JPS63190013A - Deodorant fiberus structure - Google Patents

Abstract

PURPOSE:To obtain the titled structure having excellent deodorant properties, processing properties, washing resistance, fiber-forming properties and mechani cal characteristics, containing a direct copolymer of an unsaturated carboxylic acid (anhydride) and ethylene and copper powder in a specific ratio. CONSTITUTION:The aimed fibrous structure containing (A) >=8wt.% direct copolymer of (i) an unsaturated carboxylic acid, preferably acrylic acid and/or an acid anhydride thereof and (ii) ethylene and (B) wt.% fibrous material containing >=1wt.% copper powder passing through a sieve with 50 meshes. The fibrous structure is preferably spun yarn and further woven and knitted goods.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a fiber structure having deodorizing properties, and more specifically to a direct copolymer of an unsaturated carboxylic acid and/or its anhydride and ethylene. The present invention also relates to a deodorizing fiber structure containing copper powder.

(Prior art) Bad odors that are common in daily life are a representative form of irritating pollution that directly and indirectly harms the human body.

Foul odors include nitrogen compounds such as ammonia and amines, hydrogen sulfide, sulfur compounds such as mercaptans, aldehydes, ketones, fatty acids, and hydrocarbons.Based on odor prevention methods, ■Ammonia ■Methyl mercaptan
■Hydrogen sulfide ■Methyl sulfide ■Trimethylamine ■Acetaldehyde ■Styrene ■Methyl disulfide is designated and regulated as a specific malodorous substance. Various adsorbents are used to remove these odors. For example, inorganic adsorbents such as activated carbon, silica gel, zeolite, activated clay, and molecular sieves, ion exchange resins, and liquid adsorbents whose main components are extracts of plants of the Camellia family are well known. Products into which exchange groups, anion exchange groups, etc. are introduced are also known.

(Problem to be solved by the invention) However, many of these adsorbents are only effective against the bad odor of specific substances. Since there are only adsorption points on the surface, it has many drawbacks such as small adsorption capacity and poor durability.

The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to provide a fiber structure that is excellent in deodorizing properties against various bad odors, and has excellent processability, durability (especially washing resistance), fiber forming property, and mechanical properties. It's about providing things.

(Means for Solving the Problems) As a result of extensive studies to achieve the above object, the present inventor has found that fibers containing a specific polymer and copper powder have an excellent deodorizing effect. This discovery led to the present invention.

That is, the present invention provides a fibrous material containing a direct copolymer of an unsaturated carboxylic acid and/or its anhydride with ethylene and a copper powder that passes through a 50-mesh sieve, in an amount of 8% by weight or more as the copolymer. This is a deodorizing fiber structure characterized by containing 1% by weight or more of copper powder.

In the present invention, examples of unsaturated carboxylic acids and/or anhydrides thereof that form a copolymer with ethylene include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo(2,2, 2) Oct-5-ene-2゜3-dicarboxylic acid, 1,2,3,
4.5, 8.9゜10-octahydronaphthalene-2,
3-dicarboxylic acid, bicyclo(2,2,1)octa-7
-ene-2,3,5,6-tetracarboxylic acid, 7-oxabicyclo(2,2,1) to but-5-ene-2゜3-
Examples include dicarboxylic acids. Among these, particularly preferred are acrylic acid and methacrylic acid.

The content of carboxyl groups in the direct copolymer of unsaturated carboxylic acid and/or its anhydride with ethylene is 0.2 meq/g to 6 meq/g%, preferably 0.3 meq/g to 5 meq/g.
, more preferably 0.4meq/g to 4meq
/ g.

The copper powder used in the present invention passes through a 50 mesh sieve. If the particle size of the copper powder becomes too large, it becomes difficult to add and mix it into the fiber.

In the present invention, fibers containing a direct copolymer of unsaturated carboxylic acid and/or its anhydride with ethylene ('I?') and fibers containing copper powder (n) passing through a 50 mesh sieve are used.
As a fibrous material consisting of, the fiber (1) may itself be composed of the above-mentioned copolymer, or may be a fiber blended with the above-mentioned copolymer. Furthermore, fiber (1)-
A polymer phase (AI) consisting of the above copolymer or a polyester, polyamide or polyolefin containing 40% by weight or more of the copolymer, and a polymer phase (BI) consisting of a polyester, polyamide or polyolefin having fiber-forming properties. consisting of a polymer phase (AI) and (Bl)
The composite fiber may have a weight ratio of 95:5 to 20:80.

In this case, the polymer phase (AI) may be composed only of the above copolymer, but in order to further improve its deodorizing properties, mechanical properties, and fiber forming properties, it may be composed of polyester, polyamide, or polyolefin. Can be used in combination. The polymer phase (AI) consisting of the above-mentioned copolymer and polyolefin contains the above-mentioned copolymer in an amount of 40% by weight or more, particularly preferably from 95 to 50% by weight.

