JPH01272868A - Production of deodorizing fiber - Google Patents

Abstract

PURPOSE:To impart excellent deodorizing properties to a fiber without deteriorating feeling and other functions essential to the fiber, by reacting the fiber having affinity for tannic acid with the tannic acid carrying a transition metal and adhering the resultant reaction product into the fiber. CONSTITUTION:A fiber, such as cellulosic fiber, protein fiber, such as wool or silk, or nylon, having affinity for tannic acid is pretreated with a solution of a transition metal compound, such as ferrous oxide, ferric chloride, ferrous sulfate, ferric sulfate, cuprous chloride or cupric chloride, to carry the transition metal thereon. The above-mentioned transition metal is then reacted with tannic acid in the afore-mentioned fiber to adhere the reaction product thereof into the above-mentioned fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing fibers having a deodorizing function. More specifically, the present invention relates to a method for producing deodorant fibers in which a reaction product of tannic acid and a transition metal is fixed as a deodorizing component in the fibers.

[Conventional technology]

Many deodorants have been developed as substances that remove malodorous substances such as ammonia, hydrogen sulfide, and mercaptans, such as extracts from plants of the Camellia family and mixtures of divalent iron compounds and L-ascorbic acid. Furthermore, in an attempt to impart a deodorizing function to textile products themselves, many fibers or textile products using these deodorants are being developed.

When attempting to impart a deodorizing function to fibers, there are two main ways to do so.

One is to mix a deodorant into the spinning solution when spinning synthetic fibers to make fibers, and the second is to add a deodorant to the spinning solution after it has become a fiber. It provides a deodorant.

[Problem to be solved by the invention]

In the method of mixing a deodorant into the spinning dope, the deodorant itself is required to have heat resistance and chemical resistance comparable to the spinning conditions. Furthermore, since the mixed deodorizer is covered in the polymer that forms the fibers, it is no longer able to fully demonstrate its original deodorizing ability, and more deodorant is required. It has drawbacks such as:

Furthermore, this method cannot be applied to fibers that are not spun, such as natural fibers, and in addition, from an economic standpoint, it is preferable to deodorize the fibers in the form of post-processing. .

On the other hand, when deodorizing fibers through post-processing, most deodorants do not have an affinity for the fibers themselves, so they are simply applied to the surface of the fibers, or are fixed with resin, etc. This is the most common method.

In the former case, the deodorant easily comes off not only during washing but also due to physical contact and vibration during use.

In the latter case, although the durability is improved, since the deodorant is coated with resin etc., the original deodorizing ability of the deodorant cannot be fully demonstrated, as in the case of spinning. I can't. Furthermore, depending on the resin used for fixing, the functions of the fibers themselves, such as wood-loving properties, bulkiness, and even texture, may be impaired.

On the other hand, among the methods of deodorizing fibers in post-processing,
Development is also underway to use deodorants that have an affinity for the fibers themselves.

This method depends on the affinity between the fiber and the deodorant, so it can only be applied to certain combinations, but it can be processed in post-processing, and it does not use resin for fixation. This is an excellent method in that it allows the deodorant to fully demonstrate its capabilities.

As an example, a method is actually used in which metal phthalocyanine is supported on porous rayon.
Other methods have not yet been developed, and methods that can be applied not only to synthetic fibers and recycled fibers but also to natural fibers such as cotton, linen, wool, and silk have not yet been developed.

Therefore, as a result of intensive study, the present inventors found that cotton, linen, wool,
Natural fibers such as silk, as well as some recycled fibers and synthetic fibers, can be processed with a deodorizing agent that has an affinity for them. We have developed a method for producing fibers that have a strong deodorizing function without requiring fixation, thereby causing a deterioration in the performance of the deodorant, and without impairing the original functions of the fibers.

[Means to solve problems]

That is, the present invention relates to a method for producing deodorant fibers in which a reaction product of tannic acid and a transition metal is fixed as a deodorizing component in the fibers.

Conventionally, attempts have been made to utilize tannic acid and tannic acid derivatives to deodorize malodorous substances. (Japanese Patent Application Laid-open No. 54-8725, etc.) It is thought that this effect is responsible for the fact that it can also be used as an additive for cigarette filters. (Japanese Patent Publication No. 54-18358, Japanese Patent Publication No. 57-118
785, etc.) However, these products use tannic acid or tannic acid derivatives as they are in the form of powder or granules, and are simply used in the same way as deodorants such as activated carbon.

We have confirmed that the reaction product of tannic acid and transition metals is very effective as a deodorizing component, and have investigated supporting this deodorizing component on fibers.

However, most of the reaction products of tannic acid and transition metals are water-insoluble and do not have good affinity even when applied to fibers as they are, making it practically impossible to treat them.

