JPH04370220A - Deodorant fiber - Google Patents

Abstract

PURPOSE:To provide the subject fiver having an excellent deodorant function substantially without the generation of a color, characterized in that a copolymer product by radicalcopolymerizing a copper vinylsulfonate monomer is disposed on the outer circumference of the cross setion of the fiber in a specific amount and further that the copper is contained in the outer circumference in an amount of >= a specific value. CONSTITUTION:The objecting fiver charecterized in that a copolymer produced by radica- copolymerizing a copper vinylsulfonate monomer is disposer on the cross-sectional outer circumference of the fiver forming the surface thereof so that the area of the outer circumference occupies >=1/10 of the cross section of the fiver and further that the copper is contained in the outer circumference in an amount of >=0.1 wt.%.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to deodorizing fibers used in clothing such as pajamas for the elderly, bedding such as sheets, and rugs which require deodorizing properties.

0002

[Prior Art] As a method for imparting a deodorizing function to textile products, a method using ascorbic acid and a divalent iron compound is described in JP-A-61-296111. It is particularly effective and has little effect on mercaptan odor. In addition, a method for processing fibers with a phthalocyanine copper compound in a manner similar to dyeing was disclosed in JP-A-62
It is described in Japanese Patent No. 6978. There are also methods of processing copper sulfide into acrylic fibers and methods of coordinating copper to hydrolyzed acrylic fibers. However, all of these methods had a serious drawback in that the fibers were colored green or brown. All textile products are colorfully decorated with fashion. Fibers colored green or brown cannot be dyed with light colors.

[0003] Further, as a deodorant, a deodorizing ingredient extracted from natural Camellia family plants is described in Japanese Patent Application Laid-Open No. 100060/1983. However, the deodorizing effect of natural extracts of plants of the Camellia family is an inclusion effect, and odor components are incorporated into this extract, but it is inferior to the deodorizing effect due to the catalytic action of the copper compound described above. Also, since it is a natural material, it is expensive.

0004

SUMMARY OF THE INVENTION The main object of the present invention is to provide an inexpensive deodorizing fiber that has excellent deodorizing function, has almost no coloring in the fibers, and can be freely colored by dyeing.

[0005]

[Means for Solving the Problems] The present inventors investigated a method for stably fixing copper ions having a deodorizing function in fibers, and found that by radical copolymerizing a vinyl sulfonate copper salt comonomer, It was discovered that stable fixation could be achieved, leading to the completion of the present invention.

[0006] In the deodorizing fiber of the present invention, a copolymer obtained by radical copolymerization of a vinyl sulfonate copper salt comonomer is present at the outer periphery of the fiber cross section forming the surface of the fiber, and the area of the outer periphery is the fiber cross sectional area. It is characterized by containing at least 0.1% by weight of copper in its outer peripheral portion.

Vinyl sulfonate copper salt comonomers used in the present invention include allyl sulfonic acid (hereinafter abbreviated as "AS") and methacryl sulfonic acid (hereinafter "MAS").
” is abbreviated as “. ), styrene sulfonic acid (hereinafter referred to as “SS
” is abbreviated as “. ), acrylamide methylpropylsulfonic acid (hereinafter abbreviated as "AMS"), and other copper salts. These copper salts exhibit a green or blue color, but strangely, if they are copolymerized to the extent necessary for their deodorizing effect, they become colorless or their green color becomes extremely pale. Therefore, the resulting fibers are only colored colorless or very light, and do not affect normal dyeing in any way.

[0008] The deodorizing effect depends on the amount of copper ions. It also depends on the amount of copper ions on the surface of the fiber. Therefore, when the fiber has a core-sheath structure, it exhibits almost no deodorizing effect even if the core component contains copper ions. It is sufficient if the sheath component contains the required amount of copper ions. As for the amount of copper ions, it is necessary to contain 0.1% by weight or more of copper in a portion corresponding to 1/10 of the cross-sectional area of the fiber at the outer periphery of the cross-sectional area of the fiber forming the surface of the fiber. Preferably 0
．． It is 2% by weight or more.

