JP2000226769A - Fiber structure having deodorant effect - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber structure having good feeling and deodorant effect and sustaining the effects for a long time and excellent in laundry endurance. SOLUTION: This fiber structure includes hollow fiber and at least a part of the hollow fiber has cavities dispersed through holes to the fiber surface and a sustained-releasing gel of a hydrous polymer including a component of an extract oil from a bamboo having deodorant effect is included in the cavities of the hollow fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure having a deodorizing effect, and more particularly, to a fiber structure comprising a hollow fiber, wherein a hollow portion of the hollow fiber has a water absorbing polymer having a deodorizing effect. The present invention relates to a fiber structure having a deodorizing effect in which a sustained release gel is present.

[0002]

2. Description of the Related Art In recent years, with the diversification of living environments aiming at a comfortable life, people are more and more interested in odors, and many fibers having a deodorizing function and products using the same have been proposed. For example, in order to remove malodor by using a fiber structure, a fiber raw material mainly composed of a thermoplastic polymer compound having a fiber forming ability and an adsorbent for adsorbing odor is melt-spun (Japanese Patent Laid-Open No. 2-157040). And a method in which a deodorant is applied via a polyurethane-based resin composition in post-processing (JP-A-2-269875).
And those using a polyester resin (JP-A-7-21)
No. 6751).

[0003] However, in the method of melt-spinning a fiber raw material mainly composed of the above-mentioned thermoplastic polymer compound having a fiber-forming ability and an adsorbent for adsorbing odor, although durability is obtained, deodorization is required in the spinning process. Since the thermal stability and particle size of the agent become problems, there is a problem that the selection of the deodorant is not versatile. On the other hand, in the deodorizing process by the post-processing method, although there is versatility of the deodorant, polyurethane resin,
Alternatively, the adhesiveness between the polyester resin and the material fiber is weak, causing a problem in durability. When the amount of the binder is increased in order to improve the durability, the texture becomes hard.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and has a good texture and deodorizing effect, a long-lasting effect, and excellent washing durability. Is provided.

[0005]

According to the present invention, as a result of intensive studies to achieve the above object, in a fibrous structure containing hollow fibers, at least a part of the hollow fibers is transferred from the fiber surface to the hollow part. Is formed of hollow fibers interspersed with the communication holes, and in the hollow portion of the hollow fibers, a sustained-release gel of a water-absorbing polymer containing a component having a deodorizing effect is present, and the component having the deodorizing effect is gradually added. It has been found that, by releasing the same, an excellent deodorizing effect is obtained and the washing durability is also excellent, and the present invention has been completed.

That is, according to the present invention, in a fibrous structure containing a hollow fiber, at least a part of the hollow fiber has a hollow portion in which communication holes from the fiber surface to the hollow portion are scattered. In the fibrous structure having a deodorizing effect, a sustained-release gel of a water-absorbing polymer containing a bamboo extract oil component having a deodorizing effect is present in the portion.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The fiber structure of the present invention may be a fiber aggregate provided for ordinary clothing use or industrial use, and such a fiber aggregate includes at least one part of a hollow fiber.

[0008] Examples of the hollow fibers used herein include chemical fibers such as rayon and acetate, and synthetic fibers such as polyester and polyamide. Particularly, a polyester fiber is preferably exemplified. As used herein, the polyester means a polyester containing terephthalic acid as a main dicarboxylic acid component and at least one glycol, preferably at least one alkylene glycol selected from ethylene glycol, trimethylene glycol and the like as a main glycol component. It is. If necessary, the polyester may contain a stabilizer, an antioxidant, a flame retardant, an antistatic agent, a fluorescent brightener, a catalyst, a coloring inhibitor, a heat-resistant agent, a coloring agent, inorganic particles, and the like. .

The hollow fiber can be produced by a conventionally known method. For example, actual fair 2-
As described in JP-A-43879, for a hollow fiber having an arc-shaped slit hole in which at least one portion is discontinuous, and having a semi-moon-shaped protrusion at an inner edge near an end of the slit hole. A method of melt spinning using a spinneret or the like can be arbitrarily adopted.

