JPS626986A - Deodorizing fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fiber having a deodorizing function of converting a substance emitting an unpleasant odor into an odorless substance.

[Conventional technology]

Conventionally known methods for eliminating bad odors include activated carbon adsorption, catalytic combustion, oxidation using ozone or chemicals, neutralization, decomposition using bacteria, and decomposition using enzymes, but none of them have the same deodorizing ability. They have shortcomings such as low sustainability, low deodorizing efficiency, and secondary contamination.

Malodorous substances in daily life include ammonia,
These include amines, hydrogen sulfide, mercaptans, indoles, and carbonyl compounds. These substances are described in Japanese Unexamined Patent Publication No. 5
As described in Japanese Patent No. 5-32519, biological enzymes act as oxidation catalysts and are decomposed. Among biological enzymes, metalloporphyrins and metalloporfrazins are excellent, and they are advantageous in that they can be synthesized artificially and are relatively easily available, as disclosed in JP-A-50-54590, for example. It is.

The invention of using metal porphyrins and metal porfrazines as a deodorant is based on the invention of Mizo et al.
This is already known from the above-mentioned Japanese Patent Application Laid-Open No. 55-32519. The disclosed deodorant is superior to other deodorants.

[Problem that the invention seeks to solve]

This invention was made as a result of further research,
Using the deodorant disclosed in the above-mentioned publication, the present invention aims to provide fibers that deodorize water-soluble and water-insoluble off-odor substances by decomposing them simultaneously and in a short period of time.

[Means for solving problems]

The present inventor obtained the following findings through research on the use of metal porphyrins and metal volfrazines as deodorants.

In order for a deodorant to act as an oxidation catalyst on all kinds of odor substances and decompose them in a short period of time, it is necessary to have the following functions: ■ Function as oxidase, ■ Function as peroxidase, and ■ Function as oxygenase. . It is believed that enzymes do not perform these three functions simultaneously in vivo.

Among the metal porphyrins and the metal volfrazines, the metal phthalocyanine shown in the structural formula of FIG. 1 is excellent as a deodorant because it has the possibility of simultaneously exhibiting the above-mentioned functions (1) to (3). However, it is difficult to obtain an even better deodorant using metal phthalocyanine alone. If -X in the above structural formula is a group with a small steric structure, it is shown in Figure 2 (
Metal phthalocyanine-dimer or four times (
The metal phthalocyanine-oxo dimer shown in b) is produced, which weakens the catalytic activity. Therefore, it is necessary to prevent dimers from being generated.

The metal phthalocyanine is supported and bonded to m-fibers, which are polymers, and the polymer chain causes steric hindrance between the metal phthalocyanines, thereby preventing the formation of visible dimers. However, even if metal phthalocyanine is bound to a polymer, if the amount of metal phthalocyanine bound is too large, the probability of close contact between metal phthalocyanines increases and dimers are generated, which may actually worsen deodorizing efficiency.

On the other hand, if the amount of metal phthalocyanine is too small, the deodorizing effect cannot be maintained. According to the results of various experiments, the appropriate amount of metal phthalocyanine is 0.5 to 20% by weight based on the total amount. More preferably, it is 1.0 to 10% by weight.

Among polymeric substances, mta is suitable for supporting and bonding metal phthalocyanine due to its large bulk and large surface area.

Based on the above knowledge, the present invention allows polyester fibers to support 0.5 to 20% by weight of metal phthalocyanine.

Polyester fibers have ester bonds in their constituent polymer chains, and are typified by polyethylene glycol terephthalate. It also includes those into which appropriate functional groups have been introduced. Note that the shape of the fibers may be either short fibers or long fibers.

The -X group of the supported metal phthalocyanine is a hydrogen group or a substituent. Examples of substituents include alkyl groups,
Substituted alkyl group (e.g. chloromethyl group), halogen group, nitro group, amino group, azo group, thiocyanate group, carboxyl group, carbonyl chloride group, carboxylamide group, nitrile group, hydroxyl group, alkoxyl group, phenoxydyl group, sulfonic acid group , sulfonyl chloride groups, sulfonamide groups, thiol groups, alkyl silicon groups (vinyl groups, etc.), as well as amine salts, quaternary ammonium groups or their salts, pyridine groups and their derivatives, salts thereof, etc. The types of groups are not limited, and groups on each side may be substituted. Among these, those with 2 to 8 substitutions of cationic groups such as amino groups, quaternary ammonium groups, and pyridine groups are preferable. The metal M is, for example, Fe, Go, Mn, Ti, V', Ni, Cu, Zn,
You can use No, W, Os. Preferably, it is Fe or CO, or a mixture of Fe and Co.

[Effect]

As mentioned above, since the metal phthalocyanine is supported on the fiber, the metal phthalocyanine is hindered by the polymer chains of the fiber, and dimers (see FIG. 2) are not easily generated. Furthermore, since the amount of metal phthalocyanine bound is 0.5 to 20% by weight, this is an appropriate amount of catalyst, and the probability of proximity between metal phthalocyanines is small, so that very few dimers are produced. Therefore, the function of the oxidation catalyst can be fully exhibited.

The metal phthalocyanine in the fiber has the three functions (1) to (3) mentioned above for water-soluble or water-insoluble off-odor substances, and has the following actions to decompose the off-odor substances.

