranged and fixed in a meandering parallel to form a mop-frenzied yarn, and the tufted body and the frenzied yarn are fixed to a substrate made of fabric or the like by sewing or other means. To produce a mop. Alternatively, a mop may be produced by tufting a mop yarn directly onto a substrate. In addition, it is also possible to produce a flycatcher by fixing the mop tuft to the tip of the rod. In the present invention, as long as a mop yarn mainly composed of the above-mentioned composite fiber is used,
The form of the mop or the fly and the method of producing the mop are not particularly limited, and any conventional form and method may be used.

Further, a pile mat can also be prepared by implanting the napped yarn obtained as described above as a pile yarn in a base material such as a woven fabric, a knitted fabric or a nonwoven fabric. The type of the base material, the method of implanting the pile yarn, and the apparatus used therefor are not particularly limited, and any of the base materials, methods, and manufacturing apparatuses used in the production of conventional pile mats can be used. The pile yarn implantation density is usually in the range of 1/5 to 1/12 and the stitch is 5
It is preferable that the number be in the range of 13 to 13. If the implantation density of the pile yarn is too high, a large amount of dust adheres to the pile surface, and when trampled, fine dust scatters, which easily causes re-contamination of the surroundings. On the other hand, if the implantation density of the pile yarn is too low, the dust removing function is reduced, and the dust enters the eyes of the base material, making it difficult to remove the dust. If necessary, the pile yarn mainly composed of the composite fiber of the present invention may be implanted in the base material together with the pile yarn composed of other fibers. In that case, it is preferable that the ratio of the pile yarn composed of other fibers is set to 40% or less.

The base mat into which the pile yarn is implanted can be used as a pile mat as it is. However, in general, a backing material such as rubber or resin is applied to the back surface of the base material to fix the implanted pile yarn to prevent the pile yarn from coming off. It is preferable to stabilize. Further, another cloth may be laminated on the backing material made of a polymer, if necessary. The pile yarn driven into the base material may be used in the form of a loop pile without being cut as it is, or may be cut and used in the form of a cut pile having a non-uniform shape. The pile length (length) of the pile yarn is generally about 5 to 20 mm, preferably about 8 to 15 mm. If necessary, the composition may be treated with an optional agent such as a wetting agent, an antistatic agent, a flame retardant, a fungicide, a bactericide and an insecticide.

The coloring of the napping yarn is performed during the production of the conjugate fiber.
It can be performed at any stage after the production of the conjugate fiber and before the production of the napping yarn, after the production of the napping yarn from the conjugate fiber, or after the production of the fiber product. In the case of directly producing a conjugate fiber colored by conjugate spinning, the colorant is made into, for example, a master batch or the like, and the saponified Et is used.
-It is preferable to perform melt composite spinning after mixing with one or both of the VAc-based copolymer and the polyamide. As the colorant, an inorganic pigment such as titanium oxide, carbon black, ultramarine blue, navy blue or the like, or an organic pigment such as phthalocyanine can be appropriately used according to the color tone to be exhibited in the fiber product.

The conjugate fiber of the present invention is not limited to the above-mentioned napping yarn, but can be used for applications in which the effects such as color development, color tone, gloss and light resistance can be sufficiently exhibited. .

[0037]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Each physical property in the examples was measured by the following method,
evaluated.

(1) Fiber and Fiber Product Strength Retention (%) The composite fiber or fiber product is treated with a fade meter at a black panel temperature of 83 ° C. under arc irradiation for 400 hours,
Instron (manufacturer,
(Type). The strength after treatment with respect to the strength before treatment was shown as a retention rate.

(2) Measurement of recontamination degree (DS) at the time of washing (a) Pretreatment The sample is washed once under the following conditions and pretreated. Washing conditions: Washing machine: National Automatic NA-5050 Washing liquid: temperature 40 ± 2 ° C, detergent 0.25%, monogen,
Bath ratio 1: 100 Washing time: 10 minutes Rinse: 40 ° C. × 1 minute three times (b) Recontamination treatment Six test specimens of 5 × 5 cm are taken from the pretreated sample, and this is taken as one set. Contaminated liquid (3 g in which the following artificial oily soil component and solid soil component are mixed in a 3: 1 mixture with a Launder-O-meter type washing machine and water to 7 g of detergent monogen paste to make 4 liters) ) 150ml
After putting 10 steel balls and preheating to 40 ± 2 ° C., the test pieces are put into a washing machine and rotated for 20 minutes to contaminate them. After the contamination, the test piece was taken out of the washing machine and washed with about 3 liters of water for 1 minute, and this was repeated twice.
Dry at ６０60 ° C.