The hollow ratio of such a hollow fiber is in the range of 5 to 40% so that the hollow portion can be filled with a sufficient amount of polymer while maintaining the mechanical properties of the fiber. Are preferably used, more preferably 2
Those in the range of 0 to 40% are used.

A method for forming a large number of communication holes from the fiber surface of the hollow fiber to the hollow portion is disclosed in Japanese Patent Laid-Open No. 1-20 / 1990.
As disclosed in Japanese Patent No. 319, for example, in the case of polyester fiber, a polyester obtained by copolymerizing an organic sulfonic acid compound is mixed and melt-spun to form a hollow fiber,
A method of forming a communication hole by subjecting the hollow fiber to an alkali reduction treatment is used.

Further, if a hollow fiber having a hollow ratio of 20% or more is used, the hollow fiber can be treated only with an alkali and the low fiber along the longitudinal direction of the fiber can be obtained without using an organic sulfonic acid compound as described above. A large number of communication holes can be formed as removal marks of the orientation part and / or the deformation strain concentration part.

Further, as another method of obtaining hollow fibers, a method of dissolving or decomposing the core polymer of the core-sheath type composite fiber to form hollow fibers having a communication hole in the sheath can also be used.

The communication hole thus formed preferably has a width of 0.2 to 10 μm and a length of 5 to 20 μm. When the width and the length of the communication hole are out of this range, the introduction of the sustained-release gel of the water-absorbing polymer into the hollow fiber becomes insufficient, or the sustained-release of the water-absorbing polymer filled in the hollow portion. This is not preferred because the conductive gel may easily fall off.

The sustained-release gel of the water-absorbing polymer used in the present invention includes, for example, natural water-absorbing polymer gels such as gelatin gel and synthetic water-absorbing polymer gels. The use of a synthetic water-absorbing polymer gel is preferred because it is easy to handle at the stage.

The synthetic water-absorbing polymer gel includes:
For example, (a) a water-soluble monomer having at least one group selected from the group consisting of carboxylic acid groups, carboxylic acid groups, sulfonic acid groups and sulfonic acid groups, such as acrylic acid, methacrylic acid, and croton Acid, cinnamic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, methallyl sulfonic acid, styrene sulfonic acid and their Na salts, K salts, Li salts and the like,
(B) a monomer that becomes water-soluble by hydrolysis,
Examples of a monomer having at least one hydrolyzable group (ester group, nitrile group, etc.) include (c) a starch and / or cellulose group, and (d) a crosslinking agent.
Gels of a water-absorbing polymer obtained by polymerizing (a) and / or (b) and (d) as essential components and hydrolyzing as necessary can be mentioned.

Specific examples of the gel of the water-absorbing polymer include a cross-linked neutralized salt of poly (meth) acrylic acid,
Partial hydrolyzate of cross-linked poly (meth) acrylamide, cross-linked (meth) acrylic acid- (meth) acrylamide copolymer, cross-linked sulfonated polystyrene,
Saponified vinyl ester-unsaturated carboxylic acid copolymer,
Gels such as a crosslinked (meth) acrylic acid- (meth) acrylate copolymer, a crosslinked isobutylene-maleic anhydride copolymer, a crosslinked carboxylic acid-modified polyvinyl alcohol, and the like can be given.

As synthetic water-absorbing polymer gels other than those exemplified above, for example, (a) and / or (b), (c) and (d) are polymerized as essential components,
A gel of a water-absorbing polymer obtained by hydrolyzing if necessary.
No. 6, JP-B-53-46199, JP-B-53
-46200, a water-absorbing polymer gel described in JP-B-55-21041, and the like.
A water-absorbing polymer gel obtained by polymerizing (a) and / or (b) and (c), for example, a hydrolyzate of a starch-acrylonitrile graft polymer and a hydrolyzate of a cellulose-acrylonitrile graft polymer A decomposed product, a crosslinked product of (c), for example, a crosslinked product of carboxymethylcellulose, or a polymer of (a) and / or (b) having self-crosslinking, for example, self-crosslinking Type poly (meth) acrylate and the like.

