JPH073531A - Composite fiber with excellent light resistance - Google Patents

Abstract

(57) [Summary] [Object] To provide a composite fiber having improved light resistance without losing the excellent function and characteristics of the fiber containing a saponified ethylene-vinyl acetate copolymer as one component. [Structure] Saponified ethylene-vinyl acetate copolymer,
The halide of a metal belonging to Group Ib of the periodic table is 0.0
A composite fiber comprising 1 to 5% by weight of polyamide, characterized in that the strength retention rate after carbon black irradiation treatment at a black panel temperature of 83 ° C. for 400 hours is 60% or more. .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite fiber composed of a saponified ethylene-vinyl acetate copolymer and a polyamide and having excellent light resistance. The fiber is excellent in color development, has a good color tone with deepness and gloss, is elastic and has high bulkiness, shape stability, and light resistance, and also has good washing durability. It is useful for cleaning products such as napped cloth and pile mats.

[0002]

2. Description of the Related Art Conventionally, water-retaining fibers such as cotton, rayon, and polyvinyl alcohol fibers have been widely used for cleaning articles such as napped fabrics and mops. In recent years, various functions have been provided due to diversification of cleaning. Many cleaning articles made of synthetic fibers to which the above is added have been proposed (Japanese Patent Publication No. 59-30419, Japanese Patent Publication No. 60-246725, Japanese Patent Publication No. 63-9418, and Japanese Patent Publication No. 63-92320). , JP-A-63-2
No. 81613, JP-A No. 63-28614, etc.). And wax to improve cleaning performance,
It is used by applying an oil agent for cleaning such as paraffin oil and a surfactant. Further, also in the pile mat, a pile mat is prepared by using a spun yarn mainly composed of a water-retaining fiber such as rayon or polyvinyl alcohol fiber as a pile yarn and impregnated with a lubricant or the like is used. ing.

However, a cleaning article made of synthetic fibers to which an oil agent for cleaning is applied has a problem that the fibers become sticky due to the oil agent and the usability is deteriorated, and moreover, the article to be cleaned is secondarily contaminated. In addition, the pile mat has a weak fiber stiffness, and when the pile fiber is lost, the bulkiness is lost and the matte dust removal effect and the tactile feel are greatly reduced especially when the pile falls asleep. is there. Further, since the spun yarn is used as the pile yarn, there is a lot of idle hair, and there is a problem that hair loss occurs during washing and use, and the hair loss easily causes secondary pollution in the room.

In order to solve the above-mentioned problems, excellent color developability, good deep color tone and gloss can be maintained for a long period of time, bulkiness, good handleability and touch, and good washing resistance. A composite fiber composed of a saponified ethylene-vinyl acetate copolymer and polyamide, which is good and has no hair loss and is suitable for cleaning articles and pile mats, has been proposed. However, since the composite fiber uses polyamide, there is a problem that it is extremely inferior in light resistance and deteriorates when exposed to sunlight, resulting in a decrease in strength in a short period of time.

In order to improve the light resistance, a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc. are added to the polymer as a light-resistant agent and an antioxidant. However, the addition of such a compound to the polyamide component of the composite fiber composed of the saponified ethylene-vinyl acetate copolymer and polyamide does not lead to a sufficient improvement in light resistance and deterioration in light resistance. Coloring occurs and only products with low practical value can be obtained.

[0006]

The object of the present invention is to eliminate the above-mentioned problems of the conventional cleaning articles, pile mats, etc.
It has excellent color development, can retain a good deep color tone and gloss for a long period of time, is bulky, has good handleability and touch, has good wash resistance and does not have hair loss, etc. It is to provide an excellent composite fiber.

[0007]

[Means for Solving the Problems] The present inventors have conducted research to solve the above problems. As a result, in a composite fiber composed of a saponification product of an ethylene-vinyl acetate copolymer and a polyamide, by adding a specific metal compound in the polyamide, it was found that the light resistance was significantly improved, and the present invention was completed. did. It is well known that metal compounds have a deteriorating effect on polymers.
However, it is surprising that certain metal compounds improve the light fastness of the polymer without degrading the polymer.

That is, the present invention relates to a composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide containing 0.01 to 5% by weight of a halide of a metal belonging to Group Ib of the periodic table. The composite fiber is characterized in that the strength retention after carbon black irradiation treatment at a black panel temperature of 83 ° C. for 400 hours is 60% or more.

