JP2013199718A - Acrylic deodorant fiber, and spun yarn and woven and knitted fabric containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic deodorant fiber that has excellent deodorant performance against a bad smell such as acetic acid, isovaleric acid, nonenal and ammonia, which is generated in daily life, and to provide a spun yarn and woven and knitted fabric containing the same.SOLUTION: The acrylic fiber comprises 60-90 mass% of an acrylonitrile-based polymer, 9-39 mass% of cellulose acetate and 0.5-2.5 mass% of an inorganic deodorant, and has a fiber structure in which the cellulose acetate forms an island component and the acrylonitrile-based polymer forms a sea component in a cross section in a direction perpendicular to a fiber axis.

Description

  The present invention relates to an acrylic deodorizing fiber having good deodorizing performance against bad odors such as acetic acid, isovaleric acid, nonenal and ammonia generated in daily life, and a spun yarn and a woven or knitted fabric containing the same.

  At present, acrylic synthetic fibers have a soft and warm texture, and are excellent in dyeing vividness, and thus are widely used in the clothing and bedding fields. In recent years, for example, in the sanitary field, knitted fabric products such as blankets, moquettes, mats, carpets, socks, underwear, sheets, and curtains have been strongly demanded.

  Conventionally, the following methods have been proposed as means for imparting a deodorizing effect to a textile product in order to eliminate the odor that has been regarded as a bad odor. For example, in Patent Document 1, the cellulose acetate is 10 to 40% by mass and the acrylonitrile-based polymer is 60 to 90% by mass, and the cellulose acetate is the island component and the acrylonitrile polymer is the sea component in the cross section perpendicular to the fiber axis. An acrylic composite fiber characterized by having a fiber structure is disclosed.

  In Patent Document 2, a core-sheath composite type acrylic deodorant fiber having a sheath part and a core part, wherein the sheath part is made of an acrylonitrile polymer, and the core part contains deodorant fine particles. An acrylic deodorant fiber comprising a cellulose derivative or a mixture of a cellulose derivative containing deodorant fine particles and an acrylonitrile polymer is disclosed.

  However, the method of Patent Document 1 has insufficient deodorizing performance against ammonia. Further, in the method of Patent Document 2, since the polymer containing the deodorant fine particles in the core part is covered with the polymer not containing the deodorant fine particles in the sheath part, when trying to obtain the deodorant performance, The content of the deodorant component must be increased. As a result, the cost increase by increasing the content of the deodorant component, the increase in yarn breakage in the spinning process, and the cost increase due to the increase in yarn breakage are problems. It was.

JP 2003-89924 A JP 2006-152475 A

  The present invention is an acrylic deodorizing fiber having a good deodorizing performance against bad odors such as acetic acid, isovaleric acid, nonenal and ammonia generated in daily life for the purpose of solving the above conventional problems, It is to provide a spun yarn and a woven or knitted fabric containing the same.

  The gist of the present invention consists of 60 to 90% by mass of an acrylonitrile polymer, 9 to 39% by mass of cellulose acetate and 0.5 to 2.5% by mass of deodorant fine particles, and cellulose in a cross section perpendicular to the fiber axis. The acrylic fiber has a fiber structure in which acetate is an island component and acrylonitrile-based polymer is a sea component.

  According to the present invention, an acrylic deodorizing fiber having good deodorizing performance against bad odors such as acetic acid, isovaleric acid, nonenal and ammonia generated in daily life, and a spun yarn and a woven or knitted fabric including the same are provided.

  Hereinafter, embodiments of the present invention will be described in detail.

<Acrylonitrile polymer 60-90 mass%>
The acrylic deodorant fiber of the present invention contains 60 to 90% by mass, preferably 65 to 75% by mass of acrylonitrile polymer. When the content of the acrylonitrile-based polymer is 60% by mass or more, yarn breakage and wrapping when spinning the acrylic deodorant fiber are reduced, and the fiber physical properties are improved and the spinning process passability is improved. Furthermore, the soft feeling of the woven or knitted fabric using the fiber is improved. Moreover, the dry feeling of the woven / knitted fabric using the said fiber becomes favorable because the content rate of an acrylonitrile-type polymer is 90 mass% or less.

  In the present invention, the acrylonitrile-based polymer comprises acrylonitrile and an unsaturated monomer copolymerizable therewith. Examples of such unsaturated monomers include acrylic acid, methacrylic acid, or alkyl esters thereof, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, and depending on the purpose, vinyl benzene sulfonic acid soda, methallyl sulfonic acid soda, Ionic unsaturated monomers such as sodium allyl sulfonate, sodium acrylamidomethylpropane sulfonate, sodium parasulfophenyl methallyl ether and the like can be used.

