JPH10259521A - Deodorant fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a deodorant fiber product capable of speedily degrading various smell components for a long time and making the smell components odorless, and useful for an underwear, a carpet, etc., by treating a polyester- based fiber containing a prescribed amount of specific inorganic particles, by an electric discharge processing. SOLUTION: This deodorant fiber product is obtained by treating a polyester- based fiber containing 0.5-10wt.% inorganic particles of an oxide semiconductor, etc., such as titanium oxide having photocatalystic activities and <=0.01μm average particle diameter, by an electric discharging processing such as a corona discharging processing. Preferably, the polyester-based fiber is a sheath and core conjugated fiber, and the inorganic particles are included in the sheath component. Further, the inorganic particles are preferably dispersed in a polyester-based polymer constituted of terephthalic acid and a linear >=4C glycol and the inorganic particles-dispersing polymer is mixed with the sheath component. Further, the sheath and the core consist essentially of a polyethylene terephthalate-based polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant fiber product, and more particularly to a deodorant fiber product, which can quickly decompose and remove odor components and harmful components emitted from tobacco, sweat, building materials, etc., and deodorize the product. The present invention relates to a deodorant fiber product having high durability and excellent comfort.

[0002]

2. Description of the Related Art In recent years, there has been an increasing interest in various odors in living environments such as homes, offices, and hospitals. These odorous and harmful components include numerous compounds,
For example, ammonia, nitrogen-containing compounds such as amines (eg, trimethylamine, triethylamine, etc.),
Sulfur-containing compounds such as hydrogen sulfide and methyl mercaptan,
Aldehydes such as formaldehyde and acetaldehyde, and lower fatty acids such as formic acid, acetic acid, propionic acid and valeric acid are included. Thus, in the living environment, there are various odor components such as acidic odor components such as lower fatty acids, basic odor components such as nitrogen-containing compounds, neutral odor components such as sulfur-containing compounds and aldehydes. However, it is difficult to effectively remove a plurality of different types of components.

In order to remove these substances, various deodorant fibers, for example, deodorant fibers having an adsorbent carried on the fibers have been proposed. However, such a deodorant fiber has a limit in the adsorption capacity of the adsorbent, so that when the adsorption amount of the odor component reaches the saturated adsorption capacity, it becomes impossible to deodorize. JP-A-62-6985 and JP-A-62-6986 disclose that a malodorous component is catalytically decomposed by a deodorant fiber supporting metal phthalocyanine. However, since the catalytic activity of metal phthalocyanine is small, the deodorizing effect is not sufficient.

Japanese Unexamined Patent Publication (Kokai) No. 63-295711 proposes a deodorant fiber in which zirconium phosphate particles are kneaded into fibers as a deodorant component.
Japanese Patent Application Laid-Open No. 09-80611 proposes a deodorant fiber obtained by kneading amorphous zinc silicate particles composed of zinc oxide and silicon dioxide into the fiber. A deodorant fiber in which a white hydrated oxide powder of Zn is kneaded in a fiber has been proposed. further,
Japanese Unexamined Patent Publication No. Hei 5-504091 and Japanese Unexamined Patent Publication No.
Japanese Patent Application Publication No. JP-A-2005-64131 proposes a deodorant fiber in which an absorbent composition containing a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal is compounded or blended in a fiber. However, these deodorizing fibers do not exhibit excellent deodorizing performance against all odor components including an acidic odor component, a basic odor component, and a neutral odor component.

On the other hand, a deodorant fiber capable of efficiently removing various odor components over a long period of time is disclosed in JP-A-8-2.
No. 84011. According to this, an adsorbent and a photocatalyst having a photocatalytic function such as titanium oxide and zinc oxide, particularly an adsorbent composed of a specific phosphate and hydroxide and a photocatalyst having a photocatalytic function such as titanium oxide and zinc oxide are used. It is disclosed that a fiber is used in combination with the deodorant composition. However, by using not only the adsorbent but also a photocatalyst having a photocatalytic function, various odor components can be removed efficiently and for a long period of time, as compared with the case of using only the adsorbent. As long as the adsorbent is used, its efficiency and sustainability are limited, and its deodorizing performance is still insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to remove various odor components more efficiently and for a longer period of time than conventional deodorant fibers and deodorant fiber products. To provide textile products.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in order to maximize the effect of the inorganic particles having photocatalysis, the characteristics of the particles and the particle The present inventors have found that the above-mentioned problems can be solved by combining the surface condition of a fiber containing the same and have completed the present invention.