[0009] When copper is an inorganic salt, the washing resistance against the deodorizing effect of the fibers is insufficient. Semi-permanent washing resistance is obtained by copolymerizing copper with a polymer.

Since these sulfonic acids are strong acids, copper salts can be easily produced by a neutralization reaction with copper hydroxide.

As the vinyl sulfonate comonomer, commonly used sodium salts, potassium salts, etc. may be copolymerized. For example, there is methacryl sulfonic acid sodium salt (hereinafter abbreviated as "MS"). sodium salt,
By copolymerizing potassium salts, etc., it can be easily dyed with cationic dyes. A comonomer such as vinyl sulfonate sodium salt or potassium salt as a dyeing seat for cationic dyes may be copolymerized in an amount of 0.5% by weight or more.

The main monomers to be copolymerized are acrylonitrile (hereinafter abbreviated as ``AN''), methacrylonitrile, vinyl acetate (hereinafter abbreviated as ``VA''), vinyl chloride, vinylidene chloride (hereinafter ``VD''). ), vinyl monomers such as styrene are used. For example, in the case of acrylic fiber, acrylonitrile is 85% by weight.
Used above. Furthermore, in the case of acrylic fibers, 40 to 50% by weight of acrylonitrile is used. In addition, as a second monomer to be copolymerized, methyl acrylate (hereinafter referred to as “
It is abbreviated as "MA". ), acrylic acid (hereinafter abbreviated as "AA"), methyl methacrylate, methacrylic acid, ethyl acrylate, butyl acrylate, ethyl methacrylate, etc. are used.

The copolymerization method is not particularly limited. Commonly used suspension polymerization, emulsion polymerization, and solution polymerization are used. Batch polymerization or continuous polymerization may be used. As the polymerization initiator, commonly used peroxides, azo compounds, persulfates, etc. are used. If necessary, auxiliary materials such as polymerization stabilizers and coloring inhibitors may be used. In the case of solution polymerization, the solvent used is, for example, dimethylformamide (hereinafter abbreviated as "DMF"), dimethyl sulfoxide, or the like.

The spinning method used in the present invention includes a dry spinning method, a dry-wet spinning method, and a wet spinning method, and is not particularly limited. For example, in wet spinning, staples are spun, stretched, washed, oiled, dried, crimped, and cut according to standard methods. For example, in the dry process, filaments are spun, oiled, and drawn, but are not limited thereto.

[0015]

Effects of the Invention The deodorizing fiber of the present invention has an excellent deodorizing function, and is an inexpensive deodorant fiber that has almost no coloration and can be freely colored by dyeing.

[0016]

[Example] Further details will be explained in Examples. In the examples, "%" means "% by weight" unless otherwise specified.

To evaluate the deodorizing properties of textile products, add 30 ml of ethyl mercaptan to a 100 ml sample bottle containing 1 gram of sample.
Ethyl mercaptan in the sample head was measured by gas chromatography after 30 minutes and 60 minutes had elapsed after 0 ppm was added, and the amount was determined from the weight loss.

The amount of copper in the fibers was determined using a Shimadzu Green solid sample atomic absorption measurement system SM-30. For example, when the fiber is a composite fiber with a core-sheath structure, copper is quantified by measuring the copper in the entire fiber, and distributing the copper concentration based on the area ratio of the cross section of the fiber. When the division of the fiber cross section was unclear, the area ratio was measured using a sample colored by adding 0.5% carbon black to one side.

Production Example 1 Dissolve 100g of AMS in 1kg of DMF, and dissolve 1/2
An equivalent amount of copper hydroxide was dispersed and stirred at room temperature for 2 hours so as not to exceed 30°C, and a neutralization reaction was carried out to obtain a DMF solution of copper salt of AMS (hereinafter abbreviated as "AMS copper").