<Cellulose acetate 9-39 mass%>
The acrylic deodorant fiber of the present invention contains 9 to 39% by mass of cellulose acetate, preferably 15 to 35% by mass. When the cellulose acetate content is 9% by mass or more, the deodorizing performance with respect to acetic acid, isovaleric acid and nonenal is improved, and further, the dry feeling of the woven or knitted fabric using the fibers is improved. In addition, when the cellulose acetate content is 39% by mass or less, yarn breakage and wrapping are reduced when spinning the acrylic deodorant fiber, the fiber physical properties are improved, and the spinning process passability is good. Become.

In the cellulose acetate added to the acrylic deodorant fiber of the present invention, 74% or more and less than 92% of the hydroxyl groups are acetated in consideration of solubility in a solvent generally used for spinning of acrylic fiber. It is preferable to use cellulose acetate (the degree of esterification is 2.22 or more and less than 2.76).

<Deodorant fine particles 0.5-2.5 mass%>
The acrylic deodorant fiber of the present invention contains 9 to 39% by mass of cellulose acetate and 0.5 to 2.5% by mass of deodorant fine particles, preferably 1.0 to 2. It is good to contain 0% by mass. When the content of the deodorant fine particles is 0.5% by mass or more, the deodorization rate with respect to ammonia that cannot be obtained by containing cellulose acetate is improved. When the content of the deodorant fine particles is 2.5% by mass or less, yarn breakage and wrapping during spinning of the acrylic deodorant fiber are reduced, the fiber physical properties are improved, and the spinning process passability is improved. It becomes good.

  Further, the deodorant fine particles used in the present invention include metal oxides such as Ti, Zn, AI, Sn, Si, Fe, Ca, Mg, Ba, and Zr, and inorganics containing these metals and / or metal oxides. Fine powder containing a compound as a main component, solid acid fine particles hardly soluble in water, and the like can be used. Examples of such deodorant fine particles include trade name “Kesmon” NS-10 (manufactured by Toagosei Co., Ltd., average particle size 2 μm) and trade name “Mizukanite” HF (manufactured by Mizusawa Chemical Co., Ltd., average particle size 2 μm). ).

<Fiber structure in which cellulose acetate is an island component and acrylonitrile polymer is a sea component in a cross section perpendicular to the fiber axis>
In the acrylic deodorant fiber of the present invention, it is important that cellulose acetate forms an island component and an acrylonitrile polymer forms a sea component in a cross section perpendicular to the fiber axis. The acrylic deodorant fiber adopts such a sea-island structure, so that the fragile cellulose acetate is covered with an acrylonitrile-based polymer. As a result, the fiber is reinforced, and the single fiber fineness is 1.8 cN / dtex or more. The fiber elongation is 30% or more, and a spinning process passability equivalent to that of a normal acrylic fiber is obtained. Moreover, although the size of an island is not limited at all, in order to obtain the above-described fiber properties, it is advantageous that the size of the island is small.

<Structure in which cellulose acetate communicates>
In the acrylic deodorant fiber of the present invention, the sea-island structure in the cross section (fiber weft cross section) perpendicular to the fiber axis has all or part of the cellulose acetate as the island component in the cross section (fiber longitudinal cross section) in the fiber axis direction. It is preferable in terms of improving deodorant performance that they communicate.

<Having pores inside the fiber>
The acrylic deodorant fiber of the present invention preferably has pores inside the fiber when used for the purpose of light weight heat retention. In the present invention, the term “hole” refers to a void formed inside the fiber, and a part of the hole may be opened on the fiber surface, or the hole may connect the island and the island. Good. The shape and size of the pores are not limited in any way, but it is preferable that the fiber strength is maintained at 1.8 CN / dTex or more. .

<Spun yarn containing 20% by mass or more of acrylic deodorant fiber>
The spun yarn of the present invention contains 20% by mass or more and 30% by mass or more of acrylic deodorant fiber. By containing 20% by mass or more of the acrylic deodorant fiber, the deodorization rate for acetic acid is 80% or more, the deodorization rate for isovaleric acid is 85% or more, the deodorization rate for Nonenal is 75% or more, and the deodorization for ammonia The rate can be 70% or more.