Furthermore, the polyester, polyamide or polyolefin constituting the polymer phase (Bl) may also be used as the polymer phase (AI).
The same polyester, polyamide or polyolefin used in can be used.

Furthermore, the polymer phase (AI) and (BI
) and the composite ratio is 95:5 to 20:8 by weight.
0, preferably in the range of 95:5 to 50:50. In addition, in the above composite fiber, a polymer phase (AI)
and (B1) can take any composite form, but in particular, in the cross section of the fiber, the polymer phase (AI) and (
Bl) forms at least two block shapes, and the polymer phase (AI) is present in an exposed form at least around the fiber cross section; the polymer phases (AI) and (BI) are:
At least 2 side by side in the fiber cross section
or a polymer phase (
Preferably, they form a sheath-core structure in which Bl) is the core component and the polymer phase (AI) is the sheath component.

Further, the composite fiber may have a circular cross-sectional shape, but it is preferable to have a large surface area in order to improve deodorizing performance, and the composite fiber should be non-circular and have a shape coefficient (D/d) of at least 1. 1, and the deformation coefficient preferably varies irregularly along the fiber axis direction, and the area of the cross section perpendicular to the fiber axis preferably varies irregularly along the axial direction. It is preferable to have.

Here, the degree of non-circularity of the cross-sectional shape is the circumference 2 of the cross-section.
It is expressed as an irregularity coefficient expressed as the ratio (D/d) of the maximum distance between parallel lines (D) and the minimum distance (d) between two circumscribed parallel lines.

The above-mentioned fibrous material containing a direct copolymer of ethylene with an unsaturated carboxylic acid and/or its anhydride may contain pigments, flame retardants, stabilizers, optical brighteners, etc., which are usually added to the polymer. It may also contain agents.

In addition, fibers containing copper powder that pass through a 50-mesh sieve (
U) may be a thermoplastic polymer blended with copper powder, further comprising a thermoplastic polymer phase (AII) containing 3.5 to 60% by weight of copper powder and a thermoplastic polymer having fiber-forming properties. The polymer phase (A
The weight ratio of ID) and (BII) is 95 = 5 to 30:
70 may be used.

In this case, the thermoplastic polymer phase (AI and (BII)
Examples include polyester, polyamide, polyurethane,
Examples include polyvinyl polymers, polycarbonates, polyacetals, polyurethanes, fluororesins, etc., and these can be used alone or in combination. Further, the polymer phases (An) and (BIB) may be the same polymer or may be different.

The content of copper powder in the polymer phase (AI) is 3°5-6
0% by weight. If the content of copper powder is less than 3.5% by weight, sufficient deodorizing and sterilizing effects cannot be obtained.

Furthermore, if the copper powder content exceeds 60% by weight, fiber formation becomes difficult and the cost increases.
The bactericidal effect does not improve.

Copper powder may be added and mixed into the polymer phase (AI) in advance using various mixing devices to sufficiently uniformly mix it into the polymer and form chips (or it may be mixed at the time of fiber formation). It's okay.

In addition, in the above composite fiber, the polymer phase (An) and (
Bff) can take any composite form, but in particular, in the cross section of the fiber, the polymer phase (AID) and (BIB) form at least two blocks,
The polymer phase (An) exists in an exposed form at least around the fiber cross section, and the polymer phase (An) and (BII)
refers to fibers that form at least two blocks side-by-side in the fiber cross section, or sheath-core type fibers in which the polymer phase (Bn) is the core component and the polymer phase (AI) is the sheath component. Preferably, it forms a structure.

Further, the composite fiber may have a circular cross-sectional shape, but it is preferable to have a large surface area in order to improve deodorizing performance, and the composite fiber should be non-circular and have a shape coefficient (D/d) of at least 1. 1, and the deformation coefficient preferably varies irregularly along the fiber axis direction, and the area of the cross section perpendicular to the fiber axis preferably varies irregularly along the axial direction. It is preferable to have.

Here, the degree of non-circularity of the cross-sectional shape is the circumference 2 of the cross-section.
It is expressed as an irregularity coefficient expressed as the ratio (D/d) of the maximum distance between parallel lines (D) and the minimum distance (d) between two circumscribed parallel lines.

The above-mentioned fibrous material containing copper powder may contain pigments, flame retardants, stabilizers, optical brighteners, etc., which are usually added to polymers.

The above-mentioned fibrous material containing fiber (■) and fiber (II) may be composed only of fiber (I) and fiber (II), and may further contain a third fiber component. As the third fiber component in this case, fibers such as polyester fibers, polyamide fibers, vinyl polymer fibers, cotton, wool, rayon, acetate, etc. can be used. The fibrous material containing these fibers (■), fibers (II), and/or the third fiber component contains 8% by weight or more as the above-mentioned copolymer and 1% by weight as the above-mentioned copper powder in the final fiber structure. % or more.

