JPH10155884A - Deodorant for acidic malodorous gas and deodorant fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve heat resistance and to obviate discoloration even after deodorization by constituting the deodorant of zirconium hydroxide or zirconium oxide. SOLUTION: For example, an aq. soln. of 0.5M sodium hydroxide is added to 1 liter aq. soln. of about 0.5M zirconium oxychloride until its pH value attains 11.0. The zirconium hydroxide is obtd. by filtering, washing, drying and pulverizing the soln. mixture. As a result, an amorphous deodorant is obtd. About 0.02g such deodorant is put into a 1-liter vessel and gaseous acetoaldehyde is injected into the vessel until a concn. of 200ppm is obtd. The change in the gas concn. of the gaseous acetoaldehyde is then measured. The change in the color tone is measured. Consequently, good results are obtd. with both of the gas concn. and the change in the color tone. Smell and discoloration are not admitted at all. A deodorant fiber containing the same was also obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant having an excellent deodorizing ability against acidic malodorous gases and a deodorizing fiber which can exhibit an excellent deodorizing ability by containing the same. . The deodorant fiber of the present invention can be used for various fiber products as a conjugate fiber, a woven fabric, a nonwoven fabric, etc., and is useful as a raw material for various fiber products such as clothing, sheets, covers, curtains, and carpets.

[0002]

2. Description of the Related Art In recent years, the demand for comfortable living has rapidly increased, and the function of deodorizing has attracted much attention. In particular, tobacco odors that require strong deodorization use acetaldehyde, a kind of acidic malodorous gas, as its main component. Required. Activated carbon has been known as a deodorant for a long time, and one in which an aromatic primary amine is impregnated on activated carbon, or one in which acid or base is supported on the surface of activated carbon to adjust the pH has been proposed. . Further, iron-phthalocyanine complexes and polymer compounds having an amino group or a sulfone group are also known as deodorants. However, since these deodorants have low heat resistance, they are exposed to a high-temperature treatment such as a process of kneading into a resin for fibers or a process of heating together with a binder made of a thermoplastic resin or a thermosetting resin to adhere to fibers. Then, there was a problem that the deodorizing ability was lost. As a deodorant which solves these drawbacks, there is a hydrotalcite compound or a calcined product thereof. The hydrotalcite compound is represented by the following general formula and is a compound having a hydrotalcite structure. The most preferred compound is magnesium-aluminum hydrotalcite. _{^{M 1 (1-x) M}} 2 x (OH) 2 A n- (x / n) · mH 2 O (M 1 is a divalent metal, M ² is a trivalent metal,
X is a number greater than 0 and equal to or less than 0.5; ^An- is an n-valent anion such as a carbonate ion or a sulfate ion; and m is a positive number. However, when this compound is used for deodorizing acetaldehyde, the color changes from white to yellow-brown, so that when it is contained in white fibers, there is a problem that the fibers change color, and the range of use is limited.

[0003]

An object of the present invention is to provide a deodorant for acidic malodorous gas which has improved the disadvantages of conventional deodorants and deodorant fibers, has excellent heat resistance and does not discolor after deodorization. An object of the present invention is to provide an odorous fiber.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that it is effective to use a dehydrated agent composed of hydrated zirconium oxide or zirconium oxide. The invention has been completed.
That is, the present invention is a deodorant for acidic malodorous gas comprising hydrated zirconium oxide or zirconium oxide, and a deodorant fiber comprising the same.

Hydrated zirconium oxide The hydrated zirconium oxide may be either crystalline or amorphous, and has the same meaning as zirconium oxyhydroxide, zirconium hydroxide, hydrous zirconium oxide and zirconium oxide hydrate. It is.

The hydrated zirconium oxide in the present invention is a known compound, and its production method is not particularly limited. As a preferred production method, there is a wet method, and hydrated zirconium oxide can be easily obtained by hydrolyzing a zirconium-containing aqueous solution such as an aqueous zirconium oxychloride solution with water or an aqueous alkali solution.

