JPH10245721A - Deodorant acrylic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a deodorant acrylic fiber having specific sheath-core structure, excellent in color developability, light fastness and deodorant activity sustainability, thus suitable as a material for clothing and interiors. SOLUTION: This deodorant acrylic fiber has such sheath-core structure that the sheath consists of an acrylonitrile-based polymer containing 0.5-10wt.% of a photocatalyst such as anatase-type titanium oxide and the core consists of another acrylonitrile-based polymer containing 0.1-10wt.% of an antioxidant such as phenolic compound, with the sheath polymer accounting for 1-50wt.% of the whole fiber. This acrylic fiber bas a light fastness of pref. grade 4 or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant acrylic fiber having excellent light fastness.

[0002]

2. Description of the Related Art In recent years, various deodorizing and deodorizing materials using a photocatalyst, particularly titanium oxide as a photocatalyst, have been developed for various uses because their effects are permanent due to the oxidative decomposition function of the photocatalyst. ing. For example, Japanese Patent Publication 4-466
Japanese Patent Application Laid-Open No. 2009-253544 discloses an example in which a highly active photocatalyst in which titanium oxide of a photocatalyst is doped with Pt or the like is applied to a base cloth or the like and applied to a vehicle interior odor purifying device. There is disclosed a method for obtaining an antibacterial / dirt preventing tile by heat-treating titanium oxide together with a binder. Also, in the field of textiles, JP-A-8-28401
No. 1 discloses a deodorant fiber that is kneaded with a photocatalyst such as titanium oxide and an adsorbent at the same time into a base polymer and is hardly influenced by the presence or absence of light irradiation.

[0003] On the other hand, acrylic fibers are the most light-stable dyeing fastness and strength among general-purpose synthetic fibers due to the combination of the base polymer and a basic dye which is generally called a cationic dye and has excellent color-forming properties and light fastness. Excellent retention,
Widely used for clothing, interior, materials, etc. However, in the prior art, when the acrylic fiber contains a photocatalyst, organic matter by the photocatalyst,
In particular, the decomposition of dyes is inevitable, and there is no proposal for a deodorant acrylic fiber that has the most important light-fastness and yarn quality, which are the most important in the performance of clothing, and has a deodorizing function using a photocatalyst. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a deodorant acrylic fiber having excellent light fastness and excellent deodorizing performance at the same time.

[0005]

According to the present invention, a photocatalyst is used in an amount of 0.1.
A polymer having a sheath-core structure having a sheath made of an acrylonitrile-based polymer containing 5 to 10% by weight and a core made of an acrylonitrile-based polymer containing 0.1 to 10% by weight of an antioxidant. Is in the range of 1 to 50% by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the acrylonitrile-based polymer serving as a base for a sheath and a core is an acrylonitrile homopolymer containing at least 50% by weight of acrylonitrile or an unsaturated copolymerizable with acrylonitrile and acrylonitrile. It is an acrylonitrile copolymer with a monomer. If the acrylonitrile content in the acrylonitrile-based polymer is less than 50% by weight, the coloring clarity characteristic of acrylic fibers,
As the coloring property is reduced, other physical properties such as thermal properties are also reduced. In the sheath portion and the core portion, the acrylonitrile-based polymer serving as the base does not necessarily have to have the same composition, and acrylonitrile-based polymers having different compositions from each other may be used as long as they have appropriate bonding properties.

Examples of the unsaturated monomer copolymerizable with acrylonitrile include acrylic acid, methacrylic acid or alkyl esters thereof, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride and the like. Examples include ionic unsaturated monomers such as sodium sulfonate, sodium methallyl sulfonate, and sodium acrylamidodimethylpropanesulfonate.

In the present invention, the sheath portion is composed of an acrylonitrile-based polymer containing a photocatalyst, and the content of the photocatalyst in the acrylonitrile-based polymer in the sheath portion is 0.5 to 10 with respect to the acrylonitrile-based polymer. % By weight. When the content of the photocatalyst is less than 0.5% by weight, the deodorizing performance is insufficient, and when it exceeds 10% by weight, the light fastness or the strength retention is reduced.

