JPH069604B2 - Deodorant material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to deodorization in the field of clothing and non-clothing fields, which have a bad odor and are considered a problem from the viewpoint of hygiene.

[Prior art]

Conventionally, for bad odors in the non-clothing field, such as bad odors in refrigerators and odors emitted from industrial equipment, activated carbon has been used as a deodorant and has some effects, but in the garment field, The fact is that activated carbon is difficult to use and has not been technically solved at all.

Attempts have been made to substitute a reaction product of ferrous sulfate and L-ascorbic acid for activated carbon, but the durability to washing is poor and the utility value is low.

[Problems to be solved by the invention]

The present invention is intended to provide a durable deodorizing material in the field of clothing and non-clothing based on the above background.

[Means for solving problems]

The present invention has the following configuration in order to achieve the above object.

A deodorizing material, characterized in that the acidic group contains iron ions and a reducing agent in a molded article having an acidic group of 3.2 × 10 ⁻⁴ gram equivalent / gram or more.

It will be described in more detail.

The acidic group in the present invention means a carboxylic acid or sulfonic acid group, and in a material such as synthetic fiber, a carboxylic acid group is preferable in order to stably maintain the form of clothing or the like.

The content of these acidic groups is 3.2 × 10 ⁻⁴ gram equivalent / g or more in order to impart good deodorizing performance,
It is necessary to have preferably 9.3 × 10 ⁻⁴ gram equivalent / gram or more.

The acidic group adsorbs iron ions and further reduces the iron ions with a reducing agent, so that stable ferrous iron ions (divalent iron ions) can be made to exist with good durability.

The iron ion in the present invention means ferrous (divalent iron) and ferric (trivalent iron) ions, but ferrous ion is preferred for deodorization. As these iron ions, various iron compounds such as ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous phosphate, ferric sulfate, ferric chloride and ferric phosphorus However, ferrous compounds are preferred because the objects of the present invention are preferably achieved.

Although the deodorizing behavior due to such iron ions is not clear, the following mechanism of action is considered. That is, when a ferrous ion (divalent iron ion) compound is contained in the acidic group-containing molded article according to the present invention and the ferrous ion absorbs an odor, a ferric ion (trivalent iron ion) is added. Exhibits a deodorizing effect by being oxidized to iron ions. However, in this state, the deodorizing effect disappears and the deodorizing effect cannot be sustained. Therefore, in the present invention, after containing such a ferrous ion compound or at the same time, by treating with a reducing agent, a stable ferrous ion state is maintained, and further, trivalent ferric iron is oxidized by deodorization. Even when it becomes an ion, the reducing agent works promptly to reduce it to a divalent ferrous ion, thereby maintaining the deodorizing effect.

Examples of such reducing agents include L-alcorbic acid, potassium cyanide, sodium thiosulfate, hydroxylamine and derivatives thereof, but L-alcorbic acid is preferable in order to achieve a durable and long-lasting deodorizing effect.

As the content of these iron ion compounds and reducing agents, the equivalent content of the acidic group in the present invention is theoretically the maximum content, but substantially up to the theoretical maximum content. It is not necessary to include it, and normally, 5% or more, preferably 10% or more of the gram equivalent number of the acidic group may be included.

Next, the molded article referred to in the present invention means staples, tows, spun yarns, filament yarns, and non-woven fabrics made of these,
Fiber moldings such as woven and knitted fabrics, plastic moldings such as films, cut piles (cut short fibers) and powdered granules are not particularly limited.

In addition, as a method of containing an acidic group in such a molded article, a method of co-polymerizing an acidic vinyl monomer at the time of polymerizing a fiber or a plastic, or an acidic vinyl polymer (with another monomer in advance when forming a polymer) is used. (Including copolymers), or after forming into a molded product, there is a method in which it is present on the molded product, inside or on the surface by graft polymerization or adhesion processing by affinity. From the viewpoint of stabilizing the morphology, molded article internal graft polymerization, or molded article surface graft polymerization,
The attachment processing method by affinity is preferable.

As a matter of course, as a macro form of the molded product, a product having a large number of surface irregularities, cracks or fine holes and a large surface area is preferable. Therefore, it is preferable that the fiber form has a large surface area such as a combination of hollow fibers and fine pores.

The deodorizing effect referred to in the present invention was measured by the following means.

Method A is an ammonia gas detector tube method, in which 3 g of a deodorant material is packed in a glass column, and an ammonia gas concentration of 1000 ppm is passed at a ventilation rate of 3.3 cm / sec, and the breakthrough time and This is a method of measuring the amount of excessive adsorption (Kitagawa type gas detector tube).

In method B, about 5% of ammonia water was impregnated with 0.25 ml of filter paper (3 × 6 cm) and then put into a 150 ml glass container.
At the same time, 0.5 g of the deodorizing material is put in the container, the container is tightly closed, and the odor change after standing for 4 hours is examined.