As shown in Figure 1, the fibrous material used in the present invention is a direct copolymer phase (A) of unsaturated carboxylic acid and/or its anhydride and ethylene, mixed with copper powder (C). An example is a dispersed one.

Furthermore, a composite fiber consisting of a copolymer phase (A) and a thermoplastic polymer phase (B) containing dispersed copper powder (C) may be used.

The composite ratio of polymer phases (A) and (B) in this composite fiber is preferably in the range of 95:5 to 20:80, particularly 95:5 to 50:50 in terms of weight ratio. In addition, in the above composite fiber, the polymer phases (A) and (B) can take any composite form, but especially in the cross section of the fiber, the polymer phases (A) and (B) and form at least two blocks, and the polymer phase (A
) exists in an exposed form at least around the fiber cross section, and the polymer phases (A) and (B) form at least two blocks side by side in the fiber cross section (the polymer phases 2), or the polymer phase (B
) is the core component and the polymer phase (A) is the sheath component, forming a sheath-core structure (Fig. 3), and furthermore, the sea component consisting of the polymer phase (A) is Preferably, the island components consisting of the polymer phase (B) are arranged in a sea-island pattern (FIG. 4).

In addition, in the above-mentioned composite fiber, the copper powder (C) may be dispersed in the polymer phase (A), and the copper powder may not be added to the polymer phase (B).

Further, the composite fiber may have a circular cross-sectional shape, but it is preferable to have a large surface area in order to improve deodorizing performance, and the composite fiber should be non-circular and have a shape coefficient (D/d) of at least 1. 1, and the deformation coefficient preferably varies irregularly along the fiber axis direction, and the area of the cross section perpendicular to the fiber axis preferably varies irregularly along the axial direction. It is preferable to have.

Here, the degree of non-circularity of the cross-sectional shape is the circumference 2 of the cross-section.
It is expressed as an irregularity coefficient expressed as the ratio (D/d) of the maximum distance between parallel lines (D) and the minimum distance (d) between two circumscribed parallel lines.

In the present invention, the polymer phase (A) may be composed only of the above-mentioned copolymer, but in order to further improve its deodorizing properties, mechanical properties, and fiber forming properties, it may be composed of polyester, polyamide, etc. Alternatively, it can be used in combination with polyolefin.

Furthermore, the polyester, polyamide or polyolefin constituting the polymer phase (B) can be the same as the polyester, polyamide or polyolefin used in the polymer phase (A).

The fibrous material in the present invention may contain pigments, flame retardants, stabilizers, fluorescent brighteners, etc. that are usually added to polymers.

When the fibrous material is a spun yarn, it is crimped and cut into short fibers in order to be blended with other fibers.
Usually, the number of crimps is 5/251 to 25/25 m, and the fiber length is 20 fl to 100 fl.

The method for producing the fibrous material used in the present invention includes the conventionally known orifice-type melt spinning method, as well as the production of reticulated fibers by kneading gas into a molten polymer and extruding it through a slit in a die using a burst of gas. A burst fiber method may be used to obtain a shaped product, and it can also be easily produced by the method described in the specification of Japanese Patent Application Laid-Open No. 58-91804, which was previously proposed by the present inventors.

Further, to describe an example of the method for manufacturing the above-mentioned composite fiber, it can be easily manufactured by the method described in the specification of JP-A-58-70712, which was previously proposed by the present inventors.

In other words, the polymer phase (A1
．． Extrude AI [or A), extrude the polymer phase (Bl, B■, or B) from the other extruder, and add a static mixer (for example, Ken ics) to a part of the adapter integrated with the piping.
A vertical mixer is inserted into the mold, and the molten mixture of both molds is mixed into a suitable layered state, and the mixture is sent to a summer die and uniformly discharged.

Further, the obtained fiber bundle was heated to 1.2 to 2. Stretch it to about Q times and machine p/! The crimp can also be applied by crimp or thermal crimp with hot air.

The mixing state and fineness of the polymer phases (A1.AII or A), (Bl, BI [or B)] are determined by the number of elements of the static mixer used as a mixer, the size of the mesh wire mesh used as the uneven mouthpiece, and the stretching ratio. It can be easily controlled by

The fiber thus obtained has a non-circular cross section, a shape coefficient (D/d) of at least 1.1, and the shape coefficient varies irregularly along the fiber axis direction. The area of the cross section perpendicular to the fiber axis varies irregularly along the axial direction.

As the cap, it is preferable to use a mesh (wire mesh) made of a substance that generates heat when energized.

The method for manufacturing composite fibers described above is not limited to this.

When the fiber structure of the present invention is a spun yarn or a woven or knitted fabric,
When blending or mixing the above-mentioned specific copolymer and fibrous material containing copper powder, any fiber such as cotton, wool, rayon, acetate, polyamide fiber, polyester fiber, vinyl polymer fiber, etc. can be used. Can be used.

The blending and mixing rate of the fibrous material containing the above-mentioned specific copolymer and copper powder for these fibers is such that the fibrous material contains 8% by weight or more as the copolymer and 1% by weight or more as the copper powder. Select as follows.