The photocatalyst is not particularly limited as long as it is a semiconductor having a band gap capable of generating active oxygen. However, it is desirable that the photocatalyst has high whiteness in order not to impair the color developing properties of the acrylic fiber. Oxide semiconductors such as titanium oxide, zinc oxide, tin oxide and molybdenum oxide are preferably used. In particular, anatase type titanium oxide is preferably used because of its low cost and high photocatalytic activity.

In the present invention, the core is made of an acrylonitrile polymer containing an antioxidant,
The content of the antioxidant in the acrylonitrile polymer in the core is 0.1 to 10 with respect to the acrylonitrile polymer.
% By weight. When the content of the antioxidant is less than 0.1% by weight, the light fastness is reduced. When the content is more than 10% by weight, not only is it not economical but also the fiber strength is reduced.

The antioxidant is not particularly limited as long as it has a radical chain inhibiting function, but a phenolic antioxidant is preferably used in order to avoid coloring of the acrylic fiber. As phenolic antioxidants,
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4 , 6- (1H, 3H, 5H) trione,
1,1,3-tris (2-methyl-4-hydroxy-5
-T-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [ Methylene (3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, triethylene glucose-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

The deodorant acrylic fiber of the present invention has a sheath-core structure in which an acrylonitrile-based polymer containing a photocatalyst is used as a sheath, and an acrylonitrile-based polymer containing an antioxidant is used as a core. The ratio of the acrylonitrile polymer in the sheath is 1 to 50% by weight, preferably 2 to 25% by weight. The sheath core structure in the deodorant acrylic fiber of the present invention does not necessarily require the sheath portion to have a constant or completely continuous thickness along the fiber surface.
A part of the core may be exposed on the fiber surface like a star. Further, the ratio of the acrylonitrile polymer in the sheath portion is 1
If it is less than 50% by weight, the deodorizing performance is insufficient, and
If it exceeds, the light fastness and fiber strength are significantly reduced.

The deodorant acrylic fiber of the present invention has excellent color fastness inherent in acrylic fiber and excellent light fastness of light fastness of class 4 or more, and at the same time, excellent properties based on the oxidative decomposition function of a photocatalyst. Has deodorant performance.

In producing the deodorant acrylic fiber of the present invention, there is no particular limitation on the spinning method. As in the case of producing ordinary acrylic composite fiber, wet spinning is carried out using a sheath-core composite spinning nozzle. It is manufactured by a wet spinning method or a dry spinning method. The solvent for the acrylonitrile-based polymer in the sheath portion and the core portion during the production of the deodorant acrylic fiber of the present invention is not particularly limited as long as the acrylonitrile-based polymer can be dissolved in a concentration that can be spun. Organic solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide; and inorganic solvents such as nitric acid, rhoda soda, and zinc chloride. For composite spinning,
A solution having a polymer concentration of 20 to 40% by weight is used as a spinning solution for the sheath and the core, respectively.

The addition of a photocatalyst to the acrylonitrile-based polymer serving as the sheath and the addition of an antioxidant to the acrylonitrile-based polymer serving as the core may cause deterioration of spinnability due to reaggregation of the added photocatalyst or antioxidant. In order to avoid the switching loss, it is preferable to add to each spinning dope in a state of being dispersed in a solvent or in the form of a previously prepared high-concentration master batch at a position as close to the spinning nozzle as possible. In addition, particularly when adding a photocatalyst, it is important to shield light when dispersing in a solvent, storing a dispersion, or adding a dispersion.

Also, various functional additives such as antibacterial agents and adsorbents, pigments and dyes are added to the spinning stock solution within a range not deteriorating the deodorant performance, light fastness and fiber strength retention rate, or the fiber production process. It can be added to a coagulation bath, washing bath, oil bath, and the like, and the same spinning process conditions as a coagulation bath and a coagulation method used in producing ordinary acrylic fiber, drawing, washing, and the like. The spinning process conditions such as drying and relaxation are applied.

[0017]

The present invention will be described below in more detail with reference to examples. The light fastness and deodorant performance were measured according to the following methods.