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

In the present invention, the proportion of ethylene units in the saponified Et.VAc copolymer is preferably 25 to 70 mol%, particularly 30 to 70 mol%. If the proportion of ethylene units in the copolymer is less than 25 mol%, the spinnability during fiberization becomes poor, and the number of single yarn breaks and yarn breaks during spinning or drawing increases, resulting in lack of flexibility. Becomes Moreover, when the saponified Et / VAc-based copolymer and the polyamide are melt-complexed at a usual temperature of 250 ° C. or higher to produce a composite fiber, the saponified Et / VAc-based copolymer has poor heat resistance. Therefore, it is difficult to perform spinning smoothly. On the other hand, when the proportion of ethylene units exceeds 70 mol%, the proportion of saponified vinyl acetate units (that is, vinyl alcohol units) inevitably decreases, resulting in colorability,
The bulkiness is lowered, the usability is deteriorated, and the appearance is inferior.

Further, in the saponified Et.VAc type 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 deteriorated and the fiber properties such as strength are deteriorated, which easily causes troubles during the processing step. .

Further, it is preferable to use a saponified Et.VAc type 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 one repeating unit, the total of those units in the copolymer It shows the polymer average of the number (degree of polymerization).

The upper limit of the number average molecular weight of the saponified Et.VAc copolymer is not particularly limited, but if the polymerization degree becomes too high, the melt fluidity of the polymer at the time of melt spinning will deteriorate, and the fiber forming processability will be poor. The number average molecular weight is preferably 500 or less because it tends to be poor.
Especially saponified 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 type copolymer can be obtained by polymerizing and saponifying by a known method. Further, it is commercially available from Kuraray Co., Ltd. under the trade name of EVAL ↑ R and from Nippon Synthetic Chemical Industry Co., Ltd. under the trade name of SOL ↑ R, and is easily available.

In any case, when saponified Et.VAc-based copolymer contains metal ions such as alkali metal ions such as sodium ion and potassium ion and alkaline earth metal ions such as calcium and magnesium, saponification is carried out. Excessive cross-linking, main chain scission, side chain desorption, etc. occur in the Et / VAc-based copolymer, which easily causes gelation of the copolymer, and the thermal stability becomes poor, resulting in melting. The heat resistance during composite spinning tends to decrease. Therefore, saponified Et.
In order to continuously and continuously spin a composite 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.
It is preferable to keep m or less.

In order to improve the softening point, heat resistance, hot water resistance and the like of the saponified Et.VAc type copolymer, the saponified Et.VAc type copolymer in the composite fiber is optionally crosslinked. You may stay. As a cross-linking method, any method known as a cross-linking method for a vinyl alcohol unit-containing copolymer can be adopted. For example, aldehyde compounds such as monoaldehydes and dialdehydes, crosslinking with organic crosslinking agents such as polyisocyanates such as diisocyanates, crosslinking with inorganic crosslinking agents such as boron compounds, crosslinking with radiation or light such as γ rays or electron beams. And so on. When the cross-linking treatment is performed with dialdehyde, it is preferable to use a strong acid such as sulfuric acid or hydrochloric acid. Also, the presence of unreacted aldehyde after the cross-linking treatment may cause discoloration of the dyed product. It is preferable to oxidize the carboxylic acid or its salt with an agent or the like.

In the present invention, the polyamide, which is another component of the conjugate fiber, has a good bondability with the saponified Et.VAc type copolymer, and saponified E in various composite forms.
Saponified Et · V even when spun with t · VAc-based copolymer
Interfacial peeling does not occur at the joint surface between the Ac-based copolymer and the polyamide, and the processability of fiber formation is good. Polyamide has a relatively good redeposition property during washing, and saponified Et.
Combined with the extremely excellent anti-staining property of the VAc-based copolymer, it is possible to obtain a textile product which is extremely excellent in anti-staining property during washing.

Polyamide has a very high refractive index,
The colored fiber of polyamide alone tends to have whitish luster, but by combining it with a saponified Et.VAc-based copolymer having a low refractive index, it is possible to obtain a color tone with good color development, depth, and good gloss. You can In particular, when a saponified Et.VAc-based copolymer having a refractive index of 1.55 or less is used to form a composite with a polyamide, the color tone and gloss of the resulting composite fiber are further improved.

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

In the present invention, as a halide of a metal belonging to Group Ib of the periodic table (hereinafter sometimes simply referred to as a halide) contained in polyamide as a light-proofing agent, a chloride, bromide or iodide of copper is used. , Silver chloride, bromide, iodide and the like, and these can be used alone or as a mixture of two or more kinds. 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 light resistance of the composite fiber is insufficiently improved, while when it exceeds 5% by weight, the composite spinning property and the drawability are deteriorated.
Intense coloring by halides.