If the content of the copolymer is less than 8% by weight or the content of copper powder is less than 1% by weight, a sufficient deodorizing effect cannot be obtained.

In the spun yarn, the above-mentioned copolymer and copper powder-containing fibrous material may be uniformly blended with other fibers by a conventional method, and the former may be placed in the outer layer and the latter in the center. It may also be a two-layered blended yarn.

[In terms of products, the fibrous material containing the above-mentioned specific copolymer and copper powder can be used in any form such as filament or stable fiber. In order to mix these fibrous materials into woven or knitted fabrics, for example, there are methods such as blending them with other fibers and weaving them, blending and twisting them with other fibers and weaving them, mixing them with other fibers, A method such as alternating knitting can be used.

In addition, when the fiber structure is a nonwoven fabric, it can be applied to any conventionally known nonwoven fabric such as a dry nonwoven fabric, a wet nonwoven fabric, a web made of short fibers or long fibers, a spunbond nonwoven fabric, and a burst fiber nonwoven fabric. Further, as the fibers constituting these nonwoven fabrics, arbitrary fibers such as cotton, wool, rayon, acetate, polyamide fibers, polyester fibers, vinyl polymer fibers, etc. can be mixed.

The blending ratio of the fibrous material containing the specific copolymer and copper powder to these nonwoven fabric constituent fibers is such that the fibrous material contains 8% by weight or more as the copolymer and 1% by weight or more as the copper powder. Select as follows. If the content of the copolymer is less than 8% by weight or the content of copper powder is less than 1% by weight, a sufficient deodorizing effect cannot be obtained.

In order to incorporate the above-mentioned specific copolymer and copper powder-containing fibrous material into a nonwoven fabric, it is sufficient to mix it with the fibers that make up the nonwoven fabric in the nonwoven fabric manufacturing process, or to combine it with the fibers that make up the nonwoven fabric in the spinning process. It's okay.

(Function) The deodorizing mechanism of the deodorizing fiber structure of the present invention is not a physical adsorption deodorization like conventional activated carbon, but a direct copolymer of an unsaturated carboxylic acid and/or its anhydride and ethylene. In addition, it is based on chemical deodorization using copper powder, and since it is fibrous, the surface area becomes large, so the deodorizing ability is significantly improved.

In particular, direct copolymers of unsaturated carboxylic acids and/or their anhydrides with ethylene are useful for deodorizing bad odors caused by nitrogen compounds such as ammonia and trimethylamine, and aliphatic compounds such as n-butyric acid. Since it is effective in deodorizing bad odors caused by sulfur compounds such as hydrogen sulfide and methyl mercaptan, it can exhibit deodorizing effects against almost all types of bad odors.

Furthermore, direct copolymers of unsaturated carboxylic acids and/or their anhydrides with ethylene have poor mechanical properties, poor processability, poor durability, and poor fiber-forming properties when used alone. Although it is inconvenient to use these copolymers, the drawbacks of the above copolymers can be overcome by combining them with other polymers or mixing them with other fibers.

The above copolymer has not only a deodorizing effect but also a binder effect, and can be used as various binders.

Copper powder also has a bactericidal effect and has the additional effect of suppressing the generation of bad odors.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not equally limited to these.

In addition, as an evaluation of the deodorizing property, the deodorizing rate was determined by the following method.

That is, 10 g of a spun yarn sample is placed in a desiccator 41, the pressure is reduced with an aspirator, and a certain amount of measurement gas (liquid) is injected. Thereafter, the inside of the desiccator is returned to atmospheric pressure, and the gas concentration at that time is set as the initial gas concentration. The initial concentration is 2
Adjust so that it becomes 00 to 300pp+++. Furthermore, the gas concentration in the desiccator after 3 hours was measured, compared with the initial concentration, and the deodorization rate was calculated using the following formula.

Examples 1-3. Comparative Examples 1 and 2 Composite fibers were molded using an apparatus as shown in FIG. 4 described in JP-A-58-70712. That is, two 30φ
Ethylene-acrylic acid copolymer (manufactured by Mitsubishi Yuka: Yucalon EAA A-201M) chips were fed from one extruder (A), and copper powder passing through a 50-mesh sieve was fed from the other extruder (B). Polypropylene dispersed and mixed to have the content shown in Table 1 (manufactured by Ube Industries: S-
115M) chips were quantitatively melt-extruded,
The parts were merged just before the adapter part. In this case, the discharge ratio of both was changed so that the content as an ethylene/acrylic acid copolymer was as shown in Table 1. The extrusion temperature is 210°C to 250°C for the A side extruder and 250°C for the B side extruder.
20°C to 260°C, 250°C after the adapter part to the die
It was ℃. A Ken ics type vertical mixer element (8 pieces) is placed in a part of the adapter, and both component polymers are mixed together.Next, the mixed polymer is discharged from a concave-convex mouthpiece made of 60 mesh plain weave stainless steel wire. It was pulled up at a speed of 6 m/min while blowing cooling air. At this time, a current of about 50 A was passed through the cap to generate Joule heat to control the temperature of the cap.