That is, according to the present invention, the following deodorant fiber products are provided. (1) A deodorant fiber product composed of polyester fibers containing inorganic particles having a photocatalytic action,
The polyester fiber contains 0.5 to 10% by weight of inorganic particles satisfying the following requirements (a) and (b), and is subjected to electric discharge machining. ) The inorganic particles are composed of an oxide semiconductor. (B) The average particle size is 0.01 μm or less.

(2) The deodorant fiber product according to (1), wherein the oxide semiconductor is titanium oxide.

(3) The deodorant fiber product according to (1) or (2), wherein the polyester fiber is a core-sheath conjugate fiber, and the inorganic component is contained in a sheath component.

(4) The above (3), wherein the inorganic particles contained in the sheath component are dispersed and mixed in a polyester polymer composed of terephthalic acid and a glycol having 4 or more linear carbon atoms. Deodorant fiber products.

(5) The deodorant fiber product according to the above (3) or (4), wherein the core / sheath component is a polyethylene terephthalate polymer as a main component.

(6) The deodorant fiber product according to any one of the above (1) to (5), wherein the deodorant fiber product is a nonwoven fabric.

(7) The deodorant fiber product according to any one of the above (1) to (6), wherein the electric discharge machining is corona electric discharge machining.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION It is necessary that the deodorant fiber product of the present invention is composed of polyester fibers containing inorganic particles having a photocatalytic action. Here, the form of the fiber product is not limited as long as it is composed of deodorant polyester-based fibers, but woven fabric, knitted fabric, cloth such as nonwoven fabric, pile fabric, pile fabric such as pile knitted fabric, Clothes and other body wears, interior parts, bedding, food packaging, etc., formed from fabrics, pile fabrics, etc. can be mentioned, but nonwoven fabrics and secondary processed products formed from nonwoven fabrics are particularly preferred. .

The polyester fiber constituting the deodorant fiber product of the present invention needs to contain inorganic particles having a photocatalytic action. The term “inorganic particles having a photocatalytic action (hereinafter abbreviated as photocatalyst particles)” as used in the present invention means that active oxygen is generated by irradiation with light such as ultraviolet rays, and many harmful substances and odorous substances are oxidized and decomposed to form photooxidation. It functions as a catalyst. Therefore, the photocatalyst particles often belong to the category of the oxidizing photocatalyst. When such photocatalyst particles are used, deodorization can be carried out by utilizing catalytic decomposition instead of a mere adsorption action, so that the deodorizing or deodorizing effect is maintained for a long period of time. Furthermore, the photocatalyst particles not only decompose harmful substances and malodorous substances, but also have a bactericidal action and the like.

In general, various types of optical semiconductors can be used as the photocatalyst, whether organic or inorganic, but are often inorganic optical semiconductors.

In the present invention, it is necessary that the inorganic particles having photocatalysis (photocatalyst particles) are composed of an oxide semiconductor having a specific average particle diameter. As an oxide semiconductor, TiO ₂ , ZnO, WO ₃ , CdO,
In ₂ O ₃ , Ag ₂ O, MnO ₂ , Cu ₂ O, Fe ₂ O
₃ , V ₂ O ₅ , SnO _{2 and the} like.
Particularly, TiO ₂ (titanium oxide) is preferable. The crystal structure of the optical semiconductor constituting the inorganic particles is not particularly limited. For example, TiO ₂ may be any of anatase type, brookite type, rutile type, amorphous type and the like. Preferred TiO ₂ includes anatase type titanium oxide.