Production Example 2 In the same manner as Production Example 1, AMS was changed to MAS, and MAS
A DMF solution of the copper salt (hereinafter abbreviated as "MAS copper") was obtained.

Production Example 3 AMS copper produced in Production Example 1 was 2%, AN was 90%,
With a monomer composition ratio of 0.5% MS and 7.5% MA,
DMF solution polymerization with a monomer concentration of 30% was carried out using azobisisobutyronitrile as an initiator at a polymerization temperature of 60°C and 18°C.
A dope with a polymerization rate of 53% was obtained. After recovering the monomer by a conventional method, it was diluted to a polymer concentration of 19% to produce Polymer A.

Production Example 4 In the same manner as Production Example 3, no AMS copper was added and the MA was 9.
Polymer B was produced by changing the amount to 5%.

Production Example 5 Polymer B was produced in the same manner as in Production Example 3, except that the AMS copper was replaced with the MAS copper of Production Example 2.

Production Example 6 Polymer A was produced in the same manner as in Production Example 4 except that the monomer composition ratio was changed to that shown in Table 1.

Example 1 A composite nozzle was used with Polymer A of Production Example 3 as the sheath and Polymer B of Production Example 4 as the core, and the discharge rate of the gear pump was adjusted so that the core/sheath ratio was 4:1. D by wet spinning
After spinning into a MF water-based coagulation bath and stretching 8 times in hot water,
After washing with water, drying, oiling, and crimping, the fiber was cut into a predetermined length to obtain a 3-denier fiber of the present invention containing copper ions on the surface side of the fiber cross section.

[0026] As a result of measuring the copper content of the obtained fiber, it was found that the fiber contained 0.1% copper based on the entire fiber. The sheath polymer contains 0.5%, which is 5 times that amount. The color of the obtained fiber was hardly colored even though it contained copper ions.

Next, the deodorizing effect of the obtained fibers was measured using ethyl mercaptan, and the reduction rate was 100% after 30 minutes.
It showed excellent deodorizing effect.

Furthermore, the tensile strength and elongation of the obtained fibers was measured and showed physical properties of 3.2 g/d and 38%, which are the same as those of general acrylic.

Example 2 Polymer A of Production Example 3 was wet-spun using a regular round hole spinneret in the same manner as in Example 1, and the deodorizing effect of the obtained fiber was measured using ethyl mercaptan. The rate is 30
After a few minutes, it showed an excellent deodorizing effect of 100%.

Further, the tensile strength and elongation of the obtained fiber was measured, and it was found to be 3.8 g/d, 42%, which is the same physical property as general acrylic.

Example 3 Wet-spun only Polymer A of Production Example 5 using an ordinary round hole spinneret in the same manner as in Example 1, and measured the deodorizing effect of the obtained fiber using ethyl mercaptan. The rate is 30
It showed an excellent deodorizing effect of 100% after 1 minute.

Furthermore, the tensile strength and elongation of the obtained fibers was measured and showed physical properties of 3.6 g/d and 39%, which are the same as those of general acrylic.

Example 4 Wet-spun only Polymer A of Production Example 6 using an ordinary round hole spinneret in the same manner as in Example 1, and measured the deodorizing effect of the obtained fiber using ethyl mercaptan. It is shown in Table 2. Composition No. of the present invention example. Samples 1 to 4 exhibited excellent deodorizing properties. Among them, composition N in which the amount of copper ions exceeds 1% in the entire fiber
o. Samples 1 to 3 showed excellent deodorizing properties. Composition No. Comparative Example No. 5 exhibited only slight deodorizing properties due to insufficient copper ion content.

[0034]

[Table 1]

[0035]

[Table 2]

Claims (1)

[Claims] Claim 1: A copolymer obtained by radical copolymerization of a vinyl sulfonate copper salt comonomer is present at the outer periphery of the fiber cross section forming the surface of the fiber, and the area of the outer periphery accounts for 1/10 or more of the fiber cross sectional area. A deodorizing fiber characterized by containing 0.1% by weight or more of copper in its outer peripheral portion.