By using the halide in combination with other additives such as a heat-resistant agent such as mercaptobenzimidazole, various performances can be imparted to the composite fiber. Examples of the method of adding the halide to the polyamide include a method of adding it at the time of polymerizing the polyamide and a method of directly adding to the polyamide chip at the time of composite spinning. In addition, a master chip with a high concentration added to polyamide is prepared, and this is mixed with polyamide to dilute it to a predetermined concentration.
A so-called master-batch method can be mentioned.

The ratio of the saponified Et.VAc 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 to set it to 30:70 to 70:30 (weight ratio). When the proportion of the saponified Et.VAc-based copolymer in the composite fiber is less than 20% by weight, the fiber forming processability is inferior, and the proportion of the alcoholic hydroxyl group in the composite fiber is reduced, resulting in gloss and gloss. Causing a drop in color,
The redeposition resistance during washing tends to decrease. On the other hand, saponified Et.
If the proportion of the VAc-based copolymer is more than 80% by weight, the processability such as spinning, drawing, and entanglement treatment tends to be poor, and the fiber physical properties such as fiber strength and strength retention also deteriorate.

The composite form of the composite fiber may be any form such as a core-sheath type, a sea-island type, a laminating type and a mixed type thereof. In the case of the core-sheath type, either a two-layer core-sheath type or a multi-layer 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 a part 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 length direction of the fiber, the bonding surface may be linear, arc-shaped, or any other random curved shape, and further a plurality of bonding portions may be formed. They may be parallel to each other, radial, or any other shape.

As described above, in the composite fiber, saponified E
The t · VAc-based copolymer and the polyamide are 20:80 to 8
It is preferable that the composite is made at a weight ratio of 0:20,
The saponified Et / VAc-based copolymer has a surface area of the composite fiber of 6
It is desirable to occupy 0% or more. Especially,
Polyamide with high refractive index is saponified with low refractive index Et ・ V
When the composite form is such that it is covered with an Ac-based copolymer, it is possible to obtain a product which is not whitish and has good gloss and color tone with a deep depth such as wetness.

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 a modified cross section, for example, a flat shape, a polygon such as a tri-octagon, a T-shape, a multi-lobed shape, an elliptical shape, or the like can be used. Specific examples of the composite fiber of the present invention include the composite form and the cross-sectional shape shown in FIGS. In addition, the above-mentioned conjugate fiber can optionally contain optional additives such as a fluorescent whitening agent, a stabilizer, a flame retardant, and a colorant which are usually used in the fiber-forming polymer.

The composite fiber of the present invention is saponified Et.VAc.
It can be produced by melt-composite spinning using a system copolymer and a halide-containing polyamide and, if necessary, subjecting to stretching treatment, heat treatment and the like. Various conditions such as temperature during spinning, 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 used, the type 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 conjugate fibers from two kinds of thermoplastic polymers can be used.
For example, each of a saponified Et.VAc-based copolymer and a halide-containing polyamide is melted in a separate extruder to form a respective molten polymer stream, and the molten polymer stream is spun with a composite spin pack. A composite fiber can be produced by introducing the mixture into a device, combining and spun in a spinning pack, and spinning. The melting of each polymer at that time is usually 28
It is carried out at 5 ° C. or lower, and a spinning temperature in the range of 250 to 285 ° C. is adopted.

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

The filaments of the composite 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 fiber for napping or a napped yarn (pile yarn). Further, for example, ply-twisting, air processing, mixed fiber, etc. are performed to form a thread having a predetermined thickness and this thread is used as a thread for napping, or an interlace processing using a multifilament, Stuffing processing and conventional BCF method (Bulk
ed Continuous Filament method) after applying bulkiness by crimping, etc., combine multiple bulky textured yarns, perform ply twist, air-process, mixed fiber, etc., and use this yarn as a yarn for napping be able to.

In the case of producing a napped yarn from the multifilament yarn composed of the conjugate fiber of the present invention as described above, even if the same multifilament yarns are combined with each other, the multifilament yarn composed of the conjugate fiber and another multifilament yarn You may combine filament yarn. As the multifilament yarn of other fibers, a multifilament yarn made of aromatic polyamide fiber, aliphatic polyamide fiber, polyester fiber, or the like can be used. In that case,
The mixing ratio of the multifilament yarn of the other fibers is preferably less than 50% by weight, and particularly preferably less than 40% by weight of the fibers constituting the yarn for nap.