The most characteristic feature of the inorganic particles having a photocatalytic action of the present invention is that they have an extremely fine average particle diameter of 0.01 μm or less. In general, inorganic semiconductors having a photocatalytic function are used not only in sol and gel form but also in powder form, in which case the average particle size is 0.01 μm
Most of them exceed. The cause is that when the matrix contains an inorganic semiconductor smaller than the particle size,
This is because there is substantially no difference between using particles having a large particle diameter due to aggregation of particles. In the present invention, the inorganic particles having a fine average particle size of 0.01 μm or less have a photocatalytic action by being uniformly contained in fibers, that is, an activity capable of catalytically oxidatively decomposing odorous components and harmful components. Many points can be present in the fiber, and the synergistic effect with the electric discharge machining treatment on the fiber surface described later can maintain high efficacy and sustainability.

In the present invention, it is necessary that the polyester fiber contains 0.5 to 10% by weight of the photocatalyst particles having the above characteristics.

Here, the means for incorporating the photocatalyst particles into the fiber include a method of mixing and dispersing the photocatalyst particles in the cross section of the fiber and a method of using a binder such as an adhesive resin to prevent the photocatalyst particles from falling onto the surface of the fiber. A method for attaching is included.
As a method of attaching the photocatalyst particles to the fiber surface, a conventional method such as a method of impregnating the fiber with a dispersion containing the photocatalyst particles and a binder as needed, a method of spraying the dispersion with the fiber, and a method of coating the fiber is adopted. it can. As a binder,
For example, solvent-soluble polyolefin, polyvinyl acetate,
Ethylene-vinyl acetate copolymer, vinyl polymers such as polysalt or vinyl, thermoplastic resins such as acrylic resin, styrene resin, polyester, polyamide, polyurethane; cellulose resin; epoxy resin, vinyl ester resin, silicone resin, etc. May be used.

The method of mixing and dispersing the photocatalyst particles in the cross section of the fiber is more effective than the method of adhering the photocatalyst particles on the fiber surface because the photocatalyst particles are firmly held in the fiber and easily fall off from the fiber. It is more preferable because the deodorizing action is stably exhibited over a long period of time without performing. At this time, a fiber containing the photocatalyst particles can be produced by melt-spinning the composition (spinning raw material) containing the photocatalyst particles and the polyester-based polymer. In any method, it is necessary that the polyester fiber contains 0.5 to 10% by weight of the photocatalyst particles. If the amount is less than 0.5% by weight, not only the efficiency of the deodorizing action but also the sustainability is insufficient. And 1
Exceeding 0% by weight is not preferred because the efficiency of deodorizing action and its persistence are saturated and there is no effect of increasing the weight, but also the spinning tone (spinning properties) and fiber properties are reduced.

In the present invention, the deodorant fiber preferably obtained by mixing and dispersing the photocatalyst particles in the fiber cross section may be, for example, a fiber containing the photocatalyst particles uniformly throughout the fiber. A composite fiber having a composite structure composed of a phase having a high particle concentration and a phase having a component concentration relatively lower than the high concentration phase may be used. The composite fiber has a composite structure in which the content (distribution) of the photocatalyst particles differs between the central portion and the surface portion of the fiber cross section (for example, one of the core or sheath of a sheath-core type composite fiber contains photocatalyst particles). Or a composite structure in which the photocatalyst particles are distributed in the form of sea-islands in the fiber (for example, a sea / iland or matrix composite fiber). Either the sea or the island contains photocatalyst particles, or a sea-island type structure in which the content of the photocatalyst particles differs between the sea and the island), and a composite structure in which the photocatalyst particles are distributed in fibers in a side-by-side manner (for example, a side-by-side type ( sideby side) One of the composite fibers contains photocatalyst particles, or the content of the photocatalyst particles differs in one phase and the other phase (side-by-side type structure), in the composite fiber of the kidney type (kidney) structure, and in the fiber cross section. There photocatalyst particles may have a like composite structure containing randomly. Incidentally, in the side-by-side type (side by side) conjugate fiber, the phase having a high photocatalyst particle concentration and the phase having a relatively low component concentration as compared with the high concentration phase may contain photocatalyst particles as necessary. They may be adjacent to each other in a suitable direction such as in parallel or in a circumferential direction through a good resin phase. The side-by-side type conjugate fiber may be composed of a plurality of high concentration phases and / or low concentration phases. Preferred conjugate fibers include a core-sheath type structure, a sea-island type structure, and a side-by-side type structure, particularly a core-sheath type structure in which a photocatalytic particle is contained in a sheath component.