Artificial oily soil components: stearic acid 12.5% oleic acid 12.5% hardened coconut oil 12.5% olive oil 12.5% cetyl alcohol 8.5% solid paraffin (melting point 60-61 ° C.) 21.5% cholesterol 5.0% carbon black (Tamagawa carbon) 15.0%

Solid soil component Viscous soil (dry cleaning residue diatomaceous earth adsorbed material) 55% SiO 2 (Erol) 17% Fe 2O 3 0.5% Cement 17% n-lower hydrocarbon (heptane) 8.75% Carbon Black (Tamagawa Carbon) 1.75%

(C) Measurement Four test pieces obtained above were superimposed, and an automatic recording type spectrophotometer (RC-II type, manufactured by Shimadzu Corporation) was used for measuring 100 MgO.
The reflectance (%) is measured three times and the average value is taken. The degree of contamination (DS: Degree of Soiling) is calculated by the following equation.
Was calculated.

DS (%) = ｛(R ↓ 0−R ↓ S) / R ↓ 0｝ × 100 where R ↓ 0 is the reflectance of the sample before recontamination, and R ↓ S is the reflectance of the recontaminated sample. Is shown.

(3) Soil wiping property The artificial oily soil component is prepared, and the soil component is applied to a wooden floor to form an oily soil layer. The floor surface is wiped with a sample, and the soil at that time is wiped off. The wiping state was evaluated.

(4) Evaluation of Hair Loss Four brushes each made of palm fiber and having a width of about 30 mm are fixed at opposite positions along the length direction of a cylinder having a diameter of 100 mm, and the brushes are fixed at a speed of 75 rpm. The sample was rotated while being in contact with a tar, and the sample was brushed for 5 minutes, and the state of the detachment of the fiber at that time was evaluated.

Example 1 Using methanol as a polymerization catalyst and azobis-4-methyloxy-2,3-dimethylvaleronitrile as a polymerization initiator, radically convert ethylene and vinyl acetate under pressure at 60 ° C. By polymerization, an ethylene-vinyl acetate random copolymer having an ethylene content shown in Table 1 (number average molecular weight: about 350) was produced. Next, this ethylene-vinyl acetate random copolymer was subjected to a saponification treatment in a methanol solution containing caustic soda, and the degree of saponification of vinyl acetate units in the copolymer was shown in Table 1. To produce a saponified Et.VAc copolymer in the wet state. This saponification Et
Washing the VAc copolymer with a large excess of pure water to which a small amount of acetic acid is added, and then repeating washing with a large excess of pure water to obtain alkali metal ions and alkaline earth in the copolymer. About 10 pp each
m and then water was separated from the copolymer by a dehydrator, and sufficiently dried by vacuum drying at a temperature of 100 ° C. or less (refractive index 1.53).

The obtained saponified Et.VAc copolymer,
Nylon 6 (1013BK, manufactured by Ube Industries, Ltd.) blended with 0.1% by weight of copper iodide and 0.2% by weight of 2-mercaptobenzimidazole in a separate extruder.
The mixture was melt-extruded at 50 ° C., supplied to a spin pack of a composite spinning device, and spun from a spinneret at a spinning temperature of 260 ° C.
The composite weight ratio, composite form and saponified Et.VA
A core-sheath composite fiber of nylon 6 was spun onto the c-copolymer and sheath, and a non-aqueous spinning oil agent was adhered and wound at 1500 m / min. The obtained spun yarn was drawn 2.0 times by a usual roller plate type drawing machine. The strength of the obtained drawn yarn was measured, and the strength after the treatment of light resistance measurement was also measured to calculate the strength retention. Table 1 shows the results. It can be seen that the strength retention was significantly improved by including copper iodide in nylon 6.

[0048]

[Table 1]

Example 2 Same Saponified Et.V as used in Experiment No. 7 of Example 1
Melt composite spinning using an Ac copolymer, 0.1% by weight of copper iodide, and nylon 6 chip-blended with 0.2% by weight of 2-mercaptobenzimidazole was used at a weight ratio of 1: 1. Then, a side-by-side type composite fiber was spun out, stretched 4.3 times, and then mechanically crimped to produce a crimped fiber. The crimped fiber was cut into a fiber length of 51 mm to obtain a staple fiber having a single fiber fineness of 2 denier.
80 parts by weight of this staple fiber and a heat binder conjugate fiber (core-sheath type conjugate fiber having a fineness of 2.5 denier composed of polyethylene terephthalate as a core component and copolymerized polyester as a sheath component; fiber length 51 mm) 20) parts by weight of cotton were mixed, a fiber web having an average basis weight of 45 g / m @ 2 was prepared by a dry method, and subjected to a hydroentanglement treatment to entangle the fibers to prepare a fiber-entangled nonwoven fabric. Next, a dry heat treatment was performed for 5 minutes in a hot air atmosphere at 135 ° C. for the purpose of drying, so that the bonding points of the fibers were bonded and fixed with the binder fibers, and the fibers were allowed to self-crimp. The obtained nonwoven fabric has a beautiful micro-crimped fiber, an average basis weight of 67 g / m @ 2, and an apparent density of 0.
It was a bulky nonwoven fabric of 16 g / cm @ 3. The surface of this non-woven fabric is raised by a conventional method, and then raised (nap).
A fabric was obtained (length of nap fiber: about 5 to 10 m).