[0007] Zirconium oxide The zirconium oxide may be either crystalline or amorphous, but amorphous is preferred to exhibit high deodorizing ability. As the zirconium oxide in the present invention, a commercially available product may be used as it is, or an anhydride obtained by calcining the above hydrated zirconium oxide may be used. The preferred firing temperature for firing amorphous hydrated zirconium oxide to obtain amorphous zirconium oxide is 150-350 ° C. As described above, since the deodorant of the present invention is an inorganic substance having heat resistance originally,
The deodorizing ability is not deteriorated at all by the high temperature to which the fiber is exposed.

[0008] The deodorant of the present invention is usually obtained in the form of a powder, and preferably has an average particle size of 0.01 to 20 µm, more preferably 0.01 to 10 µm, and still more preferably 0.01 to 10 µm.
5 μm. If the average particle size is less than 0.01 μm, reagglomeration tends to occur and handling is difficult, which is not preferable. Further, if it is larger than 20 μm, the dispersibility in the resin or binder for fibers described below is low, and it may be difficult to uniformly incorporate the fibers into fibers. Has a problem that a thread break occurs, which is not preferable.

The deodorant of the present invention is effective against acidic malodorous gases such as acetic acid gas, isovaleric acid gas, normal butyric acid gas and aldehyde gas, and is particularly effective against aldehyde gas. .

The deodorant fiber of the present invention is a fiber containing the above-mentioned deodorant. The fiber may be any of a natural fiber and a synthetic fiber, and may be any of a short fiber, a long fiber, and a composite fiber having a core-sheath structure. Since the deodorant of the present invention has excellent heat resistance and does not lose its deodorizing ability even at a high temperature of 300 ° C., there is no problem even if the deodorant is exposed to a high temperature when the deodorant is contained in the fiber. And can be contained in any fiber. As an example of a preferred natural fiber,
There are pulp, hemp, cotton, silk and wool, and examples of preferred synthetic fibers include polyester, nylon, acrylic, polyethylene, polyvinyl alcohol, polyvinylidene,
Examples include polyurethane and polystyrene. Synthetic fiber resin may be a homopolymer or a copolymer,
In the case of a copolymer, the polymerization ratio of each monomer component can be arbitrarily controlled according to the desired properties of the fiber. There is no particular limitation on the method of adding a deodorant to the fiber.For example, spinning such as melt spinning, dry spinning, and wet spinning is performed by using a fiber resin preliminarily blended with a deodorant, or a thermoplastic resin. An aqueous or organic suspension containing a binder made of a resin or a thermosetting resin and a deodorant is applied to the fiber surface by a method such as coating or dipping, and the solvent is removed and a desired heat treatment is applied to the fiber surface. After coating or attaching a deodorant to the surface of a fiber made of thermoplastic resin such as polyolefin resin using a flocculant, etc., the fiber surface is heated and slightly melted to fuse the deodorant particles. Can be done. If necessary, a surfactant, a dispersant, or the like may be added to the aqueous or organic suspension to improve the dispersibility of the deodorant. Any of nonionic, cationic and the like may be used. The ratio of the deodorant contained in the fibers is not particularly limited, but is preferably 0.1 to 20 parts, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the resin for natural fibers or synthetic fibers (hereinafter simply referred to as part). Department. In addition, the fiber may optionally include a matting agent, a coloring agent, an antioxidant, a fluorescent whitening agent, a stabilizer, a flame retardant, an antibacterial deodorant, a fungicide, a fragrance, an infrared absorber and an ultraviolet absorber. Various additives can be contained, and the content may be appropriately adjusted according to a conventional method.

Use The deodorant of the present invention is effective against acidic malodorous gas, and has a large deodorizing effect particularly on aldehyde gas, especially on acetaldehyde gas. Therefore, it is particularly effective in deodorizing malodors such as cigarette odors, which are the main cause of odors. The deodorant fibers of the present invention include, for example, underwear, stockings, socks, futons, duvet covers, cushions, blankets, carpets, curtains, sofas, car seats, air filters, masks, handkerchiefs, hats, mufflers, shirts,
Mattress, pillowcase, work clothes, table cloth, noren, paper,
It can be used for many textiles including corrugated cardboard, non-woven fabric, towels, bedding, pajamas, etc.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples and comparative examples.

