JPH08260347A - Production of deodorizing fibrous structural product - Google Patents

Abstract

PURPOSE: To obtain the subject fibrous structural product presenting high deodorizing effectiveness and excellent in durability to washing. CONSTITUTION: This fibrous structural product is obtained by substituting at least one kind of metal ion selected from Zn<2+> , Cu<2+> , Ni<2+> , Mn<2+> , Ag<2+> and Fe<2+> for the hydrogen ions of carboxylic acid group and/or sulfonic acid group on a fibrous structural product either after alkaline agent treatment or after dyeing under alkaline condition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a deodorant fiber structure.

[0002]

2. Description of the Related Art Conventionally, socks, underwear,
In the construction field, the odor of blankets and duvets is regarded as a problem.

As a solution to this problem, there is a concept of imparting antibacterial and antifungal properties. For example, JP-A-61-231202 discloses a method using a copper compound, JP-A-61-282474 discloses a method using a quaternary ammonium salt compound of an organic silicone, and JP-A-61-258076 discloses. Methods using various antibacterial agents have been disclosed.

As another attempt, Japanese Patent Laid-Open No. 61-296116.
JP-A-62-6953 discloses a method using a mixture of ferrous sulfide and L-ascorbic acid, and JP-A-62-6953 discloses a method using a metal phthalocyanine compound.

Further, Japanese Patent Publication No. Sho 61-22978 discloses a method using an extract from a plant of theaceae family, and Japanese Patent Laid-Open No. 59-225062 discloses a method using an extract from a coniferous plant.

However, these deodorizing / deodorizing techniques cannot always obtain a sufficient deodorizing effect, and are not practical.

In order to solve these problems, the present inventors have previously proposed a fiber material in which a polymer material having an acidic group is replaced with a specific metal ion (JP-A-5-7617). When mixed with other ordinary fibers or dyed after being mixed-knitted with other fibers, there was a case where some metal ions were dropped due to the influence of acid or alkali and the deodorizing performance was lowered.

[0008]

SUMMARY OF THE INVENTION
It is an object of the present invention to solve the problems of the technology disclosed in Japanese Patent Publication No. 5-7617 and provide a deodorizing material having a large deodorizing effect and excellent washing durability.

[0009]

In order to solve the above problems, the method of the present invention has the following constitution. That is, the hydrogen ions of the carboxylic acid group and / or the sulfonic acid group of the fiber structure having the carboxylic acid group and / or the sulfonic acid group are converted into Zn ²⁺ , Cu ²⁺ , Ni ⁺ , Mn ²⁺ , Ag ⁺ and Fe ^{2 When} substituting with one or more metal ions selected from the group consisting of ⁺ ,
A method for producing a deodorant fiber structure, which comprises replacing after treatment with an alkaline agent or dyeing under alkaline conditions.

The method of the present invention will be described in more detail below.

Examples of the fiber material of the deodorant fiber structure of the present invention include polyamide type, polyester type, acrylic type and rayon. Of these, polyamide-based and polyester-based are preferable from the viewpoint of easily introducing an acidic group.

Examples of the form of the fiber structure include staples, tows, tops, spun yarns, non-woven fabrics, woven fabrics and knitted fabrics.

The deodorant fiber structure of the present invention has a carboxylic acid group and / or a sulfonic acid group. Substituents other than these cause problems such as increased cost, insufficient deodorizing performance or poor durability even when substituted with a metal ion described later.

To introduce the carboxylic acid group and / or the sulfonic acid group into the fiber structure, a method of copolymerizing a vinyl monomer having the carboxylic acid group and / or the sulfonic acid group with the fiber polymer, the carboxylic acid group and / or There is a method of blending a polymer having a sulfonic acid group with a fiber polymer. The copolymerization includes random copolymerization, block copolymerization, and graft copolymerization, but the graft copolymerization is technically easy, the applicable range is wide, and economical, which is preferable.

As the vinyl monomer having a carboxylic acid group, acrylic acid, methacrylic acid, maleic acid, itaconic acid, butene tricarboxylic acid, etc., and as the vinyl monomer having a sulfonic acid group, allyl sulfonic acid, styrene sulfonic acid, etc. can give.

The method of graft polymerizing these vinyl monomers having an acidic group onto polyester fibers is as follows:
For example, an organic polymerization catalyst such as benzoyl peroxide is previously introduced into the polyester fiber using a swelling agent such as monochlorobenzene, and then a vinyl monomer having an acidic group is heated in an aqueous solution to perform graft polymerization or an organic method. There is a method in which fibers are heated in a liquid containing three components of a polymerization catalyst, a swelling agent, and a vinyl monomer having an acidic group to carry out graft polymerization.