Therefore, we focused on the fact that tannic acid has a strong affinity for specific fibers, and developed a method in which the relevant fibers are loaded with transition metals in advance, and then the transition metal-loaded fibers are treated with tannic acid. As a result, a method for producing strongly fixed deodorant-carrying fibers without using any fixing agent such as resin was developed.

In the present invention, fibers include natural cellulose fibers such as cotton and hemp, natural protein fibers such as wool and silk, as well as natural fibers that have an affinity for tannic acid, such as regenerated cellulose fibers and nylon. This refers to all recycled, semi-synthetic, and synthetic fibers.

In addition, regarding the form of these fibers, fibers in all forms such as fibers, slivers, threads, woven and knitted fabrics, and non-woven fabrics,
Processable.

The tannic acid that can be used in the present invention is tannic acid in a broad sense, and includes all so-called tannins including so-called hydrolyzable tannins and condensed tannins.
Examples include gallotannins, ellagitannins, quebracotannins, waratol tannins, mangrove tannins, souvre tannins, gambir tannins, red catechins, and oak bark tannins.

The transition metals referred to in the present invention have an atomic number of 21 (
Sc) ~29 (Cu), 39 (Y) ~47 (8g), 57 (La) ~79 (Au), 89
(Ac) ~103 (Lr) and 30 (Zn),
48 (Cd).

It says everything including 80 (Ilg).

Tannic acid and these transition metals are thought to form complexes, examples of which include titanium tannate, iron tannate, nickel tannate, copper tannate, palladium tannate, silver tannate, and gold tannate. Many reactants are possible. Among them, the most preferred are iron tannate and copper tannate.

Iron tannate has a particularly remarkable effect on basic odors such as ammonia, while copper tannate has a remarkable deodorizing effect not only on basic odors such as ammonia but also on hydrogen sulfide and mercaptans. demonstrate.

The method for producing deodorizing fibers by supporting a reaction product of tannic acid and transition metals on fibers consists of a first step of supporting transition metals on fibers, and a second step of reacting the transition metals in the fibers with tannic acid. a second step in which the reaction product is fixed to the fibers.

In the first step, the fibers are treated with a solution of a transition metal compound in order to load the transition metal onto the fibers that have an affinity for tannic acid. Although various solutions can be used as the solution of the transition metal compound, an aqueous solution or an alcohol solution is preferred among them. In the case of an aqueous or alcoholic solution, salts of transition metals are preferred, and examples include sulfates, nitrates, carbonates, and chlorides of transition metals. Examples of these are ferrous chloride, ferric chloride, ferrous sulfate,
Examples include, but are not limited to, ferric sulfate, cuprous chloride, cupric chloride, cuprous sulfate, cupric sulfate, and the like.

The method of treating fibers with a solution of transition metal compounds is as follows:
Possible methods include a dipping method, a pad method, a spray method, a coating method, etc., and although no limitations are intentionally placed on these methods, the dipping method and the pad method are preferred from a practical standpoint.

When fibers are treated with a solution of a transition metal compound by a dipping method, fibers in all forms such as fibers, slivers, threads, woven and knitted fabrics, and nonwoven fabrics can be treated. Specifically, the method involves immersing fibers in a 0.01 to 30% solution of a transition metal compound, and
Process for 120 minutes. At this time, the p of the processing solution may be
Adjust H in the range of 2-10. After the immersion treatment with a solution of transition metal compounds, the second stage of treatment begins;
Regarding the presence or absence of a washing process and/or a drying process,
It is not intended to impose any restrictions.

When a solution of a transition metal compound is treated by a pad method, it can be carried out particularly for mi materials and nonwoven fabrics, but specifically, the method involves padding fibers with a 0.1 to 30% solution of a transition metal compound. , perform squeezing with a mangle to achieve a uniform squeezing rate. After the pad squeezing, the second stage of treatment begins, but there is no restriction as to whether or not a washing step and/or a drying step is required.

Next, in the second step, tannic acid is allowed to act on the transition metal-supported fibers. At this time, as a solvent for the tannic acid solution,
Any solvent that dissolves tannic acid can be used, such as water, alcohol, ether/alcohol mixture, acetic acid, ethyl acetate, methyl ethyl ketone, etc., and there are no restrictions on the solvent, but water or alcohol is preferred. .

Possible methods for treating transition metal-supported fibers with a tannic acid solution include dipping, padding, spraying, and coating, and although no restrictions are placed on these methods, practically speaking, dipping is recommended. is preferred. Specifically, fibers containing the transition metal produced in the first step are immersed in an aqueous or alcoholic solution of tannic acid, and the transition metal supported in the fibers reacts with the tannic acid in the treatment solution. This allows a compound with deodorizing function to be carried on the fibers.