The sustained-release gel of the water-absorbing polymer has the following properties:
The types may be used alone, or two or more types may be used in combination. Further, the sustained-release gel of the water-absorbing polymer preferably has a water-absorbing performance with respect to pure water of at least 1 ml / g, particularly preferably in the range of 5 to 1000 ml / g.

The amount of the hollow fiber of the sustained-release gel of the water-absorbing polymer to be filled in the hollow portion is preferably 1% by weight or more (based on the base hollow fiber) in a non-swelling state in a completely dry state. And more preferably at least 5% by weight. If the filling amount is too large, the hollow fibers tend to split when the gel swells by water absorption. Therefore, the filling amount is preferably 80% by weight or less.

It is necessary that such a water-absorbing polymer used in the present invention contains a bamboo extract oil component. The bamboo extract oil component is what is known as bamboo extract,
It is used by being contained in a sustained-release gel of a water-absorbing polymer. That is, in the process of absorbing and releasing moisture generated from the human body and moisture from the outside of the clothes by the sustained-release gel of the water-absorbing polymer, the bamboo extract oil component contained in them gradually passes through the communication holes to the surface of the hollow fiber. The bamboo extract oil component is preferably blended in the range of 5 to 30% by weight based on the gel of the water-absorbing polymer. In addition, the gel of the water-absorbing polymer in the present invention may contain additives such as a fragrance, a stabilizer, an antioxidant, and an ultraviolet absorber, as necessary, in addition to the bamboo extract oil component.

Next, the following method is exemplified as a method for filling the sustained-release gel of the water-absorbing polymer containing the bamboo extract oil component into the hollow portion of the hollow fiber.

(1) The above-mentioned hollow fiber is made of an uncrosslinked product of a water-absorbing polymer and / or a monomer constituting the water-absorbing polymer;
A method of immersing in a solution containing bamboo extract oil, a cross-linking agent, and preferably a polymerization initiator or a catalyst so as to penetrate into the hollow portion of the hollow fiber; The hollow fiber is immersed in a solution containing a cross-linked product and / or a constituent monomer of the water-absorbing polymer, bamboo extraction oil, a cross-linking agent, and preferably a polymerization initiator or a catalyst, and then squeezed with a mangle or the like. (3) The hollow fiber is placed in a closed container, and the pressure is reduced. After the air in the hollow portion is removed, an uncrosslinked product of the water-absorbing polymer and / or the water-absorbing polymer is removed. A solution containing a constituent monomer, bamboo extract oil, a crosslinking agent, and preferably a polymerization initiator or a catalyst is poured into the container, filled in the hollow portion of the hollow fiber, and then heated to obtain an uncrosslinked water-absorbent. Po And allowed rise to polymerization, crosslinking reaction of the crosslinking reaction or the monomer-mer, can be exemplified a method of forming a sustained-release gel of the water-absorbing polymer containing bamboo extract oil in the hollow portion of the hollow fiber.

When the hollow fiber of the water-absorbing polymer gel is filled into the hollow portion, the hollow fiber is formed of a yarn, a spun yarn,
The treatment can be performed in any form such as a woven fabric, a knitted fabric, or a nonwoven fabric. However, it is usually appropriate to treat the fabric in a form such as a woven fabric or a knitted fabric from the viewpoint of workability.

Here, the solvent of the solution may be any solvent capable of dissolving the above components, and examples thereof include water and / or an organic solvent soluble in water. Examples of water-soluble organic solvents include alcohols such as isopropyl alcohol, ketones such as methyl ethyl ketone,
Tetrahydrofuran, N, N-dimethylformamide,
Dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned. Among them, those using water are particularly preferable because they are inexpensive and easy to handle.