As a method of graft-polymerizing the polyamide fiber, for example, there is a method of heating and graft-polymerizing in a liquid in which a catalyst such as ammonium persulfate or potassium persulfate and a vinyl monomer having an acidic group coexist.

In the method of the present invention, the fiber structure having a carboxylic acid group and / or a sulfonic acid group obtained as described above is dyed by an ordinary dyeing step, and then treated with an alkaline agent. The above-mentioned specific metal ion is substituted. When a specific metal ion is substituted before or during the dyeing step, the substituted metal ion is removed due to the influence of acid or the like in the dyeing step. If the dyeing process is performed under alkaline conditions, the treatment with an alkaline agent is not necessary.

After being treated with an alkaline agent or dyed under alkaline conditions as described above, Zn ²⁺ , Cu ²⁺ , Ni
^Immersing in a liquid containing a compound containing at least one metal ion selected from the group consisting of ⁺ , Mn ²⁺ , Ag ⁺ and Fe ²⁺ ,
Treat textile products. Even if it is replaced with a metal ion other than these, good deodorizing performance cannot be obtained.

The concentration of the metal ion compound is 0.05 to the solid content of the fiber, from the viewpoint of imparting a durable deodorizing effect and preventing a decrease in fiber strength and a change in hue.
It is preferable to adhere 3%, more preferably 0.15 to 0.6%.

This replacement process may be carried out in addition to the normal finishing process, or may be a process independent of the finishing process. In the latter case, it is preferable to perform treatment at 50 to 80 ° C. for 20 seconds to 3 minutes in a treatment bath containing a specific metal ion.

[0022]

The present invention will be described below in detail with reference to examples.

The deodorizing performance was measured as follows.

[Ammonia smell] A polyethylene container with a lid of 500 cc containing 80 μm of 0.3% aqueous ammonia solution
1 g, then 3 g of deodorized fiber structure sample in the same container
Charged and sealed, gas taken from the container after 20 minutes 1
The residual ammonia concentration in 00 cc is measured using a gas detector tube manufactured by Gastec Co., Ltd.

The initial ammonia concentration is about 200 ppm, and if the value after 20 minutes is 20 ppm or less, good ammonia deodorizing property is obtained.

[Hydrogen sulfide odor] 30 μ of 0.5% aqueous sodium sulfide solution in a 500 cc polyethylene container with a lid.
1, 100 μl of 0.5% sulfuric acid was dropped, then 3 g of the deodorizing fiber structure sample was placed in the same container and sealed, and after 20 minutes, the residual hydrogen sulfide concentration in 100 cc of the gas sampled from the container was calculated as ( Measurement is performed using a gas detector tube manufactured by Gastec Co., Ltd.

The initial hydrogen sulfide concentration is about 20 ppm,
If the value after 20 minutes is 2 ppm or less, good hydrogen sulfide deodorizing property is obtained.

(Example 1, Comparative Examples 1 to 5) Nylon 66
Staples (1.5 denier, 44 mm) were packed in an Overmeier-type package dyeing machine, scoured by a conventional method, and 4% by weight of acrylic acid was added to the staples.
A treatment bath containing 12 wt% of methacrylic acid, 1 wt% of ammonium persulfate with respect to the staple, and 3 wt% of a formalin condensate of sodium sulfite was prepared, and the treatment liquid was moved in and out, from 40 ° C to 1 ° C / min. The temperature was raised at a speed, and heat treatment was performed in the liquid at 80 ° C. for 60 minutes to perform graft processing.

Next, a 42/2 count blended yarn containing 50% each of washed and dried grafted nylon staple and ordinary polyester staple (1.5 denier, 44 mm) was spun.

A polyester filament-processed yarn of 75d-36 filaments is used as the warp, the above-mentioned mixed yarn is used as the weft, and 40% polyester / 60 cotton every 6 yarns of the mixed yarn.
% Of 42/2 count mixed yarn was woven into a plain weave fabric (Comparative Example 1). The mixing ratio of the grafted nylon staple in the woven fabric was 12.9%.