Hereinafter, it will be described in more detail with a specific example.

Example 1, Comparative Examples A to D Cut short fibers made of 3 denier × 1.0 mm nylon 6 were made into 50% owf of methacrylic acid, ammonium persulfate, and 1
% Owf, Super Light C (manufactured by Mitsubishi Gas Chemical Company) 3% ow
Under the condition of f and bath ratio of 1:15, the temperature was raised from room temperature to 75 ° C. at 1 ° C./min, and grafting was performed for 60 minutes at this temperature.

When the degree of grafting was measured by alkali-acid neutralization titration, it was confirmed that carboxyl groups were contained in an amount of 3.5 × 10 ⁻³ gram equivalent / gram fiber.

This fiber was washed with water and then treated with an aqueous solution of sodium carbonate and 30% owf at a bath ratio of 1:15 at 60 ° C. for 30 minutes. After further washing with water, 60 ° C. × 3 in an aqueous solution containing ferrous sulfate and L-alcorbic acid at 20 g / each.
A treatment was performed for 0 minutes to obtain a deodorizing material (this example).

The amount of iron ion-L ascorbic acid contained in the deodorizing material was 5% by weight.

Next, as a comparison, the cut pile made of nylon 6 of this example was treated with ferrous sulfate and L-ascorbic acid under the same conditions as in this example without being subjected to graft polymerization (Comparative Example). A). Further, under the same conditions as those of the present Example side, prototypes without ferrous sulfate and without L-ascorbic acid were produced as prototypes (Comparative Examples B and C). Furthermore, the deodorizing property of ammonia gas was measured for each of graft polymerization, sodium carbonate treatment and subsequent ferrous sulfate and L-ascorbic acid treatment (Comparative Example D). It is confirmed that the material of the present invention has a very large deodorizing effect.

Example 2 A 40-count spun yarn composed of polyester-based cut fibers of 1.5 denier x 76 mm was knitted into a knot, and methacrylic acid 50%, benzoyl peroxide, 1%, Cathiogen AN Super (manufactured by Daiichi Kogyo Co., Ltd.) Dip in a 5% aqueous solution, squeeze it with a mangle so that the pick-up rate is 100%, roll up, wrap and seal with polypropylene film, then 1 with a high-pressure steamer.
Steaming treatment was performed at 20 ° C. for 60 minutes.

A carboxyl amount of 4.07 × 10 ⁻³ gram equivalent was introduced into such polyester.

Next, this knitted fabric is treated with an aqueous solution containing 10 g of sodium carbonate at 60 ° C. for 30 minutes, washed with water, immersed in an aqueous solution of 30% ferrous chloride and L-ascorbic acid, and treated at 60 ° C. for 30 minutes. Then, the material was deodorized (this example).

When the deodorizing material was subjected to the deodorizing last by the method B, it was found that it showed a good deodorizing performance after washing.

Example 3 An acrylonitrile fiber obtained by copolymerizing 8 mol% of itaconic acid was produced as a prototype, and such staple (3 denier × 101 m
m) was treated with an aqueous solution of 1% sodium hydroxide at 90 ° C for 30 minutes, and ferrous nitrate and hydroxylamine were each added to 3%.
It was treated with a 0% aqueous solution at 90 ° C. for 30 minutes (Example 3).

This product was subjected to a deodorizing test by method B, and it was confirmed that it had deodorizing performance with excellent durability.

Example 4 A false twisted yarn (150 denier, single fiber fineness 3 denier) knit made of polyester fiber, polyacrylic acid, melamine-based resin (Sumitex Resin M-3, manufactured by Sumitomo Chemical Co., Ltd.), and ammonium persulfate were added to each 30 %, 10
%, 0.2%, and soaked in an aqueous solution containing 100% and 0.2% so that the pickup was 100%, and steaming was performed for 10 minutes in saturated steam at 100 ° C. Then, treatment with sodium carbonate 10 g / aqueous solution at 40 ° C. for 30 minutes is performed, and after washing with water, treatment is performed at 40 ° C. for 30 minutes in an aqueous solution containing 20% of ferrous sulfate and L-alcorbic acid to remove the deodorant of the invention. I got the material. When the deodorization measurement was performed on this material by the method B described in this section, it was confirmed that the material had a deodorizing performance with extremely good durability.

(Effects of the Invention) The present invention provides a molded product having both excellent durability and deodorizing effect, and can easily impart deodorizing performance to various materials regardless of the form of the molded product, so that the product design It could provide an easy one.

Claims (1)

[Claims] 1. A molded article having an acidic group of 3.2 × 10 ⁻⁴ gram equivalent / gram or more, wherein the acidic group is an iron ion,
A deodorizing material characterized by containing a reducing agent.