The cross-linking agent may be any cross-linking agent which can cross-link the water-absorbing polymer to form a water-insoluble cross-linked product. For example, two vinyl groups and / or epoxy groups per molecule may be used. Compounds having the above and polyvalent metal compounds can be exemplified. Among them, those in which the crosslinking agent itself is water-soluble are preferred.

Specific examples of such a crosslinking agent include polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diglycidyl ether, glycerin di (or tri) methacrylate, glycerin di (or tri) acrylate, glycerin di (or Tri) glycidyl ether, trimethylolpropane di (or tri) methacrylate, trimethylolpropane di (or tri) acrylate, trimethylolpropane di (or tri) glycidyl ether, and the like.

Examples of the polyvalent metal compound which can be used as the crosslinking agent include inorganic salts, organic carboxylate salts and complex salts of divalent or higher valent metals. Such 2
As the metal having a valency or higher, Ca, Mg, Zn, Mn, A
1, Ti, Sn, Cu, Fe, Cr, Ni, Zr and the like are preferably exemplified, and their chlorides, sulfates, acetates, succinates, ethylenediaminetetraacetic acid complexes and the like are preferably exemplified.

More specifically, calcium acetate, magnesium acetate, basic aluminum acetate, zinc acetate, manganese acetate, cobalt acetate, aluminum sulfate, calcium chloride, magnesium stannous sulfate, EDTA-
Ca, EDTA-Mg and the like can be mentioned. Such polyvalent metal compounds, even if only one kind is used alone,
Any of two or more of them may be used in combination.

The above-mentioned solution is obtained by dissolving, dispersing or emulsifying a monomer and a polymerization initiator in a suitable liquid such as water, and has a viscosity as low as possible to facilitate introduction into a hollow portion. Is desirable. Further, the monomer used here is one that is capable of forming a gel of the above-mentioned water-absorbing polymer, is soluble in a solvent such as an organic solvent or water, and is polymerizable in the presence of a polymerization initiator. Things are good, for example, butadiene, acrylonitrile, styrene, vinyl chloride, vinylidene chloride, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid derivative, di (meth) acrylic acid, (meth) acrylic acid derivative, etc. Those using a vinyl monomer are particularly preferably exemplified.
These monomers may be used alone or in combination of two or more.

Examples of the polymerization initiator include peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide; cerium ammonium such as ceric ammonium sulfate and ceric ammonium nitrate. Salts or α, α′-azobisisobutyronitrile and the like can be mentioned.

Examples of the above catalyst include tertiary amines, quaternary ammonium salts, imidazole compounds, boron trifluoride, Zn (BF ₄ ) ₂ , KOH, SnCl _{4 and the} like.

In the hollow fiber structure of the present invention, the sustained-release gel of the water-absorbing polymer is present only in the hollow part, and is not substantially present on the outer surface of the hollow fiber or the interfiber space. It is preferable in that the texture of the finally obtained woven or knitted fabric is maintained.

For this purpose, when the sustained-release gel of the water-absorbing polymer is filled into the hollow portion of the hollow fiber, it is preferable to dissolve and remove the constituent monomer of the water-absorbing polymer attached to the surface of the hollow fiber. The dissolving / removing method includes a method of immersing the hollow fiber in a solvent capable of dissolving the water-absorbing polymer or the constituent monomer, and a method of applying a solvent capable of dissolving the water-absorbing polymer or the constituent monomer to the surface of the hollow fiber. The method is exemplified.

The solvent used here can dissolve the water-absorbing polymer or monomer.
Crosslinking of the water-absorbing polymer introduced into the hollow portion, or does not inhibit the polymerization of the monomer, and unless the water-absorbing polymer or the monomer introduced into the hollow portion has high permeability enough to elute the monomer, Any one can be used.

Examples of such a solvent include water, acetone, dimethylformamide, dimethylsulfoxide, benzene,
Toluene or the like is used. In particular, water is preferably used because it is inexpensive and easy to handle.