Not limited to multifilament yarns, the above-mentioned composite fibers are cut into short fibers of about 30 to 100 mm, which are spun alone or mixed with natural fibers such as cotton and hemp and other synthetic fibers. It is also possible to form spun yarn and use this spun yarn as a yarn for napping. Among them, hair loss resistance,
From the viewpoint of bulkiness, morphological stability, etc., a multifilament yarn mainly composed of composite fibers is desirable.

Various products can be manufactured using the above yarn for nap. For example, a pile fabric can be formed by weaving a pile fabric using the napped yarn, and the pile fabric can be used as a cleaning article. Further, the yarn for napped yarn is knitted and woven to produce a normal woven or knitted fabric, which is raised by buffing or other means to prepare a fabric having napped (raised) made of the composite fiber of the present invention. It can also be used as a cleaning article. Further, the napped yarn is cut to form short fibers of about 30 to 100 mm, and entangled non-woven fabric, non-woven fabric fixed with binder fiber or binder resin is formed from these short fibers, and these non-woven fabrics are formed. Raised by a suitable means and raised (raised) composed of the composite fiber of the present invention
It is also possible to fabricate a cloth having the above and use it as a cleaning article. When producing the above-mentioned cleaning article, it is advisable to set the thickness of the napped or raised fibers or threads to about 2 to 20 denier. These cloths having naps or naps may be cut into a predetermined size, for example, and used as a cloth-like cleaning article, or as a mitten-shaped bag-like cleaning article, or any other The shape may be used.

In the case of a mop yarn, a multifilament yarn or a spun yarn, which is or is not mainly subjected to crimping or other treatment mainly composed of the composite fiber of the present invention, is combined and twisted to form a total denier. Produces a mop yarn of about 250-500 denier. Then, such mop yarns are arranged in parallel in a meandering manner and arranged and fixed to form a moped frenched yarn, and the tufted body or the frenched yarn is fixed to a base material made of cloth or the like by sewing or other means. Then, a mop can be produced. Alternatively, the mop may be tufted directly onto the substrate to produce the mop. 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 the mop yarn mainly composed of the above composite fiber is used,
The form of mop and hataki and its manufacturing method are not particularly limited, and any conventional form and method may be used.

Further, the piled yarn may be produced by implanting the napped yarn obtained as described above as a pile yarn on a base material made of cloth such as woven cloth, knitted cloth and non-woven cloth. The type of base material, the method for implanting pile yarns, and the apparatus used therefor are not particularly limited, and any of the base material, method, and production apparatus used in the conventional production of pile mats can be used. The pile thread density is usually in the range of 1/5 to 1/12 for the gauge interval and 5 for stitches.
It is preferable that the range is from 13 to 13. If the pile thread density is too high, a large amount of dust adheres to the pile surface, and when stepped on, fine dust is scattered to easily re-contaminate the surrounding area. On the other hand, if the pile yarn density is too low, the dust-removing function is deteriorated, and the dust enters the eyes of the base material, which makes cleaning and removal thereof difficult. In addition, if necessary, the pile yarn mainly composed of the composite fiber of the present invention may be implanted in a base material together with the pile yarn composed of other fibers. In that case, it is preferable to keep the ratio of the pile yarn made of other fibers to 40% or less.

The above-mentioned base mat in which pile yarns are implanted can be used as it is as a pile mat. Generally, a backing material such as rubber or resin is applied to the back surface of the base material to fix the implanted pile yarns to prevent the pile yarns from coming off. It is preferable to stabilize it. Further, if necessary, another cloth may be laminated on the backing material made of a polymer. The pile yarn driven into the substrate may be used as it is without being cut, in the form of a loop pile, or may be cut and used in the form of a differential cut pile. The pile yarn length (length) is generally about 5 to 20 mm, preferably about 8 to 15 mm. Further, if necessary, it may be treated with any agent such as a wetting agent, an antistatic agent, a flame retardant, an antifungal agent, a bactericidal / insecticide.

The coloring of the yarns for napped hair is
It can be performed at any stage after the production of the conjugate fiber and before the production of the napped yarn, after the production of the napped yarn from the composite fiber, or after the production of the fiber product. In the case of directly producing a composite fiber that is colored by composite spinning, the colorant is saponified Et in the form of, for example, a master-batch.
-It is advisable to carry out 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 or dark blue, or an organic pigment such as phthalocyanine can be appropriately used according to the color tone to be exhibited in the textile product.