<Woven and knitted fabric containing 20% by mass or more of acrylic deodorant fiber>
The woven or knitted fabric of the present invention contains 20% by mass or more and 30% by mass or more of acrylic deodorant fiber. By containing 20% by mass or more of the acrylic deodorant fiber, the deodorization rate for acetic acid is 80% or more, the deodorization rate for isovaleric acid is 85% or more, the deodorization rate for Nonenal is 75% or more, and the deodorization for ammonia The rate can be 70% or more.

<Deodorizing performance of woven and knitted fabric>
The woven or knitted fabric of the present invention is a woven or knitted fabric satisfying the following (1) to (4). When the woven or knitted fabric satisfies these deodorization rates, it becomes a measure that the woven or knitted fabric has a deodorizing performance of sweat odor and aging odor.
(1) Deodorization rate for acetic acid is 80% or more (2) Deodorization rate for isovaleric acid is 85% or more (3) Deodorization rate for Nonenal is 75% or more (4) Deodorization rate for ammonia is 70% or more

<Method for producing acrylic deodorant fiber of the present invention>
An example of a method for producing an acrylic deodorant fiber according to the present invention will be described.
In the method for producing an acrylic deodorant fiber in this embodiment, first, an acrylonitrile polymer stock solution, a cellulose acetate stock solution, and a deodorant fine particle master batch are prepared. At this time, the solvent used for the stock solution or the masterbatch is a common solvent. Furthermore, this solvent can be used with any of organic solvents such as dimethylacetamide, dimethylformamide, acetone, dimethylsulfoxide, inorganic solvents such as rhodan salts and nitric acid, and other solvents commonly used for spinning acrylic fibers. However, it is preferable to use an organic solvent in view of ease of recovery. Moreover, what was demonstrated above can be used suitably about the acrylonitrile-type polymer used at this time, a cellulose acetate, and a deodorizing fine particle.

  Next, the stock solution of acrylonitrile polymer, the stock solution of cellulose acetate, and the master batch of deodorant fine particles are sufficiently stirred and mixed to prepare the spinning stock solution. There is no particular limitation on the solid content concentration or temperature in the spinning dope, or the type of solvent, and the spinning dope can be adjusted by appropriately changing as necessary. Specifically, the solid content concentration in the spinning dope is preferably set to, for example, a concentration of about 15 to 35% by mass in consideration of spinning properties, productivity, and the like.

  Next, the spinning stock solution prepared as described above has a content of deodorizing fine particles contained in the acrylic deodorizing fiber using a spinneret of 0.5 to 2.5% by mass, preferably 1.0. Spinning is performed so that the content of the cellulose acetate is 9 to 39% by mass, preferably 15 to 35% by mass.

  The method for spinning is not particularly limited as long as it is solution spinning, and any of a wet spinning method, a dry wet spinning method, and a dry spinning method can be used. For example, when spinning by a wet spinning method, the spinning solution is discharged from a spinneret into a coagulating liquid composed of an organic solvent and water, and a coagulated yarn is formed in the coagulating liquid.

Then, the coagulated yarn obtained by the spinning can be subjected to the same steps as in the past, such as drying and densification after each treatment such as drawing, solvent removal, and oiling. Furthermore, after that, if necessary, for example, a heat shrink treatment for heat shrinking the fibers under pressurized steam can be performed.

By producing acrylic deodorant fibers as described above, it is possible to produce fibers with excellent spinning operability by preventing an increase in filtration pressure during spinning and clogging of nozzle holes. Moreover, the outstanding deodorizing performance can be provided, without impairing the outstanding physical property which acrylic fiber originally has.

<Method for producing spun yarn of the present invention>
The acrylic deodorant fiber of the present invention is cut into short fibers and then spun. The composition of the spun yarn may be 100% of the acrylic deodorant fiber of the present invention, and other fibers, for example, synthetic fibers such as ordinary acrylic fiber, polyester fiber, nylon fiber, rayon fiber, or chemical fiber, cotton Further, a spun yarn containing 20% by mass or more of an acrylic deodorant fiber may be blended with natural fibers such as wool and silk. The method for producing the spun yarn of the present invention is not particularly limited, and the spun yarn of the present invention can be produced by a known spinning method and spinning method.

<Method for producing woven or knitted fabric of the present invention>
Furthermore, the spun yarn of the present invention produced as described above is used as a constituent yarn of a woven or knitted fabric. In obtaining the woven or knitted fabric of the present invention, the woven structure, the knitted structure, the weaving method, the knitting method, the loom, the knitting machine or the like is not particularly limited.

  Further, the woven or knitted fabric of the present invention satisfies the deodorization rate for acetic acid of 80% or more, the deodorization rate for isovaleric acid of 85% or more, the deodorization rate for Nonenal of 75% or more, and the deodorization rate for ammonia of 70% or more. Therefore, for example, in the sanitary field, it is used for blankets, moquettes, mats, carpets, socks, underwear, sheets, curtains and the like.