[0013]

【Example】

(Example 1) 0.5 M-zirconium oxychloride aqueous solution 1
Add 0.5 M aqueous solution of sodium hydroxide to the liter
Added to 11.0. Then, filter, wash and dry (100
° C) and pulverized to obtain hydrated zirconium oxide. The product was amorphous as a result of powder X-ray diffraction measurement. Place 0.02 g of the deodorant obtained as described above in a 1-liter container, inject acetaldehyde gas so that the concentration in the container becomes 200 ppm, and detect the acetaldehyde gas concentration after 2 hours and 24 hours. Was measured. The color tone (L, a, b) before and after (24 hours) before and after the deodorization test was measured with a color difference meter.
The results are shown in Table 1. In the measurement with the above-mentioned detector tube, gas having a concentration lower than the detection limit (1 ppm) (concentration indicated as ND in Table 1) did not smell at all.

Examples 2 and 3 The hydrated zirconium oxide obtained in Example 1 was calcined at 300 ° C. (Example 2) and 500 ° C. (Example 3) for 3 hours. As a result of thermogravimetric analysis and powder X-ray diffraction measurement, the product fired at 300 ° C. was amorphous zirconium oxide, and the product fired at 500 ° C. was crystalline zirconium oxide.
Using these, deodorant performance evaluation and color tone measurement were performed in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) Deodorizing performance evaluation and color tone measurement were performed in the same manner as in Example 1 using a fired product of hydrotalcite at 700 ° C., and the results are shown in Table 1.

Example 4 A masterbatch was prepared by blending 20 parts of the deodorant obtained in Example 1 with respect to 100 parts of a fiber resin made of polyester, and the ratio of the deodorant was determined based on the total weight. The masterbatch was blended with a resin for fibers made of the same kind of resin so as to be 2.5% by weight, and melt-spun by a conventional method to obtain deodorant fibers of about 2 denier. 1.0 g of the deodorant fiber obtained as described above was placed in a container having a capacity of 1 liter, and a deodorization performance evaluation test was carried out in the same manner as in Example 1.

[0017]

[Table 1]

Note: L is light and dark, a is red-green color, b
Represents yellow to blue colors, and the larger the L, the brighter the color, and the larger the absolute value of a and b, the more the color. Also, Δ
The larger the E, the greater the discoloration.

As is clear from the results in Table 1, the deodorant and the deodorant fiber of the present invention have excellent deodorizing ability against acetaldehyde gas, which is a kind of acidic malodorous gas, and discoloration of the acetaldehyde gas after deodorization. Is much smaller than the deodorant of Comparative Example 1 (fired product of hydrotalcite), and it can be seen that it is possible to visually judge that there is no discoloration.
In addition, about Example 4, it was visually confirmed that there was no discoloration after deodorization.

[0020]

Industrial Applicability The deodorant of the present invention has high heat resistance, can retain its deodorizing ability even when exposed to a high-temperature treatment for containing it in fibers, and can maintain the deodorizing properties of acidic malodorous gas. Does not discolor. The deodorant of the present invention, regardless of natural fibers or synthetic fibers,
Fiber products that can be contained in any type of fiber, and the deodorant fibers containing the deodorant of the present invention do not discolor even after the deodorization of acidic malodorous gas, so that the color tone is a problem. And especially effective for white textile products.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshiaki Matsushima 1 at Funamicho, Minato-ku, Nagoya-shi, Aichi, Japan

Claims (3)

[Claims] 1. A deodorant for acidic malodorous gas comprising hydrated zirconium oxide or zirconium oxide. 2. A deodorant for acidic malodorous gas, wherein the hydrated zirconium oxide or zirconium oxide according to claim 1 is amorphous. 3. A deodorizing fiber comprising the deodorant for acidic malodorous gas according to claim 1 or 2.