In the present invention, when the inorganic ultrafine particles having an average particle diameter of 0.01 μm or less are contained in the fiber, a master batch method (where the compatibility parameter is similar to that of the main component of the matrix, so as not to cause aggregation of the ultrafine particles). It is preferable to employ a method in which inorganic particles are added to a master component to be added, and the master batch is added to a main component of the matrix.

Specifically, when the inorganic particles are contained in the sheath component of the core-sheath structure fiber, the inorganic particles are dispersed in a polyester polymer composed of terephthalic acid and a glycol having 4 or more straight-chain carbon atoms.・ Matter batch mixed
It is added to the polyester sheath component. On this occasion,
The core component and the main component constituting the sheath component of the core-sheath structure fiber are preferably a polyethylene terephthalate-based polymer, but if the total of the polyester components of the core-sheath structure fiber is 50% by weight or more, the sheath component and As a component of the masterbatch, for example, a fiber-forming polyolefin polymer,
Polyamide polymers may be used.

In the core-in-sheath composite structure, the ratio of the low-concentration phase (core portion in the core-in-sheath type composite fiber) and the high concentration phase (sheath portion in the core-in-sheath type composite fiber) is, for example, low concentration phase (core portion). / High-concentration phase (sheath portion) = 50/50 to 95/5 (weight ratio), preferably about 70/30 to 80/20 (weight ratio).

Further, the cross-sectional shape of the deodorant fiber of the present invention is not limited at all. For example, in addition to a round cross-section, an irregular cross-section (for example, hollow, flat, elliptical, polygonal (tri-hexagonal) Etc.), 3-14 leaf shape, T shape, H shape, V shape, dog bone shape (I shape) and the like. In order to enhance the deodorizing performance, a modified cross-section fiber having a large specific surface area is advantageous. Further, the deodorant fiber may be a fiber combining the composite structure and the cross-sectional shape, for example, a hollow fiber having a core-sheath structure or a side-by-side structure.

In the polyester-based deodorant fiber having a composite structure constituting the present invention, even if the amount of photocatalyst particles relative to the entire fiber is small, it is necessary to efficiently remove odor components by the photocatalyst particles on the surface layer of the fiber. The phase containing the photocatalyst particles is advantageously exposed on the fiber surface. For example, in the case of a deodorant fiber having a core-sheath structure, if the concentration of photocatalyst particles in the sheath is higher than that in the core (particularly when the photocatalyst particles are contained in the sheath), the odor component is increased by the photocatalyst particles in the surface layer of the fiber. Can be removed more efficiently. In the deodorant fiber having a side-by-side structure, the concentration of the photocatalyst particles in an appropriate phase exposed on the fiber surface may be increased. In the present invention, in addition to such a composite fiber structure, it is important that the surface of the composite fiber is subjected to electric discharge machining to expose the photocatalyst particles present near the surface layer to the fiber surface.

Examples of the electric discharge machining method include an energization method in which the core-sheath composite fiber having the above-described configuration is brought into contact with a high-voltage electrode to apply a high voltage, a corona discharge having a different discharge shape, a fireworks discharge, a glow discharge, and the like. Although it can be treated by a high voltage discharge treatment such as arc discharge, corona discharge machining is particularly preferred. The applied voltage is a high voltage exceeding 1 kV and a voltage of up to 100 kV can be used, and a voltage of 2 to 50 kV is preferably exemplified. The polarity of the electrode may be positive or negative (DC) or AC. The distance between the electrodes can be in the range of 0 to 10 cm, and the discharge mode and the processing speed can be arbitrarily determined according to the target surface treatment degree.