Hereinafter, the present invention will be specifically described by way of examples. The measurement items in the examples were based on the following method.

(Deodorization rate measurement of ammonia or acetic acid (detector tube method))
Put a sample (2.4g cotton, 10cm long knitted fabric x 10cm wide) into a tedlar pack, with odorous gas so that the initial concentration is 100ppm for ammonia and 50ppm for acetic acid. 3 L was added, and the odor component concentration after 2 hours was measured with a detector tube and calculated from the following equation.
Deodorization rate (%) = ((Blank test concentration after 2 hours−Sample test concentration after 2 hours) / 2 Blank test concentration after 2 hours) × 100

(Deodorization rate measurement evaluation of isovaleric acid or nonenal (gas chromatography method))
Put a sample (knitted fabric cut to 6 cm x 8 cm) into an Erlenmeyer flask (internal volume: 500 ml). In the case of isovaleric acid, the initial concentration is 38 ppm, and in the case of nonenal, the initial concentration is 14 ppm. The solution was added dropwise, sealed, and after 2 hours, the gas in the flask was sampled with a syringe, the peak area was measured with a gas chromatograph, and the following formula was calculated.
Deodorization rate (%) = ((Sb−Sm) / Sb) × 100
However, Sb = 2 peak area of blank test after 2 hours Sm = 2 peak area of sample test after 2 hours

Example 1
An acrylonitrile polymer consisting of 93% by mass of acrylonitrile and 7% by mass of vinyl acetate is dissolved in dimethylacetamide (hereinafter referred to as “DMAc”) so that the solid content concentration is 24% by mass, and the acrylonitrile polymer is obtained. Stock solutions were prepared.
Separately, cellulose acetate (produced by Daicel Corporation) in which 74% or more and less than 92% of the hydroxyl groups are acetic acid is dissolved in DMAc so as to have a solid content concentration of 18% by mass to obtain a stock solution of cellulose acetate. Was prepared.

  Further, as a deodorant fine particle, a trade name “Kesmon” NS-10 (manufactured by Toagosei Co., Ltd., average particle size 2 μm) was uniformly dispersed in a DMAc solution with a bead mill to prepare a deodorant fine particle master batch.

  The stock solution of the acrylonitrile-based polymer, the stock solution of cellulose acetate, and the master batch of deodorant fine particles are sufficiently stirred and mixed with a homomixer so that each component has the ratio shown in Table 1 below. Was prepared.

  The spinning dope thus obtained was discharged into a DMAc aqueous solution at 40 ° C. and 55% by mass from a nozzle having a hole number of 20,000 and a hole diameter of 0.06 mmφ to obtain a coagulated yarn. The coagulated yarn was subjected to each treatment of stretching in hot water at 95 ° C. (stretching ratio 5 times), solvent removal, oil agent application, and drying densification. Thereafter, the fiber was subjected to relaxation heat treatment at 120 ° C. under pressurized steam to obtain an acrylic deodorant fiber having a single fiber fineness of 1.7 dtex.

(Examples 2 to 4)
An acrylic deodorizing fiber was obtained in the same manner as in Example 1 except that the trade name “Mizukanite” HF (manufactured by Mizusawa Chemical Co., Ltd., average particle size 2 μm) was used as the deodorizing fine particles.

(Comparative Examples 1 and 2)
Thoroughly stir the stock solution of the acrylonitrile polymer prepared in Examples 1 to 4, the stock solution of cellulose acetate, and the master batch of deodorant fine particles with a homomixer so that each component has the ratio shown in Table 2. The mixture was mixed to prepare a spinning stock solution A as a core component.

  Using the acrylonitrile-based polymer stock solution prepared in Example 1 as a sheath component spinning stock solution B alone, from a core-sheath compound spinning nozzle having a pore number of 5,000 and a pore diameter of 0.07 mmφ, The spinning solution discharge ratio of the core component and the sheath component is set so that the contents of cellulose acetate and deodorant fine particles are the ratios shown in Table 2, respectively, and discharged into a DMAc aqueous solution at 40 ° C. and 55% by mass for solidification. I let you. The coagulated yarn was subjected to each treatment of stretching in hot water at 95 ° C. (stretching ratio 5 times), solvent removal, oil agent application, and drying densification. Thereafter, the fiber was subjected to relaxation heat treatment at 120 ° C. under pressurized steam to obtain an acrylic deodorant fiber having a single fiber fineness of 1.7 dtex.