The thus obtained discharged fibers were then stretched 1.3 to 2.5 times on a hot plate controlled at 85°C.

In the obtained fiber, the ethylene/acrylic acid copolymer and the copper-containing polypropylene are arranged side by side, and a part of the ethylene/acrylic acid copolymer is exposed around the cross section, so that the cross section of the fiber is The composite fiber was non-circular, had a shape factor of at least 1.4, and had a shape factor and cross-sectional area that varied irregularly along the fiber axis direction. The fiber properties were as shown in Table 1. This composite fiber was canted to a length of 95 strands and treated with hot air at 100° C. for 10 minutes to develop three-dimensional crimp. Table 1 shows the deodorization rate of this fiber.

Furthermore, when the fiber of Example 2 was subjected to a test for measuring the number of bacteria over time (measured using physiological saline at room temperature), the following effects were obtained.

No occurrence of black mold or white fungus was observed.

(This page, below margins) Table 1 Examples 4 to 6. Comparative Examples 3 to 4 Ethylene-acrylic acid copolymer (manufactured by Mitsubishi Yuka ■: Yucalon EAA A-201M) as a sheath component, polypropylene containing copper powder that passes through a 50-mesh sieve (S-115M, manufactured by Ube Industries ■) ) as a core component, an extruder type melt composite spinning machine was used to create a concentric core-sheath composite as shown in Fig.
tm) was discharged from a spinning hole and wound up at 500 m/min. At this time, the contents of the ethylene/acrylic acid copolymer and copper powder were varied as shown in Table 2. Next, this undrawn yarn was drawn 1.3 times in hot water at 70°C.

The physical properties and deodorization rate of this fiber were as shown in Table 2.

Furthermore, when a test for measuring the number of bacteria over time (measured using physiological saline at room temperature) was conducted on the fiber of Example 5, the following results were obtained.

No occurrence of black mold or white fungus was observed.

(This page, below margins) Table 2 Examples 7 to 9. Comparisons 5 to 6 51 m of composite fiber obtained by the same method as Example 1
The cotton was cut into lengths of 1.5 m and subjected to hot air treatment at 90° C. for 5 minutes to obtain pressed cotton having three-dimensional crimp of 10 crimps/251 m.

This cut cotton has a fineness of 4de, a fiber length of 64m, and a crimp rate of 1.
3 pieces/25 pieces of polyethylene terephthalate staple fiber were mixed in various proportions in a cotton batting process so that the contents of the ethylene-acrylic acid copolymer and copper powder were as shown in Table 3. A spun yarn was obtained.

The deodorization rates of these spun yarns were as shown in Table 3.

Furthermore, when the spun yarn of Example 8 was subjected to a test for measuring the number of bacteria over time (measured using physiological saline at room temperature), the following effects were obtained. No occurrence of black mold or white fungus was observed.

(This page, below margins) Table 3 Examples 10 to 12. Comparative Examples 7 to 8 Composite fibers melt-spun and drawn in the same manner as in Example 4 were crimped at 12/25 fi using a gear crimping device, and then cut to a length of 51 m to obtain cut cotton. Obtained.

This cut cotton and rayon stable fiber with a fineness of 2 des, a fiber length of 51, and a number of crimps of 10/25 fi were mixed so that the contents of the ethylene-acrylic acid copolymer and copper powder were as shown in Table 4. They were mixed in various proportions in a blending process to obtain a 20 count spun yarn.

The deodorization rate of these spun yarns was as shown in Table 4. In addition, the spun yarn of Example 11 was subjected to a test to measure the number of bacteria over time (measured using physiological saline at room temperature). When I did this, I got the following results. No occurrence of black mold or white fungus was observed.

Table 4 Examples 13-15. Comparative Example 9 Composite fibers were molded using an apparatus as shown in FIG. 4 described in JP-A-58-70712.

That is, from one of the two 30φ extruders (X), ethylene/acrylic acid copolymer (Mitsubishi Yuka side type: Yucalon EAA
A-201M) chips at a rate of 300 g/min from the other extruder (Y), polypropylene (made by Ube Industries):
Chips of S-115M) were quantitatively melt-extruded at 75 g/min and merged just before a portion of the adapter. The extrusion temperature was 210°C to 250°C for the A side extruder, 220°C to 260°C for the B side extruder, and 250°C from the part of the adapter to the die.

A Ken ics thruster mixer element (8 pieces) was placed in a part of the adapter to mix both component polymers. A stainless steel 60-mesh plain-woven wire gauze was used as the uneven mouthpiece, and the sample was taken at a speed of 6 m/min while blowing cooling air. At this time, a current of about 50A is passed through the base,
The temperature of the mouthpiece was controlled by generating Joule heat.