75d-36 filament polyester filament processed yarn is used for the warp, and nylon 66 is used for the weft.
A plain woven fabric using a 40/2 count mixed yarn of 40% staple / 60% cotton was woven (Comparative Example 2). The woven fabrics of Comparative Example 1 and Comparative Example 2 were each dyed with a normal polyester / cotton mixed fabric. According to the conditions, fried and desizing /
The dyed fabrics that were processed in the order of scouring, bleaching, mercerizing, intermediate setting, and continuous dyeing were designated as Comparative Examples 3 and 4.

In order to fix the dye on the cotton side, the dyeing process was carried out under an alkaline condition containing soda ash.

The dyed fabrics obtained in Comparative Example 3 and Comparative Example 4 were produced by using Catalyst FT (Dai Nippon Ink Co., Ltd.).
Made, containing 40% zinc nitrate) and dipped in a solution of 20 g / l, then squeezed with a mangle to obtain a pickup rate of 70%.
It was dried. A sample obtained by treating the woven fabric of Comparative Example 3 in this way was designated as Example 1 and a sample obtained by treating the woven fabric of Comparative Example 4 as described above was designated as Comparative Example 5.

Table 1 shows the results of evaluating the deodorizing performance of these samples.

[0035]

[Table 1] (Example 2, Comparative Examples 6 to 7) 50% of each of the grafted nylon staple obtained in Example 1 and a normal polyester staple (1.5 denier, 44 mm) is contained.
2/2 count mixed yarn for all wefts and 75d-for warp
A plain weave was woven using 36 filaments of polyester filament processed yarn (Comparative Example 6). The mixing ratio of the grafted nylon staple in the woven fabric was 20%.

A dyed fabric obtained by processing the dyed fabric obtained in Comparative Example 4 in the order of relaxation / scouring, intermediate setting, and dyeing in the same manner as a normal polyester fabric was designated as Comparative Example 7.

Dyeing conditions are the same as in the case of ordinary polyester fabrics, after dyeing with a disperse dye and a leveling agent, a nonionic activator 2 is added to remove the disperse dye on the nylon side.
Treatment was carried out at 80 ° C. for 30 minutes in a treatment bath containing g / l, hydrosulfite 1 g / l and caustic soda 0.5 g / l.

Next, the catalyst FT (catalyst
FT) (Dainippon Ink Co., Ltd., containing 40% zinc nitrate)
After being dipped in a solution of 20 g / l, it was squeezed with a mangle to give a pickup rate of 75% and then dried to obtain Example 2.

The results of evaluating the deodorizing performance of these samples are shown in Table 2.

[0040]

[Table 2] (Example 3, Comparative Examples 8 to 9) A half tricot made of 100% nylon 6 filament (70d) was scoured and processed in the order of an intermediate set, and then rolled into a carrier of a beam dyeing machine, and acrylic acid was treated. Against 3 wt
%, Methacrylic acid 9% by weight, ammonium persulfate as a catalyst 1% by weight with respect to the object to be treated, and a processing solution containing 3% by weight of a formalin condensate of sodium sulfite is prepared, and the beam dyeing machine is used at 80 ° C. for 60 minutes. Heat treatment was performed in the liquid.

Next, after rinsing with hot water and rinsing with water, the dyed tricot was dyed with a disperse dye according to the usual dyeing method for nylon tricot, and the obtained dyed tricot was used as Comparative Example 8.

In order to improve the fastness of the tricot obtained in Comparative Example 8, treatment was carried out at 60 ° C. for 20 minutes in a treatment bath containing 1 g / l of soda ash and 1 g / l of nonionic activator, and then washed with hot water. The sample obtained by washing with water and drying was used as Comparative Example 9.

The tricot sample obtained in Comparative Example 9 was used as a catalyst FT (catalyst FT) (manufactured by Dainippon Ink and Chemicals, Inc.).
Example 3 was carried out by immersing in a 20 g / l solution containing 40% zinc nitrate, squeezing with a mangle to obtain a pickup rate of 50%, and then drying.

Table 3 shows the results of evaluating the deodorizing performance of these samples.

[0045]

[Table 3]

[0046]

By the method of the present invention, a deodorizing material having a large deodorizing effect and excellent washing durability can be provided.

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Claims (1)

[Claims] 1. A hydrogen ion of a carboxylic acid group and / or a sulfonic acid group of a fiber structure having a carboxylic acid group and / or a sulfonic acid group is converted into Zn ²⁺ , Cu ²⁺ , Ni ⁺ , Mn ²⁺ , Ag ^+.
And a metal ion selected from the group consisting of Fe ²⁺ , when being substituted, after being treated with an alkaline agent or after dyeing under alkaline conditions, the production of a deodorant fiber structure characterized by the substitution Method.