When the hollow fiber is treated with the above-mentioned solvent, the temperature of the solvent is set to a temperature higher than the temperature at which the polymer starts to crosslink and / or the temperature at which the monomer starts to be polymerized.
In the case of the monomers exemplified above, heating to 50 to 100 ° C. dissolves and removes the polymer or monomer attached to the surface of the hollow fiber and simultaneously cross-links or polymerizes the polymer or monomer introduced into the hollow portion. This is convenient.

Further, when a polymerization inhibitor is added to the solvent when the hollow fiber is treated with the solvent, polymerization of the monomer remaining on the fiber surface is suppressed, and the removal of the monomer is further facilitated. Is preferable.

The polymerization inhibitor used herein is one capable of generating a stable radical, such as diphenylpicrylhydrazyl, galvinoxyl, and ferdazyl, as well as oxygen, which forms a stable radical by an addition reaction with a growing radical. Diphenylpicrylhydrazine, which generates a stable radical by a chain transfer reaction with sulfur, a benzoquinone derivative, a nitro compound, or a growing radical,
Examples include diphenylamine, hydroquinone, tert-butylcatechol and the like.

When a hollow fiber into which a monomer solution is introduced is treated with a solvent containing these polymerization inhibitors, the amount of the polymerization inhibitor in the solvent greatly affects the polymerizability of the monomers in the hollow portion. That is, if the amount of the polymerization inhibitor present in the solvent is too large, the polymerization inhibitor intrudes into the hollow portion from the communication hole and suppresses not only the surface of the hollow fiber but also the polymerization of the monomer in the hollow portion, As a result, a water-absorbing polymer gel may not be formed in the hollow portion.
Therefore, the amount of the polymerization inhibitor present in the solvent depends on its polymerization inhibiting ability, but can be limited to a minimum amount capable of capturing a reactive radical generated by heating from the monomer attached to the surface of the hollow fiber. preferable.

Further, it is preferable to add a soaping agent to the above-mentioned solvent since removal of the polymer or monomer attached to the surface of the hollow fiber is promoted. Examples of the soaping agent include an alkaline cleaning liquid containing sodium hydroxide or sodium carbonate as a main component, an ionic surfactant or a nonionic surfactant generally used for textile processing. The amount of the soaping agent added to the solvent is 0.
A range of 1 to 5.0% by weight is suitable. Further, the treatment with the solvent in this manner can be performed by any method as long as the polymer or monomer attached to the surface of the hollow fiber can be dissolved and removed, but a method of immersing the hollow fiber in the solvent and stirring is particularly preferably used. Can be

As described above, if necessary, a treatment is carried out with a solvent to dissolve and remove the monomer adhering to the surface of the hollow fiber, followed by heating to crosslink the polymer in the hollow portion.
Alternatively, the monomer is polymerized, and the sustained-release gel of the water-absorbing polymer containing the bamboo extract oil component introduced into the hollow portion is fixed. Of course, as described above, the temperature of the solvent is heated to a temperature equal to or higher than the temperature at which the polymer starts to crosslink, or the temperature at which the polymerization of the monomer is started. The introduced polymer or monomer can be simultaneously crosslinked or polymerized.

[0043]

According to the present invention, in a fibrous structure containing hollow fibers, at least a part of the hollow fibers is constituted by hollow fibers in which communication holes from the fiber surface to the hollow portion are scattered, and the hollow portion of the hollow fiber is formed. Is a fibrous structure in which a sustained-release gel of a water-absorbing polymer containing a component having a deodorizing effect is present. The component having the deodorizing effect is gradually released from the surface of the fiber during the process of sorbing or desorbing the moisture in the vapor and liquid phases.

In particular, since the bamboo extract oil component contained in the sustained-release gel of the water-absorbing polymer volatilizes from the fiber surface as a component having the deodorizing effect, an excellent deodorizing effect can be obtained. Such effects are not easily impaired by washing.