Subsequently, it was stretched 1.3 times using a hot plate controlled at 85° C. to obtain a stable side-by-side composite fiber.

As for the fiber properties, the average single yarn denier was 12 de, the strength was 1.2 g/de, and the elongation was 50%. Also, the irregularity coefficient is 1
．． It was 4.

Further, the fiber bundle was cut into 51 m lengths and subjected to hot air treatment at 90° C. for 5 minutes to obtain cut cotton having three-dimensional crimp. Furthermore,
A composite fiber was molded using the apparatus described in JP-A-58-70712. That is, one of the two 30φ extruders (X)
Electrolytic copper powder and polypropylene that pass through a 300-mesh sieve (Ube Industries type S-5-1l5 41J: 60
Quantitatively melt and extrude chips of polyethylene (Mitsubishi Kasei side type Noblen MK-40) at 60 g/min at a time from the other extruder (Y) at 240 g/min at a time of 240 g/min at a time of chips mixed at wt%. We merged at. A stainless steel 60 mesh plain weave wire mesh was used as the uneven base6.
The composite fibers were drawn at a speed of m/min and then stretched twice using a hot plate controlled at 120° C. to obtain composite fibers. As for the fiber properties, the average single yarn denier is 6.8 de.

The strength was 1.5 g/de and the elongation was 45%. 5 of the fibers
The cotton was cut into 11 squares and treated with hot air to obtain cut cotton having three-dimensional crimp.

This cut cotton is blended with polyethylene terephthalate cotton of 6 denier and cut length 51 nm with various contents of ethylene-acrylic acid copolymer and copper powder as shown in Table 5, and then passed through the usual short cotton spinning process. A spun yarn of number 20 was obtained. The deodorization rates of these spun yarns were as shown in Table 5.

Table 5 Examples 16-19. Comparative Example 10 Polyethylene terephthalate (manufactured by Kijin ■: (?) =
0.64) as a core component and an ethylene/acrylic acid copolymer (Mitsubishi Yuka ■: Yucalon EAA XA211S-1
) was used as a sheath component, and an extruder-type melt composite spinning machine was used to discharge it from a spinning hole with 20 holes so that a concentric core-sheath composite with a weight ratio of 6:4 was obtained.
It was wound up in 7 minutes.

At this time, the temperature of the extruder on the polyethylene terephthalate side is 270 to 295°C, and the temperature of the extruder on the ethylene/acrylic acid copolymer side is 210 to 295°C.
The temperature was 250°C. This undrawn yarn was placed in hot water at 75°C for 30 minutes.
．． It was stretched 0 times and further crimped using a push crimper. The physical properties of this composite fiber include an average single yarn denier of 6. O
de, strength was 3.2 g/de, and elongation was 40%.

The obtained fiber was cut into 51 m lengths to obtain cut cotton A.

Next, the copper powder-containing composite fiber was molded using the apparatus described in JP-A-58-70712.

That is, from one extruder (X) of two 30φ extruders, electrolytic copper powder that passes a 300 mesh sieve and polypropylene (Ube Industries type S-115M) are mixed at a ratio of 40:6.
Chips mixed at 0 wt% were quantitatively melt-extruded at a rate of 240 g/min, and chips of polypropylene (S-115M manufactured by Ube Industries, Ltd.) were quantitatively melt-extruded from the other extrusion 81 (Y) at a rate of 60 g/min at a rate of 60 g/min. We merged just before. A stainless steel 50-mesh plain-woven wire mesh was used as a concavo-convex base, and the wire was pulled at a speed of 10 m/min, and the wire was drawn continuously for 120 m/min.
The film was stretched 2.5 times using a hot plate controlled at a temperature of 0.degree. C., and crimped using a push crimper. The physical properties of this fiber include average single yarn denier of 7, Ode, and strength of 1.
．． It had an elongation of 8 g/de and an elongation of 45%. 5 of the obtained fibers
Cut cotton B was obtained by canting into one crane.

These cut cotton A and cut cotton B were blended with various contents of ethylene-acrylic acid copolymer and copper powder as shown in Table 6, and then spun into 20-count cotton through the usual short cotton spinning process. Got the thread.

However, in Example 19, cut cottons A and B were mixed with polyethylene terephthalate cotton of 6 denier and cut length of 510 mm. The deodorization rates of these spun yarns were as shown in Table 6. Further, when a test for measuring the number of bacteria over time (measured using physiological saline at room temperature) was conducted on the spun yarn of Example 17, the following results were obtained. No occurrence of black mold or white fungus was observed.

Table 6 Examples 20-22. Comparative Examples 11-12 Fibers obtained by the same method as Example 1 were
00 g/rd polyethylene terephthalate filament false-twisted yarn, knitted with ethylene,
The content as acrylic acid copolymer and copper powder is the seventh
The knitted fabrics were alternately knitted at various ratios as shown in the table, and the deodorization rate of the resulting knitted fabrics was measured. The measurement results were as shown in Table 7.

