JPS61258078A - 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. There are disadvantages such as low grass sustainability, low deodorizing efficiency, and secondary pollution.

Malodorous substances in daily life include ammonia,
These include amines, hydrogen sulfide, mercaptans, indoles, and carbonyl compounds. These substances are disclosed in JP-A IV
(As described in Japanese Patent Publication No. 55-32519, biological enzymes act as oxidation catalysts and are decomposed.Among biological enzymes, metalloporphyrins and metalvolfrazins are excellent. It is also advantageous in that it can be synthesized artificially as disclosed in the above publication and is relatively easily available.

The invention of using metal porphyrins and metal porphyrins as a deodorant is based on the invention of the present inventors.
This is already known from the above-mentioned Japanese Unexamined Patent Publication 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 publication.

The purpose of the present invention is to provide fibers that simultaneously decompose and deodorize water-soluble and water-insoluble off-flavor substances 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 metal porphyrins, 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 a better deodorant using only the tB metal phthalocyanine. If -X in the above structural formula is a group with a small steric structure, the metal phthalocyanine dimer shown in FIG. It is necessary to prevent the formation of dimers.

Metal phthalocyanine is supported and bonded to polymeric fibers, and the polymer chains cause steric hindrance between the metal phthalocyanines, thereby preventing the formation of such 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, even if the amount of metal phthalocyanine is too small, the deodorizing effect cannot be maintained.According to the results of various experiments, the amount of metal phthalocyanine is suitably 0.5 to 20% by weight based on the total amount. More preferably, it is 1.0 to 10% by weight.

Among polymeric substances, fibers are suitable for supporting and bonding metal phthalocyanines because they have a large bulk and a large surface area. M again! Among them, polyamide fibers have an amide bond (-〇〇-NH-) in the molecule and an amine group or carboxyl group at the end of the fiber molecule, so that metal phthalocyanine is easily bonded to it.

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

Polyamide fibers are fibers that have an amide bond in one molecular chain as described above, and have natural edges, II (e.g. wool, animal hair,
Protein fibers such as silk), synthetic fibers! l (e.g. nylon)
There are some known as. The shape of the fibers may be short fibers or long mIa.

The =X group of the supported metal phthalocyanine is a hydrogen group or a substituent. Wi substituents include, for example, alkyl groups, substituted alkyl groups (e.g. chloromethyl group), halogen groups, nitro groups, amino groups, azo groups, thiocyanate groups,
In addition to carboxyl groups, carbonyl chloride groups, carboxylamide groups, nitrile groups, hydrophobic groups, alkoxyl groups, phenoxydyl groups, sulfonic acid groups, sulfonyl chloride groups, sulfonamide groups, thiol groups, alkyl silicon groups, vinyl groups, etc. Examples include alkali salts of groups and sulfonic acid groups, and the substituents are not limited to one type of group, but may be substituted with different groups.

Among these, those in which 2 to 8 acidic substrates such as sulfonic acid groups and carboxyl groups are substituted are preferred.

Further, the central metal M is, for example, Fe, Go, Mn, Ti, V
, Ni, Cu.

Zn, No., W, and Og materials can be used. Preferably, it is Fe or CG, or a mixture of Fe and Go.

Note that in order to support the metal phthalocyanine on the polyamide fiber, it is preferable to use an acidic or neutral bath.

[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 Figure 2) are not easily generated. Since the weight is 20%, the amount of catalyst is appropriate, and the probability of proximity between metal phthalocyanines is small, making it easy to dive.
is produced in very small amounts, and therefore the function of the oxidation catalyst can be fully demonstrated.

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-9ub+ H2
O2-Sub in the formula is 5substrate (substrate)
Abbreviation for

Pa1-MPc: Polymer substance to which metal phthalocyanine is bound (Sub) H: Off-odor substance such as H2S, R-3H (mercaptan derivative), R-C: IO (aldehyde derivative), R-NH2 (amino derivative) , R-DH (alcohol derivative) Sub-Sub + oxidation product ■ Action as peroxidase Oxidation reaction by hydrogen peroxide (this mark) produced in Section 1 ■ (
(This occurs in conjunction with ■).

2(Sub))l + H2O2"'Sat-"' 5u
b-Sub +2H20 ■ Action as oxygenase A reaction that oxidizes and cleaves malodorous substances consisting of heterocyclic compounds with an indole nucleus or a pyridine nucleus. In the case of indole nuclei, the following reaction occurs.

The products resulting from oxidative cleavage may be further decomposed by the reactions described in ① and ②.

〔Effect of the invention〕

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

Since the base material of m-fiber is polyamide-based, metal phthalocyanine is bonded and supported to the amide bond (-Co-NH-) in the fiber molecule and the amine group or carboxyl group at the end of the fiber molecule, and the metal phthalocyanine is supported over time. Metal phthalocyanine is rarely released due to changes or washing. 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 fabric, 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.

〔Example〕

Example 1. Cobalt phthalocyanine tetrasulfonic acid 1.
A 0% by weight solution is acidified with sulfuric acid to adjust P) to 12-4. Immerse Ikg of defatted wool in a large amount of the solution and heat to approximately 70°C.
After stirring for about 10 hours while maintaining the temperature, the mixture is thoroughly washed and then dehydrated and dried. The resulting fibers are about 5 times thicker! a% of cobalt phthalocyanine tetrasulfonic acid was retained.

Example 2. A 5.0fi 1% solution of octa-sodium iron phthalocyanine octacarboxylate is neutralized with sulfuric acid.

Ikg of raw silk obtained by boiling cocoons and reeling is immersed in a large amount of the solution, stirred for about 24 hours while maintaining at about 50°C, and pulled out. After immersing it in an acidic solution of P113 or less (for example, hydrochloric acid solution), it is thoroughly washed and then dehydrated and dried. Approximately 31% of iron phthalocyanine octacarboxylic acid was supported on the obtained fiber.

Example 3. Immerse Ikg of nylon 6 fibers in a 4.0% by weight solution of iron phthalocyanine tetracarboxylic acid and soak for about 70' c.
Stir for about 24 hours while maintaining the temperature and then remove. PH it
After being immersed in an acid solution of 3 or less (for example, an acetic acid solution), it is thoroughly washed and dried. Approximately 1% by weight of iron phthalocyanine tetracarboxylic acid was supported on the obtained fiber.

The fibers obtained in Examples 1 to 3 were packed in a glass tube, and vapors of ammonia, amines, hydrogen sulfide, mercaptan, etc. were permeated through the tubes, and the gas chromatograph examination revealed that these substances were well decomposed. showed that. 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.
Shiraie Mansaku 7 Diagram (a) (b)

Claims (1)

[Claims] 1. Polyamide 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.