JPH0280611A - Deodorant acrylic synthetic fiber and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title fiber resistant to washing by homogeneously dispersing ceramic deodorant fine granules in an organic solvent solution of cellulose derivative and by adding the resultant dispersion to an organic solvent solution of acryslonitrile-based copolymer followed by spinning the resultant system. CONSTITUTION:Ceramic deodorant fine granules (pref. white fine powdery porous substance of hydrated oxide base from Ti and Zn) are homogeneously dispersed in an organic solvent solution of a cellulose derivative (e.g., acetyl cellulose). The resultant dispersion is then added to an organic solvent solution of an acrylonitrole-based copolymer and the resultant system is put to wet spinning, thus obtaining the objective fiber in which the cellulose derivative is present in a phase-separated state and the ceramic deodorant fine granules are included in the cellulose derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a deodorizing acrylic synthetic fiber having an excellent deodorizing effect and a method for producing the same.

(Prior art) Conventional methods of deodorization include masking malodors with aromatic substances, oxidative decomposition of malodorous substances with oxidizing agents such as potassium permanganate, salts, nitric acid, sodium hydroxide, A method of neutralizing with a neutralizing agent such as sodium carbonate, a method of adsorbing the bad odor with activated carbon, etc. are known.

However, among these methods, the method using a masking agent has the disadvantage of causing discomfort in places where people stay for a long time, and the other methods using oxidative decomposition neutralization, immobilization, or adsorption are highly selective for malodorous substances. There was a drawback.

On the other hand, for textile products, fibers contain anti-sagging agents,
Sanitary processing is known that prevents bad odors by preventing the growth of bacteria. However, since this method is an indirect method, it has the disadvantage that it is ineffective against bad odors caused by causes other than bacterial growth. Also, JP-A-59-
Publication No. 66 discloses that a diluted solution of deodorizing active ingredients extracted mainly from the striations of plants of the family Asperaceae, particularly tea plants, sakaki, and sasanqua flowers, is added to textile products by infiltration, coating, spraying, etc. According to this method, since the deodorizing component is attached to the surface of the fiber, there is a drawback that the effective deodorizing component is easily removed by washing with water or dry cleaning.

In addition, L'h t5) A method in which fine particulate deodorizers, typified by bundled activated carbon, are mixed and spun into the spinning dope as is or after being dispersed in a tempering solvent, has poor spinnability and is difficult to incorporate into the polymer. However, due to the coating effect of the polymer, the contact area against bad odors is small, resulting in insufficient deodorizing effect. Furthermore, when mixed with resin and processed with resin, the original texture of the synthetic fiber is damaged, and the deodorizing effect cannot be sufficiently exerted.

The present inventors completed the present invention as a result of intensive research to improve the above-mentioned drawbacks.

(Problems to be Solved by the Invention) The object of the present invention is to provide deodorizing acrylic synthetic fibers that have excellent deodorizing effects and washing resistance, and retain the fiber performance and texture of acrylic synthetic fibers. The manufacturing method is presented below.

(Means for Solving the Problems) The deodorizing acrylic synthetic fiber of the present invention is an acrylic synthetic fiber composed of a copolymer containing acrylonitrile and cellulose KM 8, in which a cellulose derivative exists in a phase-separated state. The cellulose inducer is characterized by containing fine particles of a ceramic and phosphor deodorant in the cellulose inducer.

In addition, when manufacturing acrylic synthetic fibers by hot spinning, the method of the present invention involves uniformly dispersing fine ceramic deodorant particles in an organic solvent/8 solution of a cellulose derivative, and then dispersing a copolymer containing acrylonitrile. Do you have R? ? I
It is characterized in that it is added to an M solution and then spun.

The AN copolymer component used in the present invention preferably contains at least 40% by weight of AN and has fiber-forming ability; that is, it contains at least 40% by weight of AN and other vinyl monomers such as acrylic acid and methacrylic acid. Acids 2 or their alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, sodium allylsulfonate, sodium methallylsulfonate, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamide-2-methylpropanesulfonate, etc. 60 appropriate combinations of
Examples include those copolymerized in a proportion of less than % by weight.