Further, such a discharge treatment can be carried out in the state of a yarn, a woven or knitted fabric or a non-woven fabric. Further, in the case of a yarn, it may be applied to a drawn yarn or an undrawn yarn. This discharge treatment increases the density of photocatalyst particles on the fiber surface, and increases the efficiency of catalytically oxidatively decomposing odorous and harmful components.

The thickness of the fiber in the fiber product of the present invention is not particularly limited, and can be selected from a wide range depending on the use. For example, 0.1 to 50 μm, preferably 0.5 to 30 μm
m, more preferably about 1 to 20 μm. The shape of the fiber in the longitudinal direction is not limited, and may be a fiber having substantially the same diameter in the length direction, a thick and thin thick and thin fiber, or other fibers. You may. Further, the fibers may be either short fibers or long fibers, spun yarn, multi-filament yarn,
A composite yarn of short fibers and long fibers may be used. Further, the fiber in the textile product of the present invention may be, depending on the application or the type of fiber, false twisting, interlacing, taslan processing, crimping, mercerizing, shrink-proofing, wrinkle-proofing, hydrophilic processing, waterproofing. Arbitrary processing such as processing and anti-dyeing processing may be performed. In the fiber in the fiber product of the present invention, in addition to photocatalytic particles, depending on the type of fiber, various additives used in the fiber, for example, antioxidants, flame retardants, antistatic agents, coloring agents, lubricants , An antibacterial agent, an insect / miticidal agent, a fungicide, an ultraviolet absorber, a matting agent, a heat storage agent, and the like.

As a typical example of the fiber product of the present invention formed using fibers, yarns, fabrics, etc. containing photocatalyst particles,
Underwear, underwear, sweater, jacket, pasama, yukata,
White robes, slacks, socks, gloves, stockings, aprons, masks, towels, handkerchiefs, supporters, headbands, hats, shoe insoles, interlining, and other clothing and body wear; various carpets, curtains, wallpapers, shoji paper, sliding doors ,
Textile blind slats, artificial houseplants, cloth for upholstery such as chairs, tablecloths, electric product covers, tatami mats, filling materials for futons (stuffing cotton, etc.), futon side, sheets, blankets, futon covers, pillows Pillow covers, bed covers, filling materials for beds, mats, sanitary materials, toilet seat covers, wiping cloths, filters for air purifiers and air conditioners, and the like.

[0033]

The textile product of the present invention can be obtained by irradiating light (eg, sunlight, fluorescent lamp, ultraviolet lamp, etc.) with a basic odor component such as ammonia and amines, an acidic odor component such as acetic acid, and hydrogen sulfide. Such as sulfur-containing compounds, formalin,
Many odor components such as a neutral odor component such as acetaldehyde can be decomposed quickly and for a long period of time to eliminate odor. Therefore, even tobacco odors containing a large number of odor components can be efficiently removed, which is effective for deodorizing indoors and vehicles. It is also effective for deodorizing aldehydes such as formalin and acetaldehyde generated from furniture and new building materials.

[0034]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. The odor component removal test and antibacterial test in the examples were measured by the following methods.

<Odor Component Removal Test and Antibacterial Test> Using the textiles, an ammonia (NH ₃ ), trimethylamine (TMA), acetic acid (CH ₃ COOH) removal test and an antibacterial test were conducted.

In the test for removing odor components, 60 ml of a 0.14% aqueous ammonia solution was placed in each glass container.
A 0.15% aqueous solution of trimethylamine and a 0.1% aqueous solution of acetic acid are added, and the sample solution is colored with reagents (aqueous ammonia solution, aqueous trimethylamine solution is phenolphthalein, aqueous acetic acid solution is brommol blue), and then the fiber is added to it. One product was sealed, illuminated with sunlight for 8 hours at the window, the absorbance at 550 nm (400 nm in the case of acetic acid) was measured, and based on this, the odor component removal rate was produced.