A wiping cloth was prepared by adding a wetting agent and a bactericide to the above-mentioned napkin fabric. This wiping cloth had a soft and good tactile sensation without stickiness, high liquid absorption and retention of water or a mixture of water and oil, and was excellent in wiping effect. The cloth was evaluated for dirt wiping properties and hair loss properties and found to be good.

Example 3 The same saponified Et. Produced as in Experiment No. 7 of Example 1
0.1% by weight of a VAc copolymer and copper iodide, 2-
Melt composite spinning is carried out by using a 1: 1 weight ratio of nylon 6 blended with 0.2% by weight of mercaptobenzimidazole and chip-blended, and nylon 6 is formed using a saponified Et.VAc copolymer as a core. Spinning out a sheath-core composite fiber made into a sheath,
After drawing 2.0 times, the yarns are combined and 1500 denier / 1
A multifilament of 00 filament was produced, and the multifilament was crimped by a hot air fluid treatment method to obtain a crimped yarn. The two crimped yarns were plied to form a plied yarn having a total fineness of 3000 denier / line and 100 T / MZ, which was used as a pile yarn. On the other hand, as the base material, a nonwoven fabric having an average basis weight of 160 g / m @ 2 in which a binder resin was impregnated into a fiber entangled nonwoven fabric of polyester fibers, and the pile yarn produced above was piled at a pile implantation density of 8 × 8 yarns / I planted it at inch2. Then, the pile length was cut to 9 mm and the hair was adjusted. Then, a nitrile-based synthetic rubber latex solution was applied on the back surface of the base material at a rate of 900 g / m @ 2, dried, cured at 160 ° C., and treated with rubber. A backed pile mat was made. The degree of recontamination of the obtained pile mat with washing was measured, and hair loss was also evaluated. Table 2 shows the results.

[0052]

[Table 2]

Example 4 The same saponified Et. Produced as in Experiment No. 7 of Example 1
The melt composite spinning was carried out by using a VAc copolymer, nylon iodide, and chip-blended nylon 6 in a ratio shown in Table 3 of copper iodide and 2-mercaptobenzimidazole in a weight ratio of 1: 1. A core-sheath type composite fiber in which nylon 6 is sheathed with a modified Et.VAc copolymer as a core,
Stretched 2.0 times. Measure the strength of the obtained drawn yarn,
The strength after the light resistance measurement was also measured, and the strength retention was calculated. It can be seen that by including copper iodide in nylon 6 in an amount within the range of the present invention, light resistance is improved.

[0054]

[Table 3]

[0055]

The conjugate fiber of the present invention has good light fastness, little decrease in strength, good hair loss resistance and washing resistance, and provides a clean, deep, good color tone and gloss for a long time. Can be kept.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a cross-sectional shape of a conjugate fiber of the present invention.

[Explanation of symbols]

 A: Saponified Et / VAc copolymer B: Polyamide

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // D01F 6/90 301 D01F 6/90 301 (56) References JP-A-55-1379 (JP, A) JP-A-2 -200838 (JP, A) JP 47-9748 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 8/10-8/12 D01F 1/10 D01F 6/90 301 A47L 13/16 D03D 27/00

Claims (3)

(57) [Claims] An ethylene unit having a ratio of 25 to 70 mol.
%, Saponification degree is 95% or more , number average molecular weight is 500 or less
In a ethylene - vinyl acetate copolymer saponified 20
80% by weight and a polyamide 80 to 80 % by weight containing a halide of a metal belonging to Group Ib of the periodic table in an amount of 0.01 to 5% by weight.
A composite fiber comprising 20% by weight, wherein the strength retention after carbon arc irradiation treatment at a black panel temperature of 83 ° C. for 400 hours is 60% or more. 2. A cleaning article comprising a nap fiber, a nap thread or a mop thread mainly comprising the conjugate fiber according to claim 1. 3. A pile mat mainly comprising the conjugate fiber according to claim 1.