■ Action as oxidase Oxidation reaction due to oxygen depending on the molecular state (autooxidation effect due to oxygen in the air).

2(Sub)H+ 02 □5ub-5ub+ H2O
2" In the formula, Sub is an abbreviation for 5substrate.

Po1-MPc: Polymer substance to which metal phthalocyanine is bound (Sub)■: Off-flavor substance, such as I2S, R-9R
(mercaptan derivative), R-GHO (aldehyde derivative), R-N)I2 (amine derivative), R-OH (
(alcohol rust conductor) Sub-9ub: ＠Metal substance ■Action as peroxidase Oxidation reaction by hydrogen peroxide (O mark) produced in the above ■
(This occurs in a chain reaction to ■).

2(Sub)H+ 11202φυ soil”±deception5ub−
Sub +2+120 ■ Action as oxygenase For example, reaction to oxidize and cleave malodorous substances consisting of heterocyclic compounds such as indole nucleus and pyridine nucleus. In the case of indole nuclei, the following reaction occurs.

Products resulting from oxidative cleavage may be further decomposed by the reactions described in (1) and (2) above.

〔Effect of the invention〕

The deodorizing fiber of the present invention can decompose almost all of the malodorous substances found in human daily life, regardless of whether they are water-soluble or water-insoluble, through the reactions described in (1) to (2) above.

L-fibers have appropriate voids, and metal phthalocyanine is bonded to cyanide groups and copolymer substances in m-fiber molecules and is supported, so metal phthalocyanine does not come off due to aging or washing. rare. Moreover, the fibers themselves do not absorb or store odor substances, nor are they consumed in the deodorizing reaction system. Therefore, the deodorizing effect can be maintained semi-permanently.

Since it is a fiber, it can be made into yarn, cloth, nonwoven paper, etc. by itself or by blending it with other fibers. These manufactured products can be used as raw materials for secondary products such as clothing, bedding, carpets, building materials, filters for air purifiers and sewage treatment equipment, and packaging materials, and the resulting secondary products have deodorizing functions. It turns out.

[Examples] Example 1 Three volumes of a solution in which 70 g of cobalt phthalocyanine octamine was dispersed with a nonionic surfactant were placed in an autoclave, and the pH was adjusted to 5 with acetic acid/sodium acetate. After immersing the polyester fiber fILIKg therein, it was
Stirring was carried out for about 5 hours while maintaining the temperature at 30° C., so that the cobalt phthalocyanine octamine was mixed with the fibers. After taking out the fibers, they are thoroughly washed with water and then dehydrated and dried. Approximately 5% by weight of cobalt phthalocyanine octaamine was supported on the resulting fiber.

Example 2 Boiling water in which 50 g of phenylphenol sodium salt is dissolved is added to 3 parts of a hot water solution in which 70 g of iron phthalocyanine tetraamine is dispersed with a nonionic surfactant, and the mixture is thoroughly stirred and immediately immersed in IKg of polyester fibers. While continuing to stir, gradually warm the shellfish until it boils and maintain for about 1 hour. Next, the pH of this boiling liquid was adjusted to 5 to 6 with acetic acid, and stirring was continued for about 2 hours. The fibers carrying iron phthalocyanine tetraamine in this way were taken out, thoroughly washed and dried, and then heated at about 150°C for 1
Heat treatment for an hour. Approximately 3% by weight of iron phthalocyanine tetraamine was supported on the obtained fiber.

Example 3 Put 120g of cobalt phthalocyanine octaquaternary ammonium octanodium aqueous solution into an autoclave, and add acetic acid to pH 4~? (preferably 4.5-5.5)
Adjust to. After immersing Ikg of polyester fibers into which sulfonic acid groups have been introduced, the mixture is stirred for about 10 hours while maintaining the temperature at 135° C. under high pressure, so that cobalt phthalocyanine octaquaternary ammonium is supported on the fibers. After taking out the fibers, they are thoroughly washed with water and then dehydrated and dried. The resulting fibers were loaded with about 5% by weight of cobalt phthalocyanine octaquaternary ammonium.

The fibers obtained in Examples 1 to 3 above were packed in a glass tube, and vapors of ammonia, amines, hydrogen sulfide, mercaptans, etc. were passed through the tubes, and the gas chromatograph examination revealed that these substances were well decomposed. Indicated. Performance did not deteriorate at all even after one year of continuous testing. Furthermore, it has received very good reviews for natural foul-smelling substances such as manure, fish pulp, and sewage sludge. In addition to the above-mentioned gas chromatograph, we also conducted a sensitivity test using a monitor for evaluation, and the product also received better evaluations than conventional deodorants.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the structural formula of metal phthalocyanine, and FIGS. 2 (a) and (b) are diagrams showing the structure of a dimer of metal phthalocyanine. Patent applicant: Earth Clean Co., Ltd.? (8 ×
2(

Claims (1)

[Claims] 1. Polyester fiber has a structural formula ▲ mathematical formula, chemical formula, table, etc. ▼ (in the formula, -X is hydrogen or a substituent, M is a coordinating metal) metal phthalocyanine 0.5 A deodorizing fiber characterized by carrying up to 20% by weight.