Furthermore, when the knitted fabric of Example 21 was subjected to a test for measuring the number of bacteria over time (measured using physiological saline at room temperature), the following effects were obtained.

No occurrence of black mold or white fungus was observed.

(This page, below margins) Table 7 Examples 23-25. Comparative Examples 13 to 14 Composite fibers melt-spun and drawn in the same manner as in Example 4 were given 12/25 crimps using a gear crimping device.
Cut cotton was obtained by cutting to a length of 51 inches.

This cut cotton was mixed at 50% by weight with rayon staple fiber having a fineness of 2 de, a fiber length of 51 w5, and a number of crimps of 12/25 w in a blending process to obtain a 30 count spun yarn.

This spun yarn is made of polyethylene terephthalate spun yarn,
The contents of ethylene/acrylic acid copolymer and copper powder were mixed in various ratios as shown in Table 8, and the fabric weight was 200 g/n? The deodorization rate was measured for the obtained twill fabric. The measurement results were as shown in Table 8.

In addition, when the fabric of Example 24 was subjected to a test to measure the number of bacteria over time (measured using physiological saline at room temperature), the following results were obtained.

No occurrence of black mold or white fungus was observed.

(This page, hereafter in the margin) No. 811 Examples 26-28. Comparative Example 15 Cut cotton and 6 denier obtained in the same manner as Example 13,
Polyethylene terephthalate cotton with a cut length of 51 mm is blended with various contents of ethylene-acrylic acid copolymer and copper powder, and then passed through a normal short cotton spinning process to produce 20 mm polyethylene terephthalate cotton.
A fine spun yarn was obtained. This spun yarn was mixed and woven with polyethylene terephthalate spun yarn, ethylene-acrylic acid copolymer, and copper powder in various proportions as shown in Table 9 to produce a twill fabric with a basis weight of 100 g/rd. The deodorization rate of the obtained fabric was measured. The measurement results were as shown in Table 9.

Table 9 Examples 29-32. Comparative Example 16 Cut cotton A and cut cotton B obtained by the same method as in Example 16 were mixed with various contents of ethylene-acrylic acid copolymer and copper powder, and spun using a normal short cotton spinning method. Through the process, a 20 count spun yarn was obtained. However, in Example 32, 6 denier was used for cut cotton A and B.
Polyethylene terephthalate cotton with a cut length of 51N was mixed. Using these spun yarns, we mixed and woven the contents of ethylene-acrylic acid copolymer and copper powder in various proportions as shown in Table 10 to obtain a fabric weight of 180 g/cd.
The deodorization rate of the obtained fabric was measured.

The results were as shown in Table 10.

Further, when a test for measuring the number of bacteria over time (measured using physiological saline at room temperature) was conducted on the fabric of Example 30, the following results were obtained. Furthermore, no occurrence of black mold or white fungus was observed.

(This page, below margins) Table 10 Examples 33-35. Comparative Examples 17-18 Composite fibers obtained by the same method as Example 1 were
It was canted to the length of a crane and treated with hot air at 1.00'C for 10 minutes to develop three-dimensional crimp. This was spread into a web using a card machine, and heat treated with 150 tons of hot air.
The deodorization rate was measured as a resin cotton-like nonwoven fabric of 250 g/r&. The measurement results were as shown in Table 11.

Further, when a test for measuring the number of bacteria over time (measured using physiological saline at room temperature) was conducted on the nonwoven fabric of Example 34, the following effects were obtained. No occurrence of black mold or white fungus was observed.

Table 11 Examples 36-38. Comparative Examples 19-20 Fibers obtained by the same method as in Example 4 were crimped at 12/25 crimps using a gear crimper, and then canted to a length of 51 m to obtain cut cotton. .

This cut cotton and polyethylene terephthalate staple fiber with a fineness of 4 de, fiber length of 76 fl, and number of crimps of 18 crimps/2511 m were mixed with various amounts of ethylene-acrylic acid copolymer and copper powder as shown in Table 12. Mix at a ratio of 150 to create a web using a card machine.
It was heat-treated with hot air at ℃ to obtain a resin cotton-like nonwoven fabric weighing 200 g/I. The measurement results of the deodorization rate were as shown in Table 12.

Furthermore, when the nonwoven fabric of Example 37 was subjected to a test for measuring the number of bacteria over time (measured using physiological saline at room temperature), the following results were obtained. No occurrence of black mold or white fungus was observed.

(This page, below margins) Table 12 Examples 39-41. Comparative Example 21 Cut cotton and 6 denier obtained in the same manner as Example 13,
Polyethylene terephthalate cotton with a cut length of 51 mm was mixed with various contents of ethylene-acrylic acid copolymer and copper powder as shown in Table 13 to create a web using a carding machine, and heat treated with hot air at 150°C. Alms, 220g/rr
A resin cotton-like nonwoven fabric of R was obtained.