The composite fiber of the present invention is not limited to the above-mentioned napped yarn, but can be used in applications where the effects such as color developability, color tone, gloss and light resistance can be sufficiently exhibited. .

[0037]

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

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

(2) Measurement of degree of recontamination (DS) at the time of washing (a) Pretreatment The sample is washed once under the following conditions to be 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 x 1 minute 3 times (b) Recontamination treatment Take 6 pieces of 5 x 5 cm from the pretreated sample and make one set. Launder-O-meter type washing machine equipped with a contaminated liquid (3 g of the artificial oily soil component and solid soil component mixed below in a ratio of 3: 1 and detergent monogen paste 7 g to which water was added to make 4 liters) ) 150 ml
After putting 10 steel balls and preheating to 40 ± 2 ° C., the test piece is put into a washing machine and rotated for 20 minutes to be contaminated. 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, and then 50
Dry at ~ 60 ° C.

Artificial oily stain component: 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 to 61 ° C) ) 21.5% Cholesterol 5.0% Carbon black (Tamagawa carbon) 15.0%

Solid stain component Viscous stain (dry cleaning residue diatomaceous earth adsorbate) 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 piled up, and an automatic recording type spectrophotometer (RC-II type manufactured by Shimadzu Corporation) was used to measure 100 for MgO.
The reflectance (%) is measured three times and the average value is calculated. The pollution degree (DS: Degree of Soiling) is calculated by the following formula.
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 recontamination sample Indicates.

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

(4) Evaluation of Hair Loss Four brushes having a width of about 30 mm made of palm fibers were fixed at opposing positions along the length direction of a cylinder having a diameter of 100 mm, and the brushes were rotated at a speed of 75 rpm. The sample was brushed for 5 minutes while being brought into contact with the target and rotated, and the state of fiber loss at that time was evaluated.

EXAMPLE 1 Using methanol as a polymerization catalyst and azobis-4-methyloxy-2,3-dimethylvaleronitrile as a polymerization initiator, ethylene and vinyl acetate were radically heated at 60 ° C. under pressure. Polymerization was carried out to produce an ethylene-vinyl acetate random copolymer (number average molecular weight of about 350) having an ethylene content shown in Table 1. Next, this ethylene-vinyl acetate random copolymer was subjected to saponification treatment in a caustic soda-containing methanol solution, and the saponification degree of vinyl acetate units in the copolymer is shown in Table 1. A saponified Et.VAc copolymer in the wet state consisting of values was prepared. This saponified Et
The VAc copolymer is repeatedly washed with a large excess of pure water to which a small amount of acetic acid is added, and then washed with a large excess of pure water to obtain alkali metal ions and alkaline earth in the copolymer. The content of metal ions is about 10pp each
After that, water was separated from the copolymer by a dehydrator and dried sufficiently by vacuum drying at a temperature of 100 ° C. or less (refractive index 1.53).

The obtained saponified Et.VAc copolymer,
Nylon 6 (manufactured by Ube Industries, Ltd., 1013BK) chip-blended with 0.1% by weight of copper iodide and 0.2% by weight of 2-mercaptobenzimidazole was mixed with 2 different extruders.
It is melt extruded at 50 ° C., supplied to a spinning pack of a composite spinning device, and spun from a spinneret at a spinning temperature of 260 ° C.
Composite weight ratio, composite morphology, saponified Et.VA on core shown in
The core-sheath composite fiber of nylon 6 was spun on the c copolymer and the sheath, a non-aqueous spinning oil was attached thereto, and the mixture was wound up at 1500 m / min. The obtained spun raw yarn was drawn 2.0 times with an ordinary roller plate type drawing machine. The strength of the obtained drawn yarn was measured, and the strength after the light resistance measurement treatment was also measured to calculate the strength retention rate. The results are shown in Table 1. It can be seen that the strength retention is remarkably improved by incorporating copper iodide into nylon 6.