In particular, a copolymer of a vinyl monomer and a sulfonic acid group-containing monomer containing 80% by weight or more of AN and 20% by weight or less, or a copolymer containing 40% by weight or more of AN and 20 to 60% by weight of vinylidene chloride and a sulfonic acid group-containing monomer. Copolymers are preferred.

The cellulose derivatives used in the present invention are acetyl cellulose, acetyl propionic cellulose, and acetyl butyryl cellulose;
The content is 0 to 20.0% by weight, preferably 2.0 to 15.0% by weight. The amount of cellulose derivative is 1.0% by weight
If it is less than 20%, a good phase separation state containing the ceramic deodorant cannot be obtained, and if it exceeds 20%, the fiber performance will deteriorate and it will be difficult to produce it industrially easily and at low cost.

The ceramic deodorant used in the present invention is Ti, Z
It is a porous substance in the form of a fine powder made of an inorganic compound containing metal oxides such as n, AI, Sn, Si Fe, CaMg, and Ba, and in particular, a porous substance in the form of a white fine powder of hydrated oxides of Ti and Zn. Preferably, Cerawhite (trade name, manufactured by Titanium Industry Co., Ltd.) is made of a quality material. The content of the ceramic deodorant is 1.0 to 15% by weight, preferably 2.0 to 10% by weight, based on the AN copolymer. If the content of the ceramic polymer is less than 1.0% by weight, sufficient deodorizing performance cannot be imparted to the fiber, and if it exceeds 15% by weight, the fiber performance will decrease and the spinnability and spinnability in spinning will deteriorate. descend.

The fibers of the present invention localize the ceramic deodorant in the phase-separated cellulose derivative, and also reduce the contact area between the malodorous substance and the ceramic deodorant by the macrovoids formed by the phase-separated cellulose derivative. This is achieved by taking a large amount so that the ceramic deodorant works efficiently without waste.

The method of the present invention involves uniformly dispersing a warmed ceramic deodorant in an organic solvent solution of a cellulose derivative, and then
Most of the ceramic deodorants are impregnated into the cellulose derivative by adding it to an organic solvent solution of the AN copolymer and spinning it. Examples of the solvent used in the method of the present invention include organic solvents such as dimethylformamide, dimethylacetamide, trimethylsulfoxide, and acetone. In the present invention, the concentration of the organic solvent solution of cellulose derivative is usually 5 to 40% by weight, preferably 10% by weight.
~30% by weight. If this concentration is less than 5% of double walls, the concentration of the spinning stock solution decreases, depending on the amount of cellulose derivative added, resulting in decreased spinnability and decreased fiber properties. Moreover, if it exceeds 40% by weight, not only will it become difficult to uniformly disperse the ceramic deodorant due to the increase in viscosity, but also the spinnability will decrease, making it difficult to easily produce it industrially. Spinning can be carried out under the same conditions as for ordinary acrylic synthetic fibers, and the fibers are sequentially drawn through several stages of baths, followed by washing, drying, and post-treatment.

(Effects of the Invention) The deodorizing acrylic synthetic fiber of the present invention has an excellent deodorizing effect, has the same fiber performance as ordinary acrylic synthetic fiber, and has wash resistance.

There is almost no decrease in deodorizing effect due to dry cleaning resistance. Furthermore, the method for producing deodorizing acrylic synthetic fibers of the present invention allows such fibers to be produced industrially easily and inexpensively using normal acrylic synthetic fiber production conditions and equipment.

The fibers obtained by the present invention can be used in combination with ordinary acrylic synthetic fibers, polyester, nylon, cotton, rayon, wool, etc., and can be used in clothing, blankets, and carpets with deodorizing properties. It is extremely meaningful industrially because it can be used for a wide range of purposes such as cloaks, socks, sheets, and futon cotton.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. In the Examples, [%J] means "% by weight".

[Trimethylamine (ethyl mercaptan) removal rate measurement method]

Place 1 g of fiber sample in a 100 ml vial and seal. Furthermore, 1 ml of 6% trimethylamine aq (or ethyl mercaptan) headspace gas (25° C.) is injected into the previously sealed vial using a gas-tight syringe, and after 30 minutes, 1 mi' of headspace gas is analyzed by gas chromatography.