The deodorization rates of these nonwoven fabrics were as shown in Table 13.

Table 13 Examples 42-45. Comparative Example 22 Cut cotton A and cut cotton B obtained by the same method as in Example 16 were mixed with various contents of ethylene-acrylic acid copolymer and copper powder as shown in Table 14, and carded cotton was prepared. The fibers were opened into a web using a machine. However, Example 45
In, cut cotton A.

B was further mixed with polyethylene terephthalate cotton of 6 denier and cut length of 511 m. The deodorization rate was measured using this web-like material. The measurement results were as shown in Table 14.

Further, when a test for measuring the number of bacteria over time (measured using physiological saline at room temperature) was conducted on the fibrous material of Example 43, the following results were obtained. Furthermore, no occurrence of black mold or white fungus was observed.

As is clear from the results of each example and comparative example in Table 14 and above,
The fiber structure of the present invention containing 8% by weight or more of ethylene-acrylic acid copolymer and 1% by weight or more of copper powder has excellent deodorizing performance, and also has excellent mechanical properties, durability, and processability. It had been improved.

A bactericidal effect was also observed.

(Effects of the Invention) The deodorizing fiber structure of the present invention exhibits excellent deodorizing performance against various bad odors, and also has excellent mechanical properties, processability, and durability, and also has a bactericidal effect. We have various clothing,
Sanitary napkins, disposable diaper-related sanitary materials, various filters, futon side fabrics, futon cotton and padding cotton, various felts, blankets, carpet bases, interior materials for buildings and automobiles,
Effective as a deodorizing material for shoe insoles, linings, bed mats, refrigerator deodorizing materials, various pads such as bras, girdles, body suits, bust pads, hip pads, side pads, sleeping wear, etc. can be used.

Furthermore, the deodorizing fibrous structure of the present invention does not lose its deodorizing performance even after repeated washing, and can release odors such as ammonia, trimethylamine, and n-butyric acid by washing and drying. It is possible to use the

[Brief explanation of the drawing]

1 to 4 are cross-sectional views showing examples of fibers used in the present invention. A: Direct copolymer of unsaturated carboxylic acid and/or its anhydride and ethylene Phase B: Thermoplastic polymer containing dispersed copper powder Phase C: Copper powder.

Claims (13)

[Claims] 1. A fibrous material containing a direct copolymer of unsaturated carboxylic acid and/or its anhydride and ethylene and copper powder that passes through a 50-mesh sieve, with 8% by weight or more as the copolymer and 1% by weight as the copper powder. A deodorizing fiber structure characterized by containing at least % by weight. 2. The deodorizing fiber structure according to claim 1, wherein the unsaturated carboxylic acid is acrylic acid. 3. Claim 1, wherein the fibrous material contains a fiber containing a direct copolymer of an unsaturated carboxylic acid and/or its anhydride with ethylene, and a fiber containing copper powder that passes through a 50 mesh sieve. The deodorizing fiber structure according to item 1 or 2. 4. Claim 1 or 2, wherein the fibrous material is a fiber in which copper powder is dispersed in a direct copolymer phase (A) of an unsaturated carboxylic acid and/or its anhydride and ethylene.
The deodorizing fiber structure described in Section 1. 5. The fibrous material consists of a direct copolymer phase (A) of an unsaturated carboxylic acid and/or its anhydride and ethylene, and a thermoplastic polymer phase (B) containing the copper powder dispersed therein, and both phases ( The deodorizing fiber structure according to claim 1 or 2, wherein A) and (B) form at least two blocks in the cross section of the fiber. 6. The deodorizing fiber structure according to claim 5, wherein the polymer phase (A) is exposed at least around the fiber cross section. 7. Claim 5 or 6, wherein the polymer phase (A) and the polymer phase (B) are arranged side by side.
The deodorizing fiber structure described in Section 1. 8. The deodorizing fiber structure according to claim 5 or 6, wherein the polymer phase (A) is arranged in the sheath part and the polymer phase (B) is arranged in the core part. 9. Polymer phase (B) in the sea component consisting of polymer phase (A)
7. The deodorizing fiber structure according to claim 5 or 6, wherein the island components consisting of the following are arranged in a sea-island pattern. 10. The cross section of the fiber is non-circular, and its irregularity coefficient (
D/d) is at least 1.1, the deformation coefficient varies irregularly along the fiber axis direction, and the cross-sectional area varies irregularly along the fiber axis direction. A deodorizing fiber structure according to any one of claims 3 to 9. 11. Claim 1, wherein the fiber structure is a spun yarn.
The deodorizing fiber structure according to any one of items 1 to 10. 12. Claim 1, wherein the fiber structure is a woven or knitted fabric.
The deodorizing fiber structure according to any one of items 1 to 10. 13. Claim 1, wherein the fiber structure is a nonwoven fabric.
The deodorizing fiber structure according to any one of items 1 to 10.