<Light fastness> A knitted acrylic fiber knitted fabric is added to 1 g of score roll 400 (manufactured by Kao Corporation, surfactant).
Immersion in an aqueous solution having a liquid ratio of 1:50 and a scouring treatment at 70 ° C. for 20 minutes. Next, 0.5 parts by weight of Eizen Katilon Blue KGLH (manufactured by Hodogaya Chemical Co., Ltd., cationic dye), 100 parts by weight of acetic acid, 2 parts by weight of acetic acid, 0.5 parts by weight of sodium acetate, a dyeing liquor having a liquid ratio of 1:50 with respect to 100 parts by weight of the knitted fabric. , And the temperature was raised to 100 ° C. in 30 minutes, dyed at 100 ° C. for 60 minutes, washed with water and air-dried to obtain a sample for evaluation. The light fastness of the evaluation sample was measured by irradiating a fade meter and determined in accordance with JIS L-842.

<Deodorizing performance> 1 g of the evaluation sample was
It was sealed in a liter Tedlar bag. Next, air containing ammonia was injected using a syringe to adjust the initial concentration of ammonia to 100 ppm. The Tedlar bag is allowed to stand at a distance of 15 cm from a 27 W white fluorescent lamp, and the entire test sample is irradiated with light (ultraviolet light). After one hour, the ammonia concentration in the Tedlar bag is measured using a gas detector tube (Gastec, ammonia (3L type), and the ammonia removal rate was calculated.

(Examples 1 to 4, Comparative Examples 1 to 5) Monomers having a ratio of 92.5% by weight of acrylonitrile / 7% by weight of vinyl acetate / 0.5% by weight of sodium methallylsulfonate by an aqueous suspension polymerization method. From the specific viscosity 0.17 (polymer 0.1
g was dissolved in 100 ml of dimethylformamide containing 0.1 N rhoda soda to obtain an acrylonitrile-based polymer (measured at 25 ° C.). Next, the acrylonitrile-based polymer was dissolved in dimethylacetamide to prepare a stock solution A having a polymer concentration of 25% by weight. In addition, an anatase type titanium oxide having an average particle size of about 0.2 μm and a specific surface area of about 50 m ² / g (TITANIUM manufactured by Nippon Aerosil Co., Ltd.)
DIOXIDE P25) 16 parts by weight of the acrylonitrile polymer and 10 parts by weight of the acrylonitrile polymer were dispersed in 74 parts by weight of dimethylacetamide to prepare a master batch stock solution B under light shielding.

Using a static mixer placed immediately before the spinning nozzle, the stock solution A and the stock solution B were added to the stock solution at the concentrations shown in Table 1 and mixed and dispersed to prepare a sheath spinning stock solution C. Further, a phenolic antioxidant (ADK STAB AO-50, manufactured by Asahi Denka Kogyo Co., Ltd.) was added to the stock solution A at a concentration shown in Table 1 and mixed and dispersed to prepare a core spinning stock solution D. did.

The two spinning dope solutions C and D were mixed with a pore size of 0.2
The sheath-core ratio was changed as shown in Table 1 from a sheath-core composite spinning nozzle having 60 circular holes having a diameter of 60 mm.
m air layer, dimethylacetamide 73% by weight /
It was led to a coagulation bath at 40 ° C. with 27% by weight of water. Next, it was taken up at 60 m / min by a roll outside the coagulation bath, washed in warm water, and then primary-stretched three times in boiling water. After the yarn has been sufficiently dried, it is subjected to double stretching by dry heat and a hot plate at 260 ° C. for one time.
By performing relaxation of 0%, a filament yarn having a sheath-core structure with a 150 denier / 60 filament single fiber fineness of 2.5 denier and a substantially circular single fiber cross section was obtained. The obtained filament yarn was knitted and dyed to obtain a sample for evaluation. Table 1 shows the measurement results of light fastness and deodorant performance.