[0048]

[Table 1]

Example 2 The same saponified Et.V as used in Experiment No. 7 of Example 1
Melt composite spinning was performed using an Ac copolymer and nylon 6 chip-blended with 0.1% by weight of copper iodide and 0.2% by weight of 2-mercaptobenzimidazole in a weight ratio of 1: 1. Then, the side-by-side type composite fiber was spun out, stretched 4.3 times, and mechanically crimped to produce a crimped fiber. This 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 thermal binder composite fiber (core-sheath type composite fiber having a fineness of 2.5 denier in which the core component is polyethylene terephthalate and the sheath component is copolyester; fiber length 51 mm ) 20 parts by weight were mixed, a fiber web having an average basis weight of 45 g / m ↑ 2 was prepared by a dry method, and hydroentangling treatment was performed to entangle the fibers to produce a fiber-entangled nonwoven fabric. Then, for drying as well, a dry heat treatment was performed for 5 minutes in a hot air atmosphere at 135 ° C. to bond and fix the bonding points of the fibers with a binder fiber, and the fibers were caused to self-crimp. The resulting non-woven fabric had fine crimps with fine fibers, an average basis weight of 67 g / m 2 and an apparent density of 0.
The bulky nonwoven fabric was 16 g / cm ↑ 3. A brushing treatment is applied to one surface of this non-woven fabric by a conventional method, and a brushing (raised)
A fabric was obtained (napped fiber length of about 5 to 10 m).

The above napped cloth was made to contain a wetting agent and a bactericidal agent to obtain a wiping cloth. This wiping cloth had a non-greasy and soft feeling, had a good tactile sensation, had a high liquid absorbing property and a liquid retaining property of water or a mixed liquid of water and oil, and had an excellent wiping effect. The cloth was wiped clean and the hair loss was evaluated, and it was good.

Example 3 The same saponified Et.multidot.as prepared in Experiment No. 7 of Example 1
0.1% by weight of VAc copolymer and copper iodide, 2-
Melt composite spinning was performed using 1: 1 weight ratio of nylon 6 chip-blended with mercaptobenzimidazole at 0.2% by weight, and saponified Et.VAc copolymer was used as the core to give nylon 6 Spin the core-sheath type composite fiber into a sheath,
After drawing 2.0 times, the yarn is mixed and 1500 denier / 1
A multifilament of 00 filaments was produced, and this multifilament was crimped by a hot air fluid treatment method to obtain a crimped yarn. Two crimped yarns were plied and twisted to form a plied yarn having a total fineness of 3000 denier / ply and 100T / MZ, which was used as a pile yarn. On the other hand, as the base material, a non-woven fabric having an average basis weight of 160 g / m ↑ 2 obtained by impregnating a fiber-entangled non-woven fabric of polyester fiber with a binder resin is used, and the pile yarn produced above is piled into the pile density 8 × 8 / It was planted at inch ↑ 2. Then, after trimming the pile length to 9 mm and performing hair styling, apply nitrile synthetic rubber latex liquid to the back surface of the base material at a rate of 900 g / m ↑ 2, dry and cure at 160 ° C to obtain rubber. A lined pile mat was prepared. The degree of soil redeposition of the obtained pile mat was measured, and hair loss was also evaluated. The results are shown in Table 2.

[0052]

[Table 2]

Example 4 Same saponified Et.multidot. As prepared in Experiment No. 7 of Example 1
Melt composite spinning was carried out using a VAc copolymer, and nylon 6 chip-blended with copper iodide and 2-mercaptobenzimidazole in the proportions shown in Table 3, respectively, in a weight ratio of 1: 1. A core-sheath type composite fiber in which a modified Et.VAc copolymer is used as a core and nylon 6 is used as a sheath,
It was stretched 2.0 times. The strength of the obtained drawn yarn is measured,
The strength after the light resistance measurement treatment was also measured, and the strength retention rate was calculated. It can be seen that the light resistance is improved by incorporating copper iodide into nylon 6 in an amount within the range of the present invention.

[0054]

[Table 3]

[0055]

EFFECT OF THE INVENTION The composite fiber of the present invention has good light resistance, little strength reduction, good hair loss resistance and washing resistance, and has a clean and deep color tone and luster for a long time. Can be kept.

[Brief description of 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-based copolymer B: Polyamide

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location D01F 6/90 301 7199-3B

Claims (3)

[Claims] 1. A composite fiber comprising a saponified ethylene-vinyl acetate copolymer and a polyamide containing 0.01 to 5% by weight of a halide of a metal belonging to Group Ib of the periodic table, which is black. A composite fiber having a strength retention of 60% or more after a carbon arc irradiation treatment at a panel temperature of 83 ° C. for 400 hours. 2. A cleaning article comprising napped fibers, napped yarns or mop yarns which are mainly composed of the composite fiber according to claim 1. 3. A pile mat mainly composed of the composite fiber according to claim 1.