(Comparative Examples 3-5)
The stock solution of the acrylonitrile-based polymer prepared in Examples 1 to 4, the stock solution of cellulose acetate, and the master batch of deodorant fine particles were sufficiently mixed with a homomixer so that each component had the ratio shown in Table 3 below. The mixture was stirred and mixed to prepare a spinning dope, and an acrylic deodorant fiber was obtained in the same manner as in Example 1.

The deodorization rates of ammonia and acetic acid were measured for the acrylic deodorant fibers of Examples 1 to 4 and Comparative Examples 1 to 5 thus obtained, and the results are shown in Tables 1 and 2. Furthermore, the spinning operability was also evaluated from the occurrence of yarn breakage during fiber production, and the evaluation results are shown in Tables 1 and 2.
The spinning operability was determined as follows.
○: No yarn breakage, winding, etc., good spinnability △: No yarn breakage, but winding occurred, slightly poor spinnability ×: Many yarn breakage occurred, poor spinnability

  As is clear from Table 1, each of the acrylic deodorizing fibers of Examples 1 to 4 was excellent in deodorizing performance of both ammonia and acetic acid, and the spinning operability was also good.

  On the other hand, when the core-sheath type composite fiber is used (Comparative Examples 1 and 2), it is necessary to increase the content of the deodorant fine particles in order to obtain satisfactory deodorant performance. As the value increases, the spinning operability tends to decrease.

  Further, when no deodorant fine particles are contained (Comparative Example 3), the ammonia deodorizing performance is low, and when no cellulose acetate is contained (Comparative Examples 4 and 5), both ammonia and acetic acid are satisfied. You have not reached the level you want.

(Example 5)
The acrylic deodorant fiber of Example 1 and the viscose rayon fiber having a single fiber fineness of 1.3 dtex were spun at a blending ratio of 60% / 40% to obtain 1/68 spun yarn A with a hair count. . Using this spun yarn, a milling fabric was knitted with a 22 gauge circular knitting machine.

(Example 6)
A spun yarn B was obtained in the same manner as in Example 5, except that the acrylic deodorant fiber was changed to the acrylic deodorant fiber of Example 3. The spun yarn B was knitted with the arrangement shown in Table 5, and a milled knitted fabric was knitted with a 22G circular knitting machine.

(Example 7)
A 40/1 spun yarn C was obtained with 100% cotton. The spun yarn B and spun yarn C described in Example 6 were knitted in the arrangement shown in Table 5, and a milled knitted fabric was knitted with a 22G circular knitting machine.

(Comparative Example 6)
An anti-pill acrylic fiber having a single fiber fineness of 1 dtex and a cotton fiber were spun at a blending ratio of 55% / 45%, and a spun yarn D having a hair count of 1/68 was obtained. The spun yarn B and spun yarn D described in Example 6 were knitted with the arrangement shown in Table 3, and a milled knitted fabric was knitted with a 22G circular knitting machine.

  The knitted fabrics of Examples 5 to 7 and Comparative Example 6 thus obtained were evaluated according to the method described above for the deodorizing performance of ammonia, acetic acid, isovaleric acid and nonenal. The evaluation results are shown in Table 3 below.

  The acrylic deodorant fiber of the present invention has a good deodorizing performance against bad odors such as acetic acid, isovaleric acid, nonenal and ammonia generated in daily life, for example, in the sanitary field, blankets, moquettes, Useful for mats, carpets, socks, underwear, sheets and curtains.

Claims (6)

  It is composed of 60 to 90% by weight of acrylonitrile polymer, 9 to 39% by weight of cellulose acetate and 0.5 to 2.5% by weight of deodorant fine particles, and cellulose acetate is an island component in the cross section perpendicular to the fiber axis. An acrylic deodorizing fiber having a fiber structure in which a polymer is a sea component.   The acrylic deodorant fiber according to claim 1, which has a structure in which cellulose acetate communicates.   The acrylic deodorant fiber according to claim 1 or 2, wherein the fiber has pores inside.   A spun yarn comprising 20% by mass or more of the acrylic deodorant fiber according to any one of claims 1 to 3.   A woven or knitted fabric containing 20% by mass or more of the acrylic deodorant fiber according to any one of claims 1 to 3. The woven or knitted fabric according to claim 5, which satisfies the following (1) to (4).
(1) Deodorization rate for acetic acid is 80% or more (2) Deodorization rate for isovaleric acid is 85% or more (3) Deodorization rate for Nonenal is 75% or more (4) Deodorization rate for ammonia is 70% or more