In the antibacterial test, one fiber product was put in 40 ml of water (including spontaneous bacteria) containing 0.1% by weight of the test medium, sealed, and allowed to stand still under room natural light. Propagation of the bacteria was determined by measuring the transparency 2 days later by measuring the transmittance at 600 nm.

Examples 1 to 7 and Comparative Examples 1 to 3 A polybutylene terephthalate polymer having an intrinsic viscosity of 0.88 was mixed with photocatalyst particles having different particle sizes (photocatalytic titanium oxide ST-01 manufactured by Ishihara Sangyo Co., Ltd.) at a temperature. The mixture was extruded at 260 ° C. for 5 minutes while being kneaded with an extruder to prepare master batch pellets. The pellet was mixed with polyethylene terephthalate having an intrinsic viscosity of 0.64 to prepare a resin composition for the sheath. When the composite spinning of the resin composition for the sheath portion and the polyethylene terephthalate polymer having an intrinsic viscosity of 0.64 for the core portion is performed by a conventional method, the spinning temperature is 290.
The fiber was spun at a temperature of 290 g / min at a discharge rate of 1150 m / min.

The obtained undrawn yarn is heated in 70 ° C. hot water.
After drawing twice, heat-treated at 145 ° C. for about 20 minutes and then cut into a length of 51 mm to obtain a core-sheath composite structure staple fiber having a single fiber fineness of about 3 de.

The following nonwoven fabric was obtained by a roller card method using the staple fiber according to a conventional method. Thickness 1.9 mm Density 0.52 g / cm ³ Next, a corona discharge treatment was performed on the surface of the nonwoven fabric under the conditions of a distance between electrodes of 2 cm and an applied voltage of 38 kV. At this time, the properties of the photocatalyst particles to be contained in the staple fiber and the performance change with the content are shown in Table 1.

[0041]

[Table 1]

<Evaluation Criteria> * 1) Spinning condition ◎ No spinning break ○ Slight spinning break × Spun breakage spatter * 2) Removal rate of odor components ◎ Removal rate 90% or more ○ Removal rate 90-70% △ Removal Rate: 70 to 60% × removal rate: less than 60% * 3) Growth inhibition rate of bacteria ◎: inhibition rate of 90% or more ○ inhibition rate: 90 to 50% △ inhibition rate: 50 to 26% × inhibition rate: less than 26% Indicates out of the scope of the present invention.

[Comparative Examples 4 to 5] In Examples 1 and 4, the non-woven fabric was subjected to a deodorant / antibacterial test before the corona discharge treatment, and the results are shown in Table 2.

[0044]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI D06M 10/02 D06M 10/00 H (72) Inventor Kenji Baba 77 Kitayoshida-cho, Matsuyama-shi, Ehime Pref.

Claims (7)

[Claims] 1. A deodorant fiber product composed of a polyester fiber containing inorganic particles having a photocatalytic action, wherein the polyester fiber has an inorganic particle satisfying the following requirements (a) and (b): 0.5 to 10% by weight and being subjected to an electric discharge machining treatment. (A) The inorganic particles are composed of an oxide semiconductor. (B) The average particle size is 0.01 μm or less. 2. The deodorant fiber product according to claim 1, wherein the oxide semiconductor is titanium oxide. 3. The deodorant fiber product according to claim 1, wherein the polyester fiber is a core-sheath conjugate fiber, and the inorganic component is contained in a sheath component. 4. The deodorant according to claim 3, wherein the inorganic particles contained in the sheath component are dispersed and mixed in a polyester polymer composed of terephthalic acid and a glycol having 4 or more straight-chain carbon atoms. Textile products. 5. The deodorant fiber product according to claim 3, wherein the core / sheath component comprises a polyethylene terephthalate-based polymer as a main component. 6. The deodorant fiber product is a non-woven fabric.
A deodorant fiber product according to any one of claims 1 to 5. 7. The deodorant fiber product according to claim 1, wherein the electric discharge machining is corona electric discharge machining.