100 mj in the sky as a comparison! Inject 1 ml of 7 dos space gas into a vial containing 6% trimethylamine (or ethyl mercaptan), perform gas chromatography analysis, and calculate the trimethylamine removal rate (%) based on the reduction rate of the peak area.

Examples 1 to 6, Comparative Examples 1 to 4 7crylonitrile (AN)/methyl acrylate) (
MA) / Sodium methacryl sulfonate (SMAS) =
A dimethylformamide (DMF) solution of an acrylic copolymer consisting of 91.2/8.010.8 was prepared.

Then, for the acrylic copolymer, Cerawhite (manufactured by Titan Kogyo ■) was added to a DMF solution of a cellulose derivative using a homomixer in a homogeneous molecule 1. l jlt, added to the above acrylic copolymer solution in the amount listed in Table 1 and thoroughly stirred with a homomixer to obtain a spinning stock solution.
It was spun into a DMF aqueous solution, stretched and washed with water while removing the solvent, and then dried and densified by applying an oil agent. After applying a crimp to this fiber, it was subjected to a heat treatment at 120° C. with moist heat.

Table 1 shows the results of the deodorization test for the obtained fibers.

The spinning operability was evaluated in three stages: ◎, ○, and ×, based on comprehensive evaluation of filtration pressure, single yarn breakage, roller turbulence, etc. when produced under the conditions described in the examples.

As Comparative Examples 1 to 3, CeraWhite was uniformly dispersed in DMF for the acrylic copolymer, and then added to the above acrylic polymer solution and thoroughly stirred with a homomixer to obtain a spinning stock solution. The spun layer treatment was carried out in the same manner as above. When Cerawhite was added at 30%, there was an increase in spinneret pressure and many single filament breakages occurred during spinning, and a satisfactory fiber could not be obtained. As Comparative Example 4, a deodorization test was conducted on fibers spun with 10% acetyl cellulose added to an acrylic copolymer.

As is clear from Table 1, the tested product has superior deodorizing performance compared to the comparative product. Example 7 AN/vinylidene chloride (Vclg)/sodium allylsulfonate (SAS) A DMF solution of an acrylic copolymer consisting of =57/40/3 was prepared.

After homogeneously dispersing 7% of CeraWhite into the acetyl cellulose solution, the acrylic copolymer? It was added to 8I& and sufficiently stirred to prepare a spinning stock solution. The amount of acetylcellulose added was 10% based on the acrylic copolymer.

The above spinning dope was spun into a 55% DMF aqueous solution at 25° C., stretched and washed with water while removing the solvent, and then dried and densified by applying an oil agent. After applying a crimp to this fiber, heat 1
Heat treatment was performed at 15°C.

The obtained fibers are made into a circular knitted fabric and washed at home with 0. A deodorization test was conducted after 5IO cycles. As shown in Table 2, a good deodorizing effect was exhibited even after washing <10 times.

[Washing conditions]

Using a commercially available small electric washing machine Neutral detergent 1 g/i Bath ratio temperature x time Water Wash drying : 100 0℃×5 minutes 0 minutes θ℃×1 hour

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing a ceramic deodorant dispersed in a cellulose derivative phase-separated from a porous acrylic copolymer of the fiber of the present invention. FIG. 2 is a schematic diagram showing a ceramic deodorant uniformly dispersed in a conventional acrylic copolymer as a comparative example.

Claims (2)

[Claims] (1) In acrylic synthetic fibers made of a copolymer containing acrylonitrile and a cellulose derivative, the cellulose derivative exists in a phase-separated state and ceramic deodorant fine particles are contained in the cellulose derivative. A deodorizing acrylic synthetic fiber. (2) When manufacturing acrylic synthetic fibers by wet spinning, ceramic deodorant fine particles are uniformly dispersed in advance in an organic solvent solution of a cellulose derivative, and then added to an organic solvent solution of a copolymer containing acrylonitrile, A method for producing deodorizing acrylic synthetic fiber, which comprises spinning this.