In the present invention, since hollow fibers are used,
Since the sustained-release gel of the water-absorbing polymer containing the deodorizing component is protected by the hollow portion of the hollow fiber and gives a smooth feel even when the fiber directly touches the skin,
It is extremely useful for clothing applications such as nighties, blouses, and sportswear.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to restrict the scope of the present invention. The deodorizing effect, washing durability and bamboo extraction oil content in the examples were measured by the following methods.

[0047] (1) deodorization rate of ammonia gas: Entered sealed containers (initial concentration 200 ppm, the concentration and D _1), a 2 g / l of the sample was charged, detecting the residual concentration after left for 1 hour as measured by the tube method (for the concentration and D _2), it was calculated deodorization rate (%) by the following equation. Deodorization rate (%) = {(D ₁ −D ₂ ) / D ₁ } × 100

(2) Washing durability Washing was repeated 30 times in accordance with JIS L-1018-77 6.36, Method H.

(3) Bamboo extract oil content GC / MS sample: 0.5 mg is packed in a sample tube and measured. The bamboo extraction oil content after washing 0 times and washing 30 times was measured.

[Example 1] Polyethylene terephthalate having an intrinsic viscosity of 0.61 was melted, and a hollow fiber undrawn yarn having a hollow ratio of 40% was obtained using a hollow fiber spinneret. Then, the undrawn yarn was drawn to obtain a polyester multifilament yarn having a round hollow section (50 denier / 20 filaments, titanium oxide content 0.3% by weight).

The tricot knitted fabric knitted using the multifilament yarn is scoured and preset, and is treated in hot water (105 ° C.) containing 50 g / l of sodium hydroxide for about 10 minutes to reduce the weight loss rate. Alkali weight reduction treatment was performed to 20%.

The multifilament yarn was taken out from the obtained fabric (tricot) and its surface was observed with a scanning electron microscope.
m, and at least one microgroove having a length of 10 to 150 μm was observed per 100 μm for each filament.

Next, the cloth is placed in a closed container, the pressure in the container is reduced to 0.004 mmHg using a rotary pump, and then, PEG-
Dimethacrylate: 30 parts by weight, potassium persulfate: 0.1 part by weight.
A monomer solution consisting of 1 part by weight and water: 65.9 parts by weight and 4.0 parts by weight of bamboo extraction oil (bamboo extract, manufactured by Shinki Sangyo Co., Ltd.) were injected.

[0054]

Embedded image

After injecting the monomer solution and the bamboo extraction oil, the reduced pressure was maintained for 10 minutes using a rotary pump. At this time, the pressure in the container was 0.2 mmHg. Next, the pressure in the container was returned to a constant pressure, the cloth was impregnated with the monomer liquid, and the cloth was immersed in hot water of 100 ° C. for 3 minutes with stirring, and the cloth was dried and heat-treated. The texture of the obtained fabric was soft. Also,
Table 1 shows the results of bamboo extraction oil content, washing durability, and deodorization rate of the fabric.

Comparative Example 1 The cloth (tricot) used in Example 1 was treated under the same conditions as in Example 1 except that no bamboo-extracted oil component was used. Table 1 also shows the results of the deodorization rate, bamboo extraction oil content, and washing durability of the obtained fabric.

[0057]

[Table 1]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Torukei Matsui 3-4-1, Amihara, Ibaraki-shi, Osaka Teijin Limited Osaka Research Center F-term (reference) 4L033 AB01 AC07 AC10 CA03 CA10 CA20 4L035 AA09 BB31 CC20 DD03 DD07 EE05 EE20 FF10 HH10 JJ05 JJ11 KK05

Claims (1)

[Claims] In a fibrous structure containing hollow fibers, at least a part of the hollow fibers has a hollow portion in which communication holes from the fiber surface to the hollow portion are scattered, and the hollow portion of the hollow fiber has a hollow portion. A fiber structure having a deodorizing effect, characterized in that a sustained-release gel of a water-absorbing polymer containing a bamboo extract oil component having an odor effect is present.