[0023]

[Table 1]

(Examples 5 to 7 and Comparative Examples 6 to 8) Acrylonitrile 93.5% by weight / methyl acrylate 6% by weight / sodium methallylsulfonate 0.1% by an aqueous suspension polymerization method.
An acrylonitrile polymer having a specific viscosity of 0.16 was obtained from the monomer having a ratio of 5% by weight. Next, this acrylonitrile-based polymer was dissolved in dimethylformamide to prepare a stock solution E having a polymer concentration of 30% by weight. In addition, anatase type titanium oxide having an average particle size of about 0.2 μm and a specific surface area of about 50 m ² / g (TITANIUM D, manufactured by Nippon Aerosil Co., Ltd.)
16 parts by weight of IOXIDE P25) and 14 parts by weight of the acrylonitrile-based polymer were mixed with dimethylformamide 70
A master batch stock solution F dispersed in parts by weight was prepared under light shielding.

Using a static mixer installed immediately before the spinning nozzle, the stock solution F was added to the stock solution E, and the amount of the stock solution F was changed to the concentration shown in Table 2, and mixed and dispersed to prepare a sheath spinning stock solution G. Further, a phenolic antioxidant (ADK STAB AO-50, manufactured by Asahi Denka Kogyo Co., Ltd.) was added to the stock solution E at a concentration shown in Table 2 and mixed and dispersed to prepare a core spinning stock solution H. did.

The two spinning stock solutions G and H were mixed with a pore size of 0.2
The sheath-core ratio was changed as shown in Table 2 from a sheath-core composite spinning nozzle having 600 circular holes having a diameter of 600 mm, and the mixture was discharged into an inert gas at 230 ° C. to obtain an undrawn yarn having a sheath-core structure. Was. This undrawn yarn is bundled into a fiber bundle of 480,000 denier, stretched 4 times in hot water, washed in hot water and treated with an oil agent, and then the fiber bundle is tension-free at a relative humidity of 10%. , Temperature 150 ℃
, And then subjected to mechanical crimping and cut to a length of 51 mm. The obtained short fiber had a single fiber fineness of 3 denier, a single fiber cross section of dumbbell shape, and had a sheath-core structure in which a part of the core was exposed on the surface. The obtained short fiber spun yarn was knitted and dyed to prepare an evaluation sample. Table 2 shows the measurement results of light fastness and deodorant performance.

[0027]

[Table 2]

[0028]

The deodorant acrylic fiber of the present invention has excellent light fastness together with excellent color development inherent in acrylic fiber, and at the same time has excellent permanent deodorant performance.
It is suitable as a material for clothing, interiors, materials, etc., and is blended or mixed with synthetic or chemical fibers such as animal fibers such as wool, natural fibers such as cotton and linen, polyester fibers, polyamide fibers, and acetate fibers. It can also be compounded by fiber or blending, and can be used in a wide range of fields.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B01J 35/06 D01F 6/54 Z D01F 1/10 B01D 53/36 J 6/54 ZABH (72) Inventor Hiroshi Hosokawa Otake, Hiroshima 20-1, Miyuki-cho, Mitsubishi-rayon Co., Ltd. Otake Works (72) Inventor Kozo Mise 20-1, Miyukicho, Otake-shi, Hiroshima Pref. Inside Otake Works, Mitsubishi Rayon Co., Ltd. (72) Inventor Teruyuki Yamada Otake, Hiroshima Pref. 20-1 Miyuki-cho, Yokohama City Central Research Laboratory, Mitsubishi Rayon Co., Ltd.

Claims (3)

[Claims] An acrylonitrile polymer containing a photocatalyst in an amount of 0.5 to 10% by weight is used as a sheath, and an antioxidant is added in an amount of 0.1 to 0.1% by weight.
A sheath-core structure having a core of an acrylonitrile-based polymer containing 10 to 10% by weight, and a ratio of the polymer in the sheath is 1 to 50.
Deodorant acrylic fiber characterized by weight%. 2. The deodorant acrylic fiber according to claim 1, wherein the photocatalyst is an anatase type titanium oxide. 3. The deodorizable acrylic fiber according to claim 1, which has a light fastness of a light fastness class 4 or higher.