That is, a solution containing 0.1 to 30% of tannic acid was
Adjust to H2-1O, at a temperature of 20-100°C, 5
Treat for ~120 minutes. After performing the second stage treatment, dehydrating and drying are performed to obtain deodorizing fibers. At this time, no restrictions are intentionally placed on the presence or absence of a water washing step for the purpose of removing insufficiently fixed components.

For the deodorizing fibers produced by the above method, the deodorizing function must not be significantly impaired by normal finishing treatments such as softener application, resin processing, coating, and other functional finishes. Well, there's no harm in going there.

〔Example〕

The present invention will be explained below with reference to Examples.
The invention is not limited to these examples.

Example 1: Silkesoto treated cotton fabric (basis weight 120g/m) was CLIC
Pad with a 2% aqueous solution of I2 ・2H20 and
It was squeezed to 70% Quanop and dried.

This copper-supported cotton fabric is used for tannic acid in the Japanese Pharmacopoeia.
% aqueous solution at a bath ratio of 1:30 and p + -1 of 5.
0 and treated at 40°C for 30 minutes. After the treatment, it was washed with water, deliquified, and dried to obtain a copper tannate-supported cotton fabric.

Example 2: Commercially available absorbent cotton was immersed in a 1% aqueous solution of FeSO4.7H□0 at a bath ratio of 1:30, and the pH was adjusted to 5.0.
It was treated for 0.720 minutes. Subsequently, the liquid was removed, and the iron-supported absorbent cotton was placed in a 2% aqueous solution of tannin MMR (hydrolyzable ellagu tannin) manufactured by Fuji Chemical Industry ■ at a bath ratio of 1:30.
The sample was immersed in water, adjusted to pH 5.0, and treated at 60"C for 0 minutes. After the treatment, it was washed with water, dehydrated, and dried to obtain iron tannate-supported absorbent cotton.

Example 3: Syrup shear wool cotton was immersed in a 1% aqueous solution of CLISO4.511□0 at a bath ratio of 1:30, and p I (4.
5 and treated at 50°C for 60 minutes. After the treatment, the water was removed and the copper-supported wool cotton was immersed in a 3% aqueous solution of tannic acid according to the Japanese Pharmacopoeia at a bath ratio of 1:30, the pH was adjusted to 6.0, and the mixture was treated at 60° C. for 60 minutes.

After the treatment, it was washed with water, dehydrated, and dried to obtain copper tannate-supported wool cotton.

Confirmation of deodorizing effect: Confirmation of the deodorizing effect of the deodorant fibers obtained in the above examples was carried out as follows.

As shown in Figure 1, 500m7! 1.0 g of deodorant fiber is suspended in an Erlenmeyer flask and the flask is sealed. Next, place the following odor source into the bottom of the Erlenmeyer flask using a microsyringe or pipette, being careful not to let the odor source come into contact with the deodorant fibers. After the odor source at the bottom was completely vaporized or reacted using a dryer, it was left to stand at room temperature for 60 minutes.

The measurements were performed using a Kita-type gas detection tube.

Odor source: ■ Ammonia 50 μl of 6% ammonia aqueous solution
injection.

■After injecting hydrogen sulfide -800ppm -Na2S 1m E, IN -112SO40,1m j! Inject and react.

■Methyl meru Methyl mekabutane manufactured by Wako Pure Chemical Industries ■
Rukabutan label fJ-? f11μg/μE (benzene)
100μ of liquid)! The injection measurement results are shown in Table-1.

〔Effect of the invention〕

As seen in the confirmation results of the deodorizing effect in Examples (Table 1), the deodorizing effect of the deodorant fibers of the present invention is very excellent.

Furthermore, unlike deodorants that are fixed using resins, they have excellent features such as texture, hydrophilicity, and other properties that do not impair the original functions of fibers.

In addition, all forms of fiber, sliver, yarn, woven and knitted fabrics, and non-woven fabrics can be obtained, so they can be used in many fields that require deodorizing performance, such as futon cotton, insulation for winter clothing, sheets, It is very effective for Kujiki, air purifier filters, etc.

[Brief explanation of the drawing]

FIG. 1 shows experimental equipment for confirming the deodorizing effect of the present invention. In the figure, (1) 500ml Erlenmeyer flask (2) Sample (untreated fiber or deodorizing fiber) (3) Odor source (4) Airtight seal (5) North type gas detection tube

Claims (1)

[Claims] By loading a transition metal in advance on fibers that have an affinity for tannic acid, and then reacting the transition metal with tannic acid in the fiber, the reaction product of tannic acid and transition metal deodorizes. A method for producing deodorizing fibers